69451 weinheim, germany carbohydrate microarray analysis of 24 lectins joseph c. manimala, timothy...

Supporting Information copy Wiley-VCH 2006

69451 Weinheim Germany

High-Throughput Carbohydrate Microarray Analysis of 24 Lectins

Joseph C Manimala Timothy A Roach Zhitao Li and Jeffrey C Gildersleeve

Laboratory of Medicinal Chemistry National Cancer Institute 376 Boyles St Bldg 376 Rm 109

Frederick MD 21702

S1

Materials and General Methods Unless otherwise stated reagents were obtained from

commercial suppliers and used without purification All aqueous solutions were prepared from distilled

deionized water filtered with a Milli-Q purification system and sterile filtered through a 02 microm filter

Blood group A-BSA Lea-BSA Leb-BSA SLex-BSA Galβ1-4GlcNAc-BSA Galα1-3Gal-BSA

mannotriose-BSA Globotriose-HSA and Siaα2-3Galβ1-4GlcNAc-BSA were purchased from Dextra

Labs OSM Galβ1-3GalNAc-HSA and Ley-HSA were purchased from Isosep (Tullinge Sweden) KLH

(keyhole limpet hemocyanin) BSA (bovine serum albumin) HSA (human serum albumin catA3782

ge99 pure essentially globulin free ~0005 fatty acids) BSM (bovine submaxillary mucin) Galα1-

4Galβ-CETE-BSA (CETE = carboxyethylthioethyl linker) and Glcα1-6Glcα1-4Glcα1-4Glcβ-CETE-

BSA were purchased from Sigma Galβ1-4Glcβ ndash BSA (Lac) and Galβ1-3GlcNAcβ ndash BSA (Lec) were

purchased from Glycorex (Lund Sweden) Blood Group B ndash BSA [Galα1-3(Fucα1-2)Galβ-10 atom

spacer] was purchased from EMD (San Diego CA) 3rsquoSialyllactose-APD-HSA 6rsquoSialyllactose-APD-

HSA Sia-LeA-APD-HSA (SLea) Blood Group H2 Lex-APD-HSA Di-Lex-APE-BSA and Blood group

H1-APD-HSA were purchased from Glycotech (Gaithersburg Maryland) Fatty acid binding protein

(FABP) was purchased from Spectral Diagnostics (Toronto Canada) Prostate Specific Antigen (PSA)

was purchased from Fisher Scientific Heat shock protein 90 (HSP90) was purchased from US

Biologicals (Swampscott MA) Thyroblobulin (Tgl) alpha-fetoprotein (AFP) and carcinoembryonic

antigen (CEA) were purchased from Biodesign (Saco Maine) The preparation of Cy3-BSA Cy5-BSA

Glcβ-BSA GalNAcα-BSA Glcα-BSA Manα-BSA GlcNAcβ-BSA Tn-BSA GalNAcα1-6Gal-BSA

GalNAcα1-3Gal-BSA and GlcNAcα1-4Gal-BSA was previously reported[1] Cy3 and Cy5 labeled BSA

were used as positive controls while unmodified BSA and HSA were used as the negative control

Helix aspersa agglutinin (HAA) Lima bean agglutinin (LBA also known as Phaseolus lunatus)

and Salvia sclarea Agglutinin (SSA) were purchased in their pure form from EY Laboratories (San

Mateo CA) All the other lectins were purchased as a biotinylated conjugate Amaranthus caudatus

lectin (ACL) Byronia purpurea lectin (BPL) Concanavalin A (Con A) Sambucus nigra Lectin (SNL)

S2

Erythrina cristagalli lectin (ECL) Griffonia simplicifolia lectin I Isolectin B4 (GSL I) Griffonia

simplicifolia lectin II (GSL II) Lotus tetragonolobus lectin (LTL) Maclura pomifer lectin (MPL) Peanut

agglutinin (PNA) Psophocarpus tetragonolobus lectin I (PTL) Ricinus communis agglutinin I (RCA

120) Soybean agglutinin (SBA) Ulex europaeus agglutinin I (UEAI) Vicia villosa lectin (VVL)

Wisteria floribunda lectin (WFL) and wheat germ agglutinin (WGA) were purchased from Vector

Laboratories (Burlingame CA) Dolichos biflorus lectin (DBL) and Helix pomatia lectin (HPL) were

purchased from Sigma (St Louis MO) HAA LBA and SSA were biotinylated as follows Each

reaction was carried out at a ratio of 20 biotin NHS esters (Biotin-X-NHS was purchased from

Calbiochem San Diego CA) for every molecule of lectin Briefly to a solution of lectin (045 micromoles)

in PBS buffer at pH 72 was added biotin-X-NHS (5 mg 9 micro moles) in DMF The reaction mixture was

incubated for two hours and the excess biotin-X-NHS and salts were removed using a desalting spin

column (Pierce Rockford IL)

Streptavidin-HRP was purchased from Southern Biotech (Birmingham AL) Cyanine 3-

Tyramide labeling reagent was purchased from PerkinElmer Life Sciences Inc (Boston MA) The

epoxide derivatized Nunc ArrayCote 16 well microarray slides were purchased from Nalge Nunc

International (Rochester NY) and the arrays were printed by KamTek Inc (Gaithersburg MD)

NMR spectra were recorded on a Unity Inova 400 Fourier transform NMR spectrometer All

proton NMR data was obtained at 400 MHz and all carbon NMR data was obtained at 100 MHz Proton

chemical shifts are reported in parts per million (ppm) downfield from tetramethylsilane (TMS) unless

otherwise noted Carbon chemical shifts are reported in parts per million (ppm) downfield from TMS

using the CDCl3 as an internal reference unless otherwise noted Coupling constants (J) are reported in

hertz (Hz) Multiplicities are abbreviated as follows singlet (s) doublet (d) triplet (t) quartet (q)

quintuplet (p) multiplet (m) and broadened (br) High resolution mass spectra were obtained on a VG

ZAB (University of California Riverside Mass Spectrometry Facility) MALDI-TOF analysis of the

BSA conjugates was obtained by the Protein Chemistry Laboratory at the NCI-Frederick

S3

Preparation of Glycoconjugates and Glycoproteins for the Array

Coupling of Oligosaccharides to BSA via Reductive Amination Xylβ1-4Xylβ1-4Xylβ1-

4Xylβ1-4Xyl Araα1-5Araα1-5Araα1-5Araα1-5Araα1-5Ara Xylα1-6Glcβ1-4(Xylα1-6)Glcβ1-

4(Xylα1-6)Glcβ1-4Glc Manβ1-4Manβ1-4Manβ1-4Manβ1-Man and Manβ1-4(Galα1-6)Manβ1-

4(Galα1-6)Manβ1-4Manβ1-4Man were purchased from Megazyme International (Co Wicklow Ireland)

LNT LSTa and LSTb were purchased from Glycotech (Gaithersburg Maryland) LSTc and GA1 were

purchased from Dextra Labs (Reading UK) Reductive aminations were carried out following the

procedure of Roy et al[2]

Preparation of aBSM aOSM aGn Bovine submaxillary mucin (BSM) was purchased from

Sigma Ovine submaxillary mucin (OSM) was purchased from IsoSep (Tullinge Sweden) and

glycophorin (Gn) was purchased from Sigma BSM OSM and Gn were de-sialylated with mild acid

treatment to produce asialo-BSM (aBSM) asialo-OSM (aOSM) and asialo-glycophorin (aGn) following

the literature procedure[3]

De-O-Acetylated BSM BSM (4 mg) was dissolved in water (1 mL) and cooled to 4degC 1M

NaOH (10 microL) was added and the reaction was allowed to sit for 1 hr De-O-acetylated BSM

(deAcBSM) was dialyzed extensively with PBS

S4

Chemical Synthesis of Carbohydrate Epitopes and Coupling to BSA

OAcO

AcONHAc

OAc

OAcO

R1O

R1ONHAc

S

OR1

S2S3 R1 = Ac R2 = Me S4 R1 = H R2 = H

NH

OR2

O OHS

NH

OMe

O O

S1

[2-(methyl 4-carbamoylbutanoyl)ethyl] 2-acetamido-2-deoxy-1-thio-345-tri-O-acetyl-β-D-

galactopyranoside (S3) 2-deoxy-2-N-acetyl-1346-tetra-O-acetyl-1-thio-β-D-galactopyranose (800

mg 206 mmol) and linker S1[4] (422 mg 200 mmol) were dissolved in dichloromethane (5 mL) SnCl4

(31 mL of 1M solution in CH2Cl2 31 mmol) was added and the reaction was stirred at room temperature

for 7 days The reaction mixture was diluted with dichloromethane (~30 mL) and sat NaHCO3 (5 mL)

was added After bubbling ceased the reaction was washed with 1M K2CO3 (~20 mL) The organic

layer was dried over sodium sulfate and then concentrated in vacuo The product was purified by column

chromatography (40 acetone in dichloromethane) to yield an alphabeta mixture (640 mg) The pure

beta anomer was obtained by repeated column chromatography to afford S3 (280 mg 28) Rf = 030

(40 acetone in dichloromethane) 1H NMR (CDCl3) δ 638 (br t J = 56 Hz 1H NH-linker) 596 (d J

= 95 Hz 1H NHAc) 540 (dd J = 25 33 Hz 1H H4) 512 (dd J = 33 108 Hz 1H H3) 463 (d J

= 106 Hz 1H H1) 430 (ddd J = 95 106 106 Hz 1H H2) 412 (m 2H H6) 395 (app t J = 69 Hz

1H H5) 368 (s 3H OCH3) 362 (m 1H) 339 (m 1H) 296 (m 1H) 275 (m 1H) 240 (t J = 72 Hz

2H) 228 (t J = 72 Hz 2H) 218 (s 3H) 205 (s 3H) 200 (s 3H) 196 (s 3H) 192 (m 2H) 13C NMR

(CDCl3) δ 1739 1728 1709 1708 1706 1704 845 749 716 671 619 518 495 384 355

333 303 235 211 209 208

[2-(4-carbamoylbutanoyl)ethyl] 2-acetamido-2-deoxy-1-thio-β-D-galactopyranoside (S4)

S3 (120 mg 023 mmol) was dissolved in methanol (4 mL) and 1M NaOH (15 mL) was added The

reaction was stirred for 2 hours and then neutralized with amberlyst acid resin The reaction was filtered

and the resin was washed with methanol The filtrate was concentrated in vacuo The product was

S5

purified by column chromatography (20 methanol in dichloromethane + 1 acetic acid) to afford S4

(80 mg 88) Rf = 015 (20 methanol in dichloromethane + 1 acetic acid) 1H NMR (CDCl3) δ 444

(d J = 103 Hz 1H H1) 403 (dd J = 103 103 Hz 1H H2) 385 (d J = 31 Hz 1H H4) 375 (dd J =

72 115 Hz 1H H6a) 366 (dd J = 48 115 Hz 1H H6b) 352 (m 2H) 338 (m 2H) 286 (app q J =

67 Hz 1H) 267 (app q J = 67 Hz 1H) 228 (t J = 73 Hz 2H) 222 (t J = 73 Hz 2H) 194 (s 3H)

188 (app q J = 73 Hz 2H) 13C NMR (CDCl3) δ 1757 1740 862 809 744 700 630 528 409

364 351 309 231 228 HRMS Calcd for C15H26N2O8SNa (MNa+) 4171308 found 4171311

S6

O

OAc OAcOAc

S5 S6 R1 = Ac R2 = Me S7 R1 = H R2 = Me S8 R1 = H R2 = H

NH

OR2

O OHSNH

OMe

O O

S1Br

O

OR1 OR1OR1

S

[2-(methyl 4-carbamoylbutanoyl)ethyl] 234-tri-O-acetyl-1-thio-β-L-fucopyranoside (S6)

Linker S1 (229 mg 111 mmol) was dissolved in 10 Na2CO3 solution (8 mL) and tetrabutylammonium

hydrogensulfate (227 g 67 mmol) was added To this mixture was added 234-tri-O-acetyl-α-L-

fucopyranosyl bromide (0790 g 220 mmol) dissolved in ethyl acetate (8 mL) The mixture was stirred

at room temperature until all glycosyl bromide was consumed as judged by TLC The mixture was then

extracted with ethyl acetate and the crude product was purified by column chromatography (tolueneethyl

acetate 11) to give S6 (760 mg 72 yield) as a viscous oil Rf = 04 (301 chloroformmethanol) 1H

NMR (CDCl3) δ 611 (m 1H) 529-528 (d J = 32 Hz 1H) 524-519 (t J = 80 Hz 1H) 643 (t J =

104 Hz 1H) 506-503 (dd J = 32 32 Hz 1H) 446 (d J = 100 Hz 1H) 389-384 (q J = 64 Hz 1

H) 367 (s 3H) 350 (m 2H) 294 (m 1H) 275 (m 1H) 238 (app t J = 72 2H) 225 (app t J = 76

Hz 2H) 218 (s 3H) 207 (s 3H) 199(s 3H) 196 (t J = 72 2H) 122 (d J = 6 3H) 13C NMR

(CDCl3) δ 1734 1720 1704 1699 1697 833 733 720 702 670 514 388 352 330 300

2078 2072 2061 2054 163 HRMS calcd for C20H32NO10S 4781746 [M+H]+ found 4781728

[2-(methyl 4-carbamoylbutanoyl)ethyl] 1-thio-β-L-fucopyranoside (S7) S6 (115mg 0240

mmol) was dissolved anhydrous methanol (3 mL) and a catalytic amount of NaOMe was added The

mixture was stirred at room temperature for 5 hrs and then neutralized with Amberlite IR-120 (H+)

filtered and the solvent removed in vacuo The resulting residue was purified by flash column

chromatography (chloroform-methanol 91) to give S7 (79 mg 94 yield) as a viscous oil Rf = 02 (91

chloroformmethanol) 1H NMR (D2O) δ 430-427 (d J = 10 Hz 1H) 365-362 (app m 5H) 353 (s

3H) 353-347 (dd J = 156 32 Hz 1H) 337-333 (t J = 10 Hz 1H) 328-325 (m 2H) 273-266 (m

S7

2H) 228-22 (t J = 76 Hz 2H) 215-211 (t J = 76 Hz 2H) 175-171 (q J = 72 Hz 2H) 108-106

(d J = 68 Hz 1H) 13C NMR (D2O) δ 1738 859 749 747 717 696 506 394 345 325 290

207 156 HRMS calcd for C14H26NO7S 3521499 [M+H]+ found 3521423

[2-(4-carbamoylbutanoyl)ethyl] 1-thio-β-L-fucopyranoside (S8) S7 (90 mg 0256 mmol)

was dissolved in water and LiOH (10mg) was added and the mixture stirred at room temperature

overnight The solution was then neutralized with Amberlite IR-120 (H+) and filtered The product was

purified by by reverse phase HPLC (Atlantistrade dC18 column 5 microm 10 x 100 mm) using a flow rate of 8

mLmin and a gradient from 0 to 20 CH3CN in H2O (with 01TFA) over 40 minutes while

monitoring using a Waters 2420 ELS detector S8 (47 mg 54 yield) was obtained as a white cottony

substance after lyophilization Retention time = 76 min 1H NMR (D2O) δ 430-427 (d J = 112 Hz

1H) 366-362 (d J = 32 Hz 1H) 524-519 (t J = 80 Hz 1H) 643 (t J = 104 Hz 1H) 506-503 (dd

J = 32 32 Hz 1H) 349-346 (qd 1H) 338-326 (m 3H) 276-265 (m 2H) 227-225 (t J = 72 Hz

2H) 217-213 (t J = 72 Hz 2H) 173 (q J = 72 Hz 2H) 108-106 (d J = 68 2H) 13C NMR (D2O) δ

1777 1758 856 748 739 713 692 392 347 327 292 205 156 HRMS calcd for

C13H24NO7NS 3381273 [M+H]+ found 3381272

S8

O

OH OHOH

S9 S10 R1 = Me S11 R1 = H

HSNH

OMe

O O

S1O N

MeO

NH

OR1

O O

O

OH OHOH

S

[2-(methyl 4-carbamoylbutanoyl)ethyl] 1-thio-α-L-fucopyranoside (S10) To a solution of

linker S1 (434 mg 15 mmol) dissolved in anhydrous CH2Cl2 (5 mL) and 150 microL of TfOH was added

drop wise 3-methoxy-2-pyridyl β-L-fucopyranoside S9[5] (140 mg 0516 mmol) dissolved in CH2Cl2 over

a period of 15 minutes The mixture was stirred at room temperature for 4 hours after which 2 drops of

pyridine were added the solvent was removed in vacuo and the residue purified by flash column

chromatography (chloroformmethanol 91) to give S10 (333 mg 63 yield) as a viscous oil Rf = 025

(91 chloroformmethanol) 1H NMR (CDCl3) δ 80 (bs 1H) 531-530 (d J = 56 Hz 1H) 423-422 (q

J = 68 Hz 1H) 402-398 (dd J = 56 56 Hz 1H) 362 (s 3H) 357-353 (dd J = 32 32 Hz 1H)

(app t J = 64 Hz 2 H) 268-256 (m 2H) 235-231 (t J = 72 2H) 221-218 (t J = 72 2H) 188-

184 (q J = 76 2H) 120-118 (d J = 64 3H) 13C NMR (CD3OD) δ 1738 1737 863 719 708

680 667 505 389 345 324 292 207 151 HRMS calcd for C14H26NO7S 3521499 [M+H]+

found 3521423

[2-(4-carbamoylbutanoyl)ethyl] 1-thio-α-L-fucopyranoside (S11) S10 (50 mg 0142 mmol)

was dissolved in water and LiOH (15 mg) was added and the solution stirred at room temperature





substance after lyophilization Retention time = 62 min 1H NMR (D2O) δ 527-526 (d J = 56 Hz 1H)

420-415 (q J = 64 68 Hz 1H) 392-388 (dd J = 56 56 Hz 1H) 364 (d J = 33 Hz 1H) 357-

354 (dd J = 34 34 Hz 1H) 328-325 (t J = 64 Hz 2H) 268-254(m 2H) 228-225 (t J = 74 Hz

S9

2H) 217-213 (t J = 73 Hz 2H) 177-169 (m 2H) 107-105 (d J = 65 Hz 2H) 13C NMR (D2O) δ

1778 1758 860 715 701 675 672 388 347 327 295 206 152 HRMS calcd for

C13H24NO7S 3381273 [M+H]+ found 3381272

S10

OAcO

AcOOAc

S12

NH

OR2

O OHSNH

OMe

O O

S1 OR1O

R1O OR1

OAc

S13 R1 = Ac R2 = MeS14α S14β R1 = H R2 = MeS15α S15β R1 = H R2 = H

S

[2-(methyl 4-carbamoylbutanoyl)ethyl] 234-tri-O-acetyl-1-thio-L-rhamnopyranoside

(S13) To a solution of 1234-tetra-O-acetyl-rhamnopyranose S12 (03 g 09 mmol) in dichloromethane

(20 mL) was added BF3OEt2 (3 mL 24 mmol) drop wise and was incubated overnight The reaction

mixture was washed with water (50 mL) and brine (50 mL) The solvent was then rotary evaporated and

the product was purified using silica gel chromatography to afford S13 as an inseparable αβ mixture (280

mg 65) Rf = 05 (100 ethyl acetate) 1H NMR (CDCl3) δ 605 (s 1 H) 595 (s 1H) 546 (dd 1H J

=18 16 Hz) 529 (dd 1H J =18 16 Hz) 517 (d 1H J = 16 Hz) 514 (d 1H J =31 Hz) 509 (s

1H) 505 (dd 1H J = 36 114 Hz) 502 (S 1H) 497 (dd 1H J = 36 114 Hz) 473 (d 1H J =18

Hz) 417 (m 1H) 364 (s 3H) 351 (m 1H) 339 (m 1H) 285 (m 2H) 276 (m 2H) 235 (t 2 H

J=72 Hz) 222 (t 2 H J=72 Hz) 211 (s 3H) 202 (s 3H) 201 (s 3H) 195 (m 2H)

[2-(methyl 4-carbamoylbutanoyl)ethyl] 1-thio-L-rhamnopyranoside (S14) The αβ mixture

S13 (170 mg 036 mmol) was dissolved in methanol (4 mL) and sodium methoxide (~20 mg) was added

After 3 h the reaction was neutralized by addition of amberlyst acidic resin (100 mg) The suspension

was filtered and rinsed with methanol (50 mL) The filtrate was concentrated in vacuo The product was

purified by column chromatography to afford S14α (85 mg 67) and S14β (35 mg 27) S14β Rf =

035 (5 methanol in dichloromethane) 1Η NMR (CDCl3) 469 (d 1H J = 1 Hz) 385 (dd 1H J = 09

25 Hz) 363 (s 3H) 345 (m 2H) 328 (m 3H) 276 (m 2H) 233 (t 2H J = 67 Hz) 220 (t 2H J =

72 Hz) 186 (p 2H 74 Hz) 127 (d 3H J = 57 Hz) S14α Rf = 032 (5 methanol in

dichloromethane) NMR (CDCl3) δ 515 (d 1H J = 14 Hz) 387 (m 2H) 362 (s 3H) 355 (dd 1H J =

33 61 Hz) 335 (m 2H) 327 (m 2H) 269 (m 2H) 233 (t 2H J = 74 Hz) 220 (t 2H J = 74 Hz)

186 (p 2H J = 72 Hz) 123 (d 3H J = 62 Hz)

S11

[2-(4-carbamoylbutanoyl)ethyl] 1-thio-L-rhamnopyranoside (S15) Separately S14α (85

mg 024 mmol) and S14β (35 mg 01 mmol) were dissolved in methanol (4 mL) and lithium hydroxide

(1 mL of 1M aqueous) was added to each The reaction was stirred for 5 h and then neutralized with

amberlyst acidic resin The suspension was filtered rinsed and the filtrate was concentrated in vacuo

The products were purified by column chromatography to afford S15β (32 mg 95) and S15α (75 mg

92) S15α Rf = 020 (30 methanol in dichloromethane + 05 acetic acid) NMR (D2O) δ 508 (d

1H J = 14 Hz) 387 (m 2H) 355 (dd 1H J = 35 63 Hz) 328 (m 3H) 264 (m 2H) 215 (p 4H J =

74 Hz) 168 (p 2H J = 76 Hz) 112 (d 3H J = 63 Hz) 13C (D2O) δ 1799 1761 849 723 718

706 690 386 350 345 303 214 165 HRMS calcd for C13H23NO7NaS 3601093 [M+Na]+

found 3601083 S15β Rf = 020 (30 methanol in dichloromethane + 05 acetic acid) NMR (D2O) δ

467 (s 1H) 386 (d 1H J = 35 Hz) 344 (dd 1H J = 35 59 Hz) 328 (m 4H) 269 (m 2H) 226 (t

2H J = 74 Hz) 215 (t 2H J = 72 Hz) 173 (p 2H J = 74 Hz) 113 (d 3H J = 59 Hz) 13C (D2O) δ

1779 1758 842 763 734 722 718 390 347 328 301 206 169 HRMS calcd for

C13H23NO7NaS 3601093 [M+Na]+ found 3601086

S12

OHO

HOOH

O

OHO

HO

HOOH

S

OH

S16

NH

OR1

O O

HSNH

OMe

O O

S1

NMeO

S17 R1 = MeS18 R1 = H

[2-(methyl 4-carbamoylbutanoyl)ethyl] 1-thio-α-D-galactopyranoside (S17) To a solution of

linker S1 (132 g 64 mmol) dissolved in anhydrous CH3NO2 (5 mL) and 142 microL of TfOH was added

drop wise the donor 3-methoxy-2-pyridyl β-D-galactopyranoside S16[5] (233 mg 080 mmol) dissolved in

DMF (2 mL) over a period of 10 minutes The mixture was stirred at room temperature overnight after

which 5 drops of pyridine were added the solvent was removed in vacuo and the residue purified by

flash column chromatography (chloroformmethanol 82) to yield S17 along with a minor amount of the

beta anomer (αβ = 51 125 mg 59) which were separated using reverse phase HPLC (Atlantistrade dC18

column 5 microm 10 x 100 mm Flow rate = 8 mLmin Gradient = 0 to 20 CH3CN in H2O (with

01TFA) over 40 minutes while monitoring using a Waters 2420 ELS detector) Retention time = 135

min Rf = 025 (41 chloroformmethanol) 1H NMR (CD3OD) δ 538-53s (d J = 56 Hz 1H) 417-414

(bt J = 68 Hz 1H) 406-402 (dd J = 56 56 Hz 1H) 383-382 (d J = 32 Hz 1H) 375-371 (dd J

= 73 73 Hz 1H) 369-365 (dd J = 46 46 Hz 1H) 362 (s 3H) 355-352 (dd J = 33 33 Hz 1H)

344-331 (m 2H) 281-274 (m 1H) 264-257 (m 1H) 235-232 (t J = 73 2H) 222-218 (t J = 75

2H) 190-182 (m 2H) 13C NMR (D2O) δ 1762 1755 868 788 737 695 686 610 520 393

347 327 293 205

[2-(4-carbamoylbutanoyl)ethyl] 1-thio-α-D-galactopyranoside (S18) S17 (70 mg 0190

mmol) was dissolved in water (35 mL) and LiOH (9 mg) was added The solution was then stirred at

room temperature overnight neutralized with Amberlite IR-120 (H+) and filtered Purification by reverse

phase HPLC [Atlantistrade dC18 column 5 microm 10 x 100 mm Flow rate = 8 mLmin Gradient = 0 to

20 CH3CN in H2O (with 01TFA) over 40 minutes while monitoring using a Waters 2420 ELS

S13

detector] yielded S18 (26 mg 38) as a white cottony substance after lyophilization Retention time =

47 min (CH3CN-H2O) NMR (D2O) 1H δ 535-533 (d J = 57 Hz 1H) 413-410 (t J = 61 Hz 1H)

396-392 (dd J = 56 56 Hz 1H) 381 (d J = 25 Hz 1H) 361-359 (app d J = 68 Hz 2H) 357-353

(dd J = 34 34 Hz 1H) 335-322 (m 2H) 271-255 (m 2H) 228-224 (t J = 74 Hz 2H) 217-213

(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677

610 386 347 328 292 206 HRMS calcd for C13H23NO8NaS 3761042 [M+Na]+ found 3761053

S14

S20 R1 = Ac R2 = MeS21 R1 = H R2 = MeS22 R1 = H R2 = H

OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1

[2-(methyl 4-carbamoylbutanoyl)ethyl] 234-tri-O-acetyl-1-thio-β-D-galactopyranoside

(S20) Galactose pentaacetate (500 mg 128 mmol) and linker S1 (328 mg 16 mmol) were dissolved in

anhydrous CH2Cl2 (20 mL) the mixture was cooled to 0˚C and BF3Et2O (321microL 256 mmol) was added

drop wise After 24 hours the mixture was diluted with CH2Cl2 (120 mL) washed with saturated aqueous

NaHCO3 (2 x 150 mL) dried over Na2SO4 and concentrated The crude oil (51 βα mixture) was

purified by flash chromatography on silica gel using chloroform-methanol (101) to yield S20 (440 mg

64) as an oil Rf = 015 (91 chloroformmethanol) 1H NMR (CDCl3) δ 621-618 (t J = 52 Hz 1H)

544 (d J = 32 Hz 1H) 526-521 (t J = 10 Hz 1H) 507-504 (dd J = 36 36 Hz 1H) 453-450 (d

J = 100 Hz 1H) 420-416 (dd J = 68 72 Hz 1H) 411-407 (dd J = 56 56 Hz 1H) 399-396 (t J

= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)

241-237 (t J = 72 Hz 2H) 228-224 (t J = 76 Hz 2H) 217 (s 3H) 208 (s 3H) 205 (s 3H) 367

(s 3H) 199 (s 3H) 199-194 (m 2H) 13C NMR (CDCl3) δ 1735 1721 1703 1700 1698 1696

839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810

[2-(methyl 4-carbamoylbutanoyl)ethyl] 1-thio-β-D-galactopyranoside (S21) S20 (400 mg

0746 mmol) was dissolved anhydrous methanol (10 mL) and a catalytic amount of NaOMe was added

The mixture was stirred at room temperature for 6 hrs and then neutralized with Amberlite IR-120 (H+)

filtered and the solvent removed in vacuo The resulting residue was purified by reverse phase HPLC

[Atlantistrade dC18 column 5 microm 10 x 100 mm Flow rate = 8 mLmin Gradient = 0 to 20 CH3CN in

H2O (with 01TFA) over 40 minutes while monitoring using a Waters 2420 ELS detector] to yield S21

S15

(150 mg 54 yield) as a white cotton after lyophilization Retention time = 13 min Rf = 025 (82

chloroform-methanol) 1H NMR (D2O) δ 434-432 (d J = 10 Hz 1H) 382-381 (d J = 32 Hz 1H)

363-356 (m 2H) 353 (bs 3H) 350-347 (dd J = 36 32 Hz 1H) 342-337 (t J = 96 Hz 1H) 331-

328 (t J = 64 Hz 2H) 281-265 (2m 2H) 229-225 (t J = 76 Hz 2H) 216-212 (t J = 76 Hz 2H)

178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205

[2-(4-carbamoylbutanoyl)ethyl] 1-thio-β-D-galactopyranoside (S22) S21 (100 mg 0142

mmol) was dissolved in water and LiOH (20 mg) was added The solution was then stirred at room

temperature overnight neutralized with Amberlite IR-120 (H+) and filtered Purification by reverse



detector] yielded S22 (23 mg 47 yield) as a white cottony substance after lyophilization Retention

time = 52 min 1H NMR (D2O) δ 430-4285 (d J = 96 Hz 1H) 378 (d J = 32 Hz 1H) 358-351 (m

3H) 346-343 (dd J = 33 33 Hz 1H) 338-333 (t J = 95 Hz 1H) 328-325 (t J = 67 Hz 2H) 276-

264 (2m 2H) 209-206 (t J = 74 Hz 2H) 203-199 (t J = 742 Hz 2H) 168-160 (m 2H) 13C

NMR (D2O) δ 1824 1764 859 789 740 697 688 610 393 365 353 292 222 HRMS calcd

for C13H23NO8NaS 3761042 [M+Na]+ found 3761036

S16

S28 R1 = Bz R2 = MeS29 R1 = H R2 = MeS30 R1 = H R2 = H

HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz

S25 R = PhS26 R = OHS27 R = OC(NH)CCl3

OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O

Phenyl (2346-tetra-O-benzoyl-β-D-galactopyranosyl)-(1rarr6)-234-tri-O-benzoyl-1-thio-α-

D-mannopyranoside (S25) A mixture of donor S23[6] (270 mg 036 mmol 12 eq) and acceptor S24[7 8]

(150 mg 030 mmol 1 eq) was dried under vacuum for 1 hr and then dissolved in dichloromethane (2

mL) Molecular sieves was added to the solution and cooled to minus20 degC TMSOTf (0036 mmol 01 eq)

was added and the mixture was stirred at minus20 degC for 05 hr The reaction was quenched by saturated

NaHCO3 (1 mL) and worked up The crude product was purified by column chromatography (11 ethyl

acetatehexanes) to give the desired product S25 (210 mg 70 yield) Rf = 03 (12 ethyl

acetatehexanes) 1H NMR (CDCl3) δ 806-799 (m 6H) 793-787 (m 4 H) 779-777 (m 4 H) 763-

724 (m 26 H) 595-580 (m 5 H) 566 (d J = 16 Hz 1 H) 553 (dd J = 104 36 Hz 1 H) 492-489

(m 2 H) 456 (dd J = 112 64 Hz 1 H) 434 (dd J = 112 64 Hz 1 H) 423-416 (m 2 H) 404 (dd J

= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617

HRMS Calcd for [M+Na]+ C67H54O17NaS 11852974 Found 11853022

S17

2346-tetra-O-benzoyl-β-D-galactopyranosyl-(1rarr6)-234-tri-O-benzoyl-D-mannopyranose

(S26) NBS (43 mg 024 mmol 12eq) was added to solution of compound S25 (220 mg 02 mmol 1

eq) in 6 mL of acetone The reaction mixture was stirred at room temperature for 1 hr and worked up

The crude product was purified by chromatography to give compound S26 (160 mg 80 yield) Rf =

02 (11 ethyl acetatehexanes) 1H NMR (CDCl3) δ 803-799 (m 8 H) 792-789 (m 2 H) 780-776 (m

4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-

562 (m 2 H) 556 (dd J = 32 16 Hz 2 H) 499-497 (m 2 H) 465 (dd J = 112 60 Hz 1 H) 451-

446 (m 1 H) 442-432 (m 2 H) 422 (dd J = 112 16 Hz 1 H) 389 (dd J = 120 84 Hz 1 H) 13C

NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709

708 7033 7025 696 681 675 619 HRMS Calcd for [M+Na]+ C61H50O18Na 10932913 Found

10932940

2346-tetra-O-benzoyl-β-D-galactopyranosyl-(1rarr6)-234-tri-O-benzoyl-1-thio-α-D-

mannopyranosyl trichloroacetoimidate (S27) To a mixture of compound S26 (220 mg 02 mmol) and

trichloroacetonitrile (1 mL 10 mmol) in 6 mL of dichloromethane was added DBU (30 microL 02 mmol)

The reaction mixture was stirred at room temperature for 30 min The crude product was purified by

chromatography (40 ethylacetatehexanes 01 triethylamine) to give compound S27 (220 mg 88

yield) Rf = 03 (12 ethyl acetatehexanes) 1H NMR (CDCl3) δ 846 (s 1 H) 810-808 (m 2 H) 805-

803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721

(m 21 H) 637 (d J = 20 Hz 1 H) 598 (dd J = 36 08 Hz 1 H) 592-579 (m 4 H) 557 (dd J =

104 36 Hz 1 H) 496 (d J = 80 Hz 1 H) 462-454 (m 2 H) 438-424 (m 3 H) 392 (dd J = 112

68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696

695 688 686 680 665 617 HRMS Calcd for [M+Na]+ C63H50NO18NaCl3 12361986 Found

12361980

S18

[2-(methyl 4-carbamoylbutanoyl)ethyl] (2346-tetra-O-benzoyl-β-D-galactopyranosyl)-

(1rarr6)-234-tri-O-benzoyl-1-thio-α-D-mannopyranoside (S28) To a mixture of compound S27 (320

mg 026 mmol) linker S1 (60 mg 029 mmol) and molecular sieves in dichloromethane (5 mL) was

added BF3Et2O (30 microL 026 mmol) at minus20 degC The reaction mixture was warmed to 0 degC in 1 hr and

quenched by adding triethylamine (50 microL) The crude product was purified by chromatography to give

the desired product S28 (210 mg 64 yield) Rf = 03 (ethyl acetate) 1H NMR (CDCl3) δ 805-803 (m

4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14

H) 732-723 (m 7 H) 653 (t J = 60 Hz 1 H) 598 (dd J = 36 08 Hz 1 H) 579-573 (m 2 H) 568-

563 (m 2 H) 558 (dd J = 108 36 Hz 1 H) 521 (d J = 12 Hz 1 H) 491 (d J = 80 Hz 1 H) 481

(m 1 H) 458 (dd J = 114 60 Hz 1 H) 438 (dd J = 112 68 Hz 1 H) 432 (m 1 H) 422 (dd J =

108 20 Hz 1H) 395 (dd J = 108 96 Hz 1 H) 356 (s 3 H) 349-342 (m 1 H) 340-332 (m 1 H)

286-279 (m 1 H) 262-254 (m 1 H) 235 (t J = 72 Hz 2 H) 228 (t J = 72 Hz 2 H) 196 (m 2 H)

13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679

676 617 514 390 353 332 314 208 HRMS Calcd for [M+Na]+ C69H63NO20NaS 12803556

Found 12803593

[2-(4-carbamoylbutanoyl)ethyl] (β-D-galactopyranosyl)-(1rarr6)-1-thio-α-D-

mannopyranoside (S30) NaOMe (1 mg 002 mmol) was added to a solution of compound S28 (70 mg

0056 mmol) in methanol (2 mL) The reaction mixture was stirred at room temperature for 3 hrs The

reaction mixture was neutralized by ion exchange resin (Amberlite 15 50 mg) The mixture was filtered

and the filtrate was concentrated The residue was dissolved in mixture of water and acetonitrile (2 mL

1 1) and extracted by hexanes (2 mL times 4) until all methyl benzoate was removed The aqueous phase

was concentrated and the residue was dissolve in 1 M NaOH (1 mL) solution and stirred at room

temperature overnight The solution was neutralized by ion exchange resin (Amberlite 15 100 mg) and

filtered The filtrate was concentrated and purified by reverse phase HPLC [Atlantistrade dC18 column 5

S19

microm 10 x 100 mm Flow rate = 8 mLmin Gradient = 0 to 20 CH3CN in H2O (with 01TFA) over

40 minutes while monitoring using a Waters 2420 ELS detector] to give the desired product S30 (15 mg

52 yield) Retention time = 825 min 1H NMR (D2O) δ 515 (d J = 12 Hz 1 H) 427 (d J = 76 Hz 1

H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268

(m 1 H) 266-259 (m 1 H) 220 (t J = 72 Hz 2 H) 214 (t J = 72 Hz 2 H) 171 (pent J = 72 Hz 2

H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20

S35 R1 = Bz R2 = Ac R3 = MeS36 R1 = H R2 = H R3 = MeS37 R1 = H R2 = H R3 = H

HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O

Phenyl (2346-tetra-O-acetyl-α-D-mannopyranosyl)-(1rarr6)-234-tri-O-benzoyl-1-thio-α-D-

mannopyranoside (S32) A mixture of donor S31[9] (270 mg 055 mmol 17 eq) and acceptor S24 (190

mg 030 mmol 1 eq) was dried under vacuum for 1 h and then dissolved in dichloromethane Molecular

sieves was added to the solution and cooled to minus20 degC TMSOTf (0030 mmol 01 eq) was added and the

mixture was stirred at minus20 degC for 05 hr The reaction was quenched by saturated NaHCO3 (1 mL) and

worked up The crude product was purified by column chromatography (11 ethyl acetatehexanes) to

give the desired product S32 (226 mg 77 yield) Rf = 03 (12 ethyl acetatehexanes) 1H NMR

(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3

H) 742-732 (m 5 H) 729-722 (m 3 H) 601 (t J = 100 Hz 1 H) 594 (dd J = 32 16 Hz 1 H) 580

(dd J = 104 32 Hz 1 H) 571 (s 1 H) 536 (dd J = 100 32 Hz 1 H) 531 (dd J = 36 16 Hz 1 H)

522 (t J = 104 Hz 1 H) 484-480 (m 2 H) 405 (dd J = 124 56 Hz 1 H) 398 (dd J = 112 52 Hz

1 H) 386-381 (m 2 H) 363 (dd J = 108 12 Hz 1 H) 208 (s 3 H) 204 (s 3 H) 198 (s 3 H) 188

(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21

706 695 693 688 671 669 660 623 2101 2096 209 207 HRMS Calcd for [M+Na]+

C47H46O17NaS 9372348 Found 9372348

(2346-tetra-O-acetyl-α-D-mannopyranosyl)-(1rarr6)-234-tri-O-benzoyl-D-mannopyranose

(S33) NBS (68 mg 038 mmol 12eq) was added to solution of compound 3 (290 mg 032 mmol 1 eq)

in 10 mL of acetone The reaction mixture was stirred at room temperature for 1 hr and worked up The

crude product was purified by chromatography to give compound S33 (260 mg 99 yield) as a mixture

of anomers Rf = 02 (11 ethyl acetatehexanes) HRMS Calcd for [M+Na]+ C41H41O18Na 8452263

Found 8452239

(2346-tetra-O-acetyl-α-D-mannopyranosyl)-(1rarr6)-234-tri-O-benzoyl-D-mannopyranosyl

trichloroacetoimidate S34 To a mixture of compound S33 (260 mg 031 mmol) and


The reaction mixture was stirred at room temperature for 30 mins The crude product was purified by



798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724

(m 2 H) 650 (s 1 H) 604 (m 1 H) 596-593 (m 2 H) 537 (dd J = 100 32 Hz 1 H) 530-526 (m

2 H) 484 (d J = 12 Hz 1 H) 449 (m 1 H) 414 (dd J = 120 48 Hz 1 H) 402 (m 1 H) 400-390

(m 2 H) 373 (dd J = 112 20 Hz 1 H) 213 (s 3 H) 207 (s 3 H) 200 (s 3 H) 194 (s 3 H) 13C

NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685

661 658 621 208 2075 2067 205 HRMS Calcd for [M+Na]+ C43H42NO18NaCl3 9881360

Found 9881359

[2-(methyl 4-carbamoylbutanoyl)ethyl] (2346-tetra-O-acetyl-α-D-mannopyranosyl)-




S22

quenched by adding triethyl amine (50 microL) The crude product was purified by chromatography to give

the desired product S35 (140 mg 61 yield) Rf = 03 (ethyl acetate) 1H NMR (CDCl3) δ 810 (m 2H)

798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1

H) 287-280 (m 1 H) 240 (t J = 72 Hz 2 H) 228 (t J = 72 Hz 2 H) 213 (s 3 H) 207 (s 3 H) 201

(s 3 H) 200 (m 2 H) 198 (s 3 H) 13C NMR (CDCl3) δ1736 1723 1705 1701 1699 1697 1655

1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206

HRMS Calcd for [M+Na]+ C49H55NO20NaS 10322930 Found 10322940

[2-(4-carbamoylbutanoyl)ethyl] (α-D-mannopyranosyl)-(1rarr6)-1-thio-α-D-mannopyranoside

(S37) NaOMe was added to a solution of compound S35 (50 mg 005 mmol) in methanol (2 mL) The

reaction mixture was stirred at room temperature for 3 hrs The reaction mixture was neutralized by ion

exchange resin (Amberlite 15 50 mg) The mixture was filtered and the filtrate was concentrated The

residue was dissolved in mixture of water and acetonitrile (2 mL 1 1) and extracted by hexanes (2 mL times

4) until all methyl benzoate was removed The aqueous phase was concentrated and the residue was

dissolve in 1 M NaOH solution and stirred at room temperature overnight The solution was neutralized

by ion exchange resin (Amberlite 15 200 mg) and filtered The filtrate was concentrated and purified by

reverse phase HPLC [Atlantistrade dC18 column 5 microm 10 x 100 mm Flow rate = 8 mLmin Gradient =

0 to 20 CH3CN in H2O (with 01TFA) over 40 minutes while monitoring using a Waters 2420 ELS

detector] to give the desired product S37 (11 mg 43 yield) Retention time = 821 min 1H NMR

(CDCl3) δ 516 (d J = 12 Hz 1 H) 474 (d J = 12 Hz 1 H) 400 (m 1 H) 390 (dd J = 28 12 hz 1

H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323

(m 2 H) 271-256 (m 2 H) 211 (t J = 72 Hz 2 H) 205 (t J = 72 Hz 2 H) 167 (p J = 72 Hz 2 H)

13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O

S47 R1 = Ac R2 = Me R3 = BzS48 R1 = H R2 = Me R3 = HS49 R1 = H R2 = H R3 = H

S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc

S45 R = NTCPS46 R = NHAc

OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44

11-dimethyl-222-trichloroethyl N-(2-mercaptoethyl)carbamate (S38) A solution of

NaHCO3 (714g 85 mmol) in 75 mL of H2O was added to a vigorously stirred mixture of 2-

aminoethanethiol hydrochloride (32 282 mmol) in 250 mL of deoxygenated Et2O under argon at minus10degC

After 35 minutes of stirring 222-trichloro-11-dimethylethyl chloroformate (10g 416 mmol) dissolved

in 150 mL of Et2O was added drop wise over 45 minutes The ice bath was then removed and the

reaction stirred vigorously under argon for 6 hrs The organic and aqueous layers were then separated and

the organic layers washed with 2M HCl (3 x 200 mL) After drying over Na2SO4 the solvent was

removed to leave a clear semi-viscous oil that was relatively pure by TLC Purification by flash

chromatography on silica gel using heptane-ethyl acetate (gradient of 5-50) yielded 2-(mercapto-ethyl)-

11-dimethyl-222-trichloroethyl carbamate S38 (513 g 65) as an oil Rf = 059 (32 ethyl acetate-

hexanes stains with KMnO4) 1H NMR (CDCl3) δ 521 (bs 1H) 337-333 (q J = 64 Hz 2H) 271-

S24

265(q 2H) 192 (s 6H) 139-135(t J = 84 Hz 1H) 13C NMR (CDCl3) δ = 1539 1064 881 437

247 2171 2160 HRMS calcd for C7H13NO2SCl3 2799732 [M+H]+ found 2799740

11-dimethyl-222-trichloroethyl N-(2-mercaptoethyl)carbamate-(2346-tri-O-acetyl)-1-

thio-β-D-galactopyranoside (S39) Galactose pentaacetate (298 g 764 mmol) and linker S38 (225 g

80 mmol) were dissolved in anhydrous CH2Cl2 (20 mL) the mixture was cooled to 0˚C and BF3Et2O

(916 mL 729 mmol) was added drop wise After 24 hours the mixture was diluted with CH2Cl2 (120

mL) washed with saturated aqueous NaHCO3 (2 x 150 mL) dried over Na2SO4 and concentrated The

crude oil after concentration was purified by flash chromatography on silica gel using hexanes-ethyl

acetate (32) to yield S39 (396 g 85) as a viscous clear oil Rf = 026 (32 ethyl acetate-hexanes) 1H

NMR (CDCl3) δ 544-543 (d J = 32 Hz 1H) 541-538 (t J = 54 Hz 1H) 528-521(t J = 99 Hz

1H) 506-503 (dd J = 33 33 Hz 1H) 452-449 (d J = 99 Hz 1H) 418-410 (m 2H) 398-395 (t J

= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)

205 (s 3H) 198 (s 3H) 192 (bs 6H) 13C NMR (CDCl3) δ 1702 1700 1699 1539 1064 880

842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for

C21H30NO11NaSCl3 6320497 [M+Na]+ found 6320504

11-dimethyl-222-trichloroethyl N-(2-mercaptoethyl)carbamate-(46-O-benzylidene)-1-

thio-β-D-galactopyranoside (S41) S39 (200 g 33 mmol) was dissolved anhydrous methanol (20 mL)

and a catalytic amount of NaOMe was added The mixture was stirred at room temperature for 8 hrs and

then neutralized with Amberlite IR-120 (H+) filtered and the solvent removed in vacuo The crude

residue was dissolved into anhydrous CH3CN (15 mL) and benzaldehyde dimethyl acetal (104g 68

mmol) added followed by a catalytic amount camphor sulfonic acid After stirring overnight at room

temperature 3mL of Et3N was added and the solvent was removed in vacuo To the residue was added

200 mL of ethyl acetate which was washed with saturated aqueous NaHCO3 (2 x 150 mL) dried over

Na2SO4 and concentrated Purification by flash chromatography on silica gel using hexanes-ethyl acetate

(30-100) yielded S41 (174 g 82) as a white foam Rf = 024 (14 toluene-ethyl acetate) 1H NMR

S25

(CDCl3) δ 749-746 (m 2H) 741-736 (t 3H) 566-563 (t J = 60 Hz 1H) 555(s 1H) 439-435(app

dd J = 12 9 Hz 2H) 428-427 (d J = 36 Hz 1H) 406-403 (dd J = 17 17 Hz 1H) 384-379 (3 x d

J = 17 Hz 1H) 371-366 (3 x d J = 36 Hz 1H) 362-355 (m 2H) 345-330 (m 1H) 296 (d J = 17

1H) 292-287 (m 2H) 261-259 (d J = 85 1H) 192 (s 3H) 191 (s 3H) 13C NMR (CDCl3) δ 1543

1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216

HRMS calcd for C20H26NO7NaSCl3 5520388 [M+Na]+ found 5520394

11-dimethyl-222-trichloroethyl N-(2-mercaptoethyl)carbamate-(23-di-O-acetyl-46-O-

benzylidene)-1-thio-β-D-galactopyranoside (S42) S41 (229 g 43 mmol) was dissolved in anhydrous

pyridine (20 mL) and then cooled to 0degC in an ice bath To this solution was added Ac2O (10 mL) and a

catalytic amount of DMAP After 24 hours the mixture was poured into ice-water and extracted with

ethyl acetate (2 x 100 mL) The extracts were then successively washed with water aqueous HCl and

water dried over Na2SO4 and then concentrated The residual viscous oil was purified by flash

chromatography on silica gel using hexanes-ethyl acetate (35-65) to yield S42 (265 g 77) as a white

foam Rf = 035 (91 chloroform-methanol) 1H NMR (CDCl3) δ 749-746 (m 2H) 739-737 (m 3H)

550(s 1H) 548-541 (m 2H) 500-497 (dd J = 33 33 Hz 1H) 449-446 (d J = 98 Hz 1H) 442-

441 (d J = 33 Hz 1H) 437-434 (d J = 125 Hz 1H) 403-400 (d J =125 Hz 1H) 360 (s 1H)

352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for



benzoyl)-1-thio-β-D-galactopyranoside (S43) S42 (200 g 32 mmol) was dissolved in acetic acid

(80 aqueous solution 10 mL) and heated at 70 degC for 4 h The solvent was evaporated and the residue

was dried by azeotropic distillation with toluene (4 x 150 mL) The white precipitate was then suspended

(insoluble in CH2Cl2) in dichloromethane (20 mL) cooled -20degC and triethylamine (566 microL 40 mmol)

S26

and benzoyl chloride (415 microL 35 mmol) were added The solution was kept at minus20 degC for 15 h and then

allowed to warm to room temperature and stirred an additional 24 hours The solution was then diluted

with additional CH2Cl2 (150 mL) washed with sat NaHCO3 brine and then dried over anhydrous

Na2SO4 The solvent was evaporated and residue was purified by column chromatography (gradient of

30-60 ethyl acetatehexanes) to yield S43 (119g 58) Rf = 024 (14 tolueneethyl acetate) 1H NMR

(CDCl3) δ 803-801 (d J = 72 Hz 2H) 76-755 (m 1H) 747-745 (t J = 78 Hz 2H) 552 (t J = 51

Hz 1H) 543-538 (t J = 99 Hz 1H) 504-501 (dd J = 30 30 Hz 1H) 464-449 (m 3H) 418 (t J =

38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210

(s 3H) 207 (s 3H) 190 (s 6H) 13C NMR (CDCl3) δ 1700 1697 1663 1541 1333 1297

12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for


11-dimethyl-222-trichloroethyl N-(2-mercaptoethyl)carbamate-(346-tri-O-acetyl-2-

deoxy-2-tetrachlorophthalimido-β-D-galactopyranosyl)-(1rarr4)-23-di-O-acetyl-6-O-benzoyl-1-thio-

β-D-galactopyranoside (S45) A mixture of donor 346-tri-O-acetyl-2-deoxy-2-tetrachlorophthalimido-

αβ-D-galactopyranosyl chloride S44[10] (168 g 28 mmol) acceptor S43 (895 mg 141 mmol) and di-

tert-butylmethylpyridine (145 70 mmol) were dissolved in anhydrous CH2Cl2 (30 mL) and activated 4

Aring powdered molecular sieves added After stirring for 3 hr at room temperature under argon the reaction

was cooled to minus78 degC stirred an additional 20 minutes and then AgOTf (22 g 85 mmol) added The

reaction mixture was allowed to warm to 0 degC over 25 h and then filtered through a bed of Celite The

mixture was then diluted with additional CH2Cl2 (150 mL) washed with sat NaHCO3 and then dried

over anhydrous Na2SO4 After removal of the solvent the residue was purified by column

chromatography (gradient from 0-25 toluene in ethyl acetate) to yield S45 (128 g 76) as an off white

solid Rf = 030 (32 tolueneethyl acetate) 1H NMR (CDCl3) δ 805-803 (d J = 71 Hz 2H) 760-756

(m 1H) 749-745(t 2H) 591-580 (m 2H) 547 (d J = 32 Hz 1H) 522-520 (d J = 83 Hz 1H)

498-495 (app d J = 101 Hz 1H) 481-476 (t J = 99 Hz 1H) 459-451 (m 2H) 445-440 (dd J =

S27

601 602 Hz 1H) 427 (br s 1H) 425 (br s 1H) 408-397 (m 3H) 391-388 (t J = 55 Hz 1H) 346-

342 (q 2H) 270-263 (m 1H) 254-247 (m 1H) 219 (s 3H) 213 (s 3H) 197 (br s 3H) 196 (br s

3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051

2032 HRMS calcd for C44H45N2O19NaSCl7 120500 [M+Na]+ found 120500


acetamido-2-deoxy-β-D-galactopyranosyl)-(1rarr4)-23-di-O-acetyl-6-O-benzoyl-1-thio-β-D-

galactopyranoside (S46) To S45 (469 mg 0395 mmol) dissolved in 10 mL of a mixture of anhydrous

CH3CNEtOHTHF (211) was added ethylenediamine (270 microL 395 mmol) The mixture was then

stirred at 80degC for 15 hours cooled to room temperature and then concentrated This crude product was

dissolved in anhydrous pyridine (15 mL) and then cooled to 0degC in an ice bath To this solution was

added Ac2O (7 mL) and a catalytic amount of DMAP After 24 hours the mixture was diluted with ethyl

acetate (175 mL) and successively washed with aqueous HCl and the organic layers dried over Na2SO4

and concentrated The residual viscous oil was purified by flash chromatography on silica gel using

CHCl3MeOH (951) to yield S46 (247 mg 65) as an off white solid Rf = 04 (951 CHCl3-MeOH)

1H NMR (CDCl3) δ 800-797 (d J = 74 Hz 2H) 754-750 (m 1H) 742-738 (t J = 78 Hz 2H) 672-

670 (d J = 71 Hz 1H) 589-586 (dd J = 33 33 Hz 1H) 549-546 (t J = 63 Hz 1H) 543-538 (t J

= 98 Hz 1H) 534-533 (d J = 31 Hz 1H) 507-505 (d J = 81 Hz 1H) 502-498 (dd J = 26 26 Hz

1H) 457-453 (dd J = 53 53 Hz 1H) 441-435 (m 3H) 423 (d J = 20 Hz 1H) 399-389 (m 3H)

386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-

245 (m 1H) 212 (s 3H) 208 (s 3H) 201 (s 3H) 199 (s 3H) 196 (s 3H) 188 (s 3H) 159 (s

3H) 157 (s 3H) HRMS calcd for C38H49N2O18NaSCl3 9811659 [M+Na]+ found 9811614

Methyl pentafluorophenyl glutarate To a solution of mono-methyl glutarate (11g 752 mmol)

and pentafluorophenol (208 g 1129 mmol) dissolved in 100 mL of anhydrous THF was added drop wise

S28

over 1 hr a 1M CH2Cl2 solution of dicyclohexylcarbodiimide (DCC 112 mL 113 mmol) The reaction

was allowed to stir at room temperature for 24 hr and then solid oxalic acid (102 g 1129 mmol) was

added very slowly to rid the reaction of excess DCC The solvent was then removed in vacuo to leave

crude product that was dissolved into 250 mL of ethyl acetate (250 mL) washed with saturated aqueous

NaHCO3 (3 x 200 mL) dried over Na2SO4 filtered and concentrated The residue was purified by flash

chromatography on silica gel using hexanes-ethyl acetate (71) to yield methyl pentafluorophenyl

glutarate (14 g 63) as a viscous oil that solidifies upon storing at 0degC Rf = 031 (71 hexanesethyl

acetate) 1H NMR (CDCl3) δ 366 (s 3H) 274-270 (t J = 73 Hz 2H) 245-241 (t J = 72 Hz 2H)

209-202 (q J = 74 72 Hz 2H)

[2-(methyl 4-carbamoylbutanoyl)ethyl] (346-tri-O-acetyl-2-acetamido-2-deoxy-β-D-

galactopyranosyl)-(1rarr4)-23-di-O-acetyl-6-O-benzoyl-1-thio-β-D-galactopyranoside (S47)

Compound S46 (244 mg 0271 mmol) was dissolved in CH2Cl2 (9 mL) and 4 ml of AcOH was added

followed by the addition of zinc metal (50 mg) The mixture was allowed to stir for 3 hr at room

temperature and then additional zinc metal (75 mg) was added The reaction was followed by TLC

(CHCl3MeOH 91) to follow the deprotection of TCBOC from the amino group After 8 hr the reaction

was diluted with additional CH2Cl2 (70 mL) washed with saturated K2CO3 the organic and aqueous

layers separated and the organic layers dried over Na2SO4 filtered and concentrated to yield an oil This

oil was dissolved in 5 mL of anhydrous CH2Cl2 and methyl pentafluorophenyl glutarate (127 mg 0407

mmol) added The mixture was stirred for 3 hr and then concentrated The residue was purified by flash

chromatography on silica gel using CHCl3-MeOH (gradient of 0-10) to yield S47 (179 mg 80) as a

white foam Rf = 050 (91 CHCl3-MeOH) 1H NMR (CDCl3) δ 804-802 (d J = 94 Hz 2H) 759-753

(t J = 8 Hz 1H) 747-743 (t J = 76 Hz 2H) 711-709 (d J = 78 Hz 1H) 677-674 (t J = 572 Hz

1H) 573-569 (dd J = 35 35 Hz 1H) 547-543 (t J = 98 Hz 1H) 536-535 (d J = 34 Hz 1H)

508-504 (dd J = 26 26 Hz 1H) 501-499 (d J = 82 Hz 1H) 460-456 (dd J = 51 51 Hz 1H)

446-440 (m 2H) 428-427 (d J = 24 Hz 1H) 406-400 (dd J = 87 45 Hz 1H) 397-388 (m 3H)

S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205

(s 3H) 200 (s 3H) 193 (s 3H) 13C NMR (CDCl3) δ 1734 1724 1716 1704 1703 1702 1701

1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for

C39H52N2O19NaS 9072777 [M+Na]+ found 9072770

[2-(methyl 4-carbamoylbutanoyl)ethyl] (2-acetamido-2-deoxy-β-D-galactopyranosyl)-

(1rarr4)-1-thio-β-D-galactopyranoside (S48) S47 (100 mg 113 micromol) was dissolved anhydrous

methanol (3 mL) and a catalytic amount of NaOMe was added The mixture was stirred at room

temperature for 8 hrs and then neutralized with Amberlite IR-120 (H+) filtered and the solvent removed

in vacuo The resulting oil was purified by reverse phase HPLC [Atlantistrade dC18 column 5 microm 10 x

100 mm Flow rate = 8 mLmin Gradient = 0 to 20 CH3CN in H2O (with 01TFA) over 40 minutes

while monitoring using a Waters 2420 ELS detector] to yield S48 (49 mg 76) as a white cottony solid

after lyophilization Retention time = 103 min 1H NMR (D2O) δ 447-458 (d J = 84 Hz 1H) 433-

431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-373 (m 2H) 367-355 (m 7H) 353 (s

3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t

J = 73 Hz 2H) 189 (s 3H) 177-170 (m J = 74 73 Hz 2H) 13C NMR (CDCl3) δ 1763 1758 1747

1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205

HRMS calcd for C22H38N2O13NaS 59319927 [M+Na]+ found 5931994

[2-(4-carbamoylbutanoyl)ethyl] (2-acetamido-2-deoxy-β-D-galactopyranosyl)-(1rarr4)-1-thio-

β-D-galactopyranoside (S49) S48 (40 mg 70 micromol) was dissolved in water (20mL) and LiOH (1 mg)

was added The solution was then stirred at room temperature overnight neutralized with Amberlite IR-

120 (H+) and filtered Purification by reverse phase HPLC [Atlantistrade dC18 column 5 microm 10 x 100

mm Flow rate = 8 mLmin Gradient = 0 to 20 CH3CN in H2O (with 01TFA) over 40 minutes

while monitoring using a Waters 2420 ELS detector] yielded S49 (26 mg 66) as a white cottony

S30

substance after lyophilization Retention time = 645 1H NMR (D2O) δ 447-445 (d J = 84 Hz 1H)

433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73

Hz 2H) 189 (s 3H) 176-169 (m J = 74 73 Hz 2H) 13C NMR (CDCl3) δ 1782 1759 1747 1026

858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS

calcd for C21H36N2O13LiS 5632098 [M+Li]+ found 5632101

S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1

[2-(methyl 4-carbamoylbutanoyl)ethyl] (2346-tetra-O-acetyl-β-D-glucopyranosyl)-(1rarr4)-

234-tri-O-acetyl-1-thio-β-D-glucopyranoside (S51) A mixture of cellobiose octacetate (678 mg 10

mmol) linker S1 (240 mg 12 mmol) and SnCl4 (13 mL of 1 M solution in dichloromethane) in

dichloromethane (10 mL) was stirred at room temperature for overnight The reaction mixture was

washed with 1 N HCl (10 mL) saturated NaHCO3 (15 mL times 2) and brine (10 mL) The solvent was

removed and crude product was purified by chromatography to give the desired product S51 (500 mg 61

yield) Rf = 03 (ethyl acetate) 1H NMR (CDCl3) δ 611 (m 1 H) 519 (t J = 92 Hz 1 H) 516 (t J

= 94 Hz 1 H) 495-490 (m 2 H) 462 (dd J = 120 20 Hz 1 H) 454 (d J = 80 Hz 1 H) 447 (d J =

100 Hz 1 H) 438 (dd J = 124 40 Hz 1 H) 410-403 (m 2 H) 375 (t J = 100 Hz 1 H) 370-365

(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)

275-269 (m 1 H) 239 (t J = 72 Hz 2 H) 226 (t J = 72 Hz 2 H) 212 (s 3 H) 209 (s 3 H) 205 (s

3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)

[2-(4-carbamoylbutanoyl)ethyl] (β-D-glucopyranosyl)-(1rarr4)-1-thio-β-D-glucopyranoside










S32


(CDCl3) δ 441 (d J = 100 Hz 1 H) 435 (d J = 76 Hz 1 H) 381 (dd J = 124 20 Hz 1 H) 375 (dd

J = 124 20 Hz 1 H) 364 (dd J = 124 48 Hz 1 H) 357 (dd J = 124 56 Hz 1 H) 354-342 (m 3

H) 337-313 (m 7 H) 281-265 (m 2 H) 210 (t J = 76 Hz 2 H) 204 (t J = 76 Hz 2 H) 167 (m 2

H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605

600 393 366 353 292 223 HRMS Calcd for [M+Na]+ C19H33NO13NaS 5381570 Found

5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1


[2-(methyl 4-carbamoylbutanoyl)ethyl] (2346- tri-O-acetyl-α-D-glucopyranosyl)-(1rarr4)-

236- tri-O-acetyl-1-thio-αβ-D-glucopyranoside (S54) Maltose 4-O-α-D-glucopyranosyl-D-glucose

(2 g 58 mmol) was dissolved in anhydrous pyridine (25 mL) and then cooled to 0degC in an ice bath To

this solution was added Ac2O (10 mL) and a catalytic amount of DMAP After 24 hours the mixture was

poured into ice-water and extracted with ethyl acetate (2 x 100 mL) The extracts were then successively

washed with water aqueous HCl and water dried over Na2SO4 and then concentrated The residual

viscous oil was purified by flash chromatography on silica gel using toluene-ethyl acetate (gradient of 0-

45) to yield maltose octaacetate (20 g 50) as a viscous oil The maltose octaacetate (300 mg 044

mmol) and linker S1 (272 mg 13 mmol) were then dissolved in anhydrous CH2Cl2 (5 mL) cooled to

0degC and BF3Et2O (444 microL 34 mmol 8eq) added After stirring for 24 hours the reaction was diluted

with CH2Cl2 (100 mL) washed with sat aq NaHCO3 (2 x 300 mL) dried over Na2SO4 and concentrated

to yield viscous oil Purification by flash chromatography on silica gel using chloroform-methanol (91)

yielded an inseparable mixture of anomers (51 βα) of S54 (175 mg 48) as an oil Rf = 020 (101

ethyl acetatehexanes) 1H NMR (CDCl3) for the major component (β anomer) δ 621-618 (t J = 57 Hz

3H) 545-540 (dd J = 96 96 Hz 1H) 538-537 (d J = 37 Hz 3H) 509-504 (t J = 97 Hz 1H)

500-497 (dd J = 37 37 Hz 3H) 486-481 (t J = 66 Hz 1H) 461-458 (d J = 126 Hz 1H) 444-

441 (d J = 10 Hz 1H) 427-423 (dd J = 42 42 Hz 1H) 417-406 (m 4H) 383-379 (t J = 87 Hz

1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-

269 (m 1H) 240-237 (t J = 72 Hz 1H) 227-224 (t J = 72 Hz 1H) 213 (s 3H) 209-208 (s 6H)

206 (s 3H) 203 (s 3H) 201 (s 3H) 199-192 (m 2H) 13C NMR (D2O) for the major component (β

S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501

[2-(methyl 4-carbamoylbutanoyl)ethyl] (α-D-glucopyranosyl)-(1rarr4)-1-thio-β-D-

glucopyranoside (S55) S54 (60 mg 72 micromol) was dissolved anhydrous methanol (3 mL) and a catalytic

amount of NaOMe was added The mixture was stirred at room temperature for 6 hrs and then

neutralized with Amberlite IR-120 (H+) filtered and the solvent removed in vacuo The resulting oil was

purified by reverse phase HPLC [Atlantistrade dC18 column 5 microm 10 x 100 mm Flow rate = 8 mLmin

Gradient = 0 to 20 CH3CN in H2O (with 01TFA) over 40 minutes while monitoring using a Waters

2420 ELS detector] to yield S55 (28 mg 73 yield) as a white cottony solid after lyophilization

Retention time = 762 min 1H NMR (D2O) δ 525-524 (d J = 38 Hz 1H) 441-439 (d J = 98 Hz 1H)

377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265

(2m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t J = 72 Hz 2H) 178-170 (m 2H) 13C NMR

(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347

327 292 205 HRMS calcd for C20H35NO13NaS 5521726 [M+Na]+ found 5521742

[2-(4-carbamoylbutanoyl)ethyl] (α-D-glucopyranosyl)-(1rarr4)-1-thio-β-D-glucopyranoside

(S56) S55 (25 mg 47 micromol) was dissolved in water (20mL) and LiOH (2 mg) was added The solution

was then stirred at room temperature overnight neutralized with Amberlite IR-120 (H+) and filtered

Purification by reverse phase HPLC [Atlantistrade dC18 column 5 microm 10 x 100 mm Flow rate = 8

mLmin Gradient = 0 to 20 CH3CN in H2O (with 01TFA) over 40 minutes while monitoring using

a Waters 2420 ELS detector] yielded S56 (20 mg 83) as a white cottony substance after lyophilization


377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73

Hz 2H) 217-213 (t J = 74 Hz 2H) 176-169 (m 2H) 13C NMR (D2O) δ 1777 1759 994 851

S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O


234- tri-O-acetyl-1-thio-β-D-glucopyranoside (S58) Isomaltose 6-O-α-D-glucopyranosyl-D-glucose



poured into ice water and extracted with ethyl acetate (2 x 100 mL) The extracts were then successively


viscous oil was purified by flash chromatography on silica gel using toluene-ethyl acetate (0-80) to

yield maltose octaacetate (20 g 50) as viscous oil The isomaltose octaacetate (350 mg 051 mmol)

and linker S1 (318 mg 15 mmol) were then dissolved was then dissolved into anhydrous CH2CL2 (5

mL) cooled to 0degC and BF3Et2O (260 microL 20 mmol 4eq) added After stirring for 24 hours the

reaction was diluted with CH2Cl2 (100 mL) washed with sat aq NaHCO3 (2 x 300 mL) dried over

Na2SO4 and concentrated to yield viscous oil Purification by flash chromatography on silica gel using

hexanes-ethyl acetate (gradient of 0-80) yielded S58 (152 mg 36) as an oil Rf = 015 (91 ethyl

acetate-hexanes) 1H NMR (CDCl3) δ 653-651 (t J = 56 Hz 3H) 547-542 (dd J = 97 97 Hz 1H)

526-521 (t J = 93 93 Hz 1H) 511-494 (m 5H) 488-483 (dd J = 36 36 Hz 3H) 458-455 (d J =

10 Hz 1H) 428-424 (dd J = 44 44 Hz 1H) 410-403 (m 2H) 376-370 (m 2H) 366 (s 3H) 359-

352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-

223 (t J = 72 2H) 212 (s 3H) 210 (s 3H) 206 (s 3H) 205 (s 3H) 203(s 3H) 202 (s 3H) 201

(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37

2067 2064 2062 2057 2051 2049 HRMS calcd for C34H49NO20NaS 8462461 [M+H]+ found

8462451


glucopyranoside (S59) S58 (86 mg 0104 mmol) was dissolved anhydrous methanol (3 mL) and a

catalytic amount of NaOMe was added The mixture was stirred at room temperature for 8 hrs and then






382-379 (dd J = 44 44 Hz 1H) 371-367 (dd J = 22 22 Hz 1H) 362-348 (m 5H) 354 (s 3H)

341-324 (m 6H) 318-313 (app t J = 87 1H) 280-265 (m 2H) 229-225 (t J = 74 Hz 2H) 216-

212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for



(S60) S59 (50 mg 94 micromol) was dissolved in water (20mL) and a catalytic amount of LiOH (2 mg) was

added The solution was then stirred at room temperature overnight neutralized with Amberlite IR-120

(H+) and filtered Purification by reverse phase HPLC [Atlantistrade dC18 column 5 microm 10 x 100 mm

Flow rate = 8 mLmin Gradient = 0 to 20 CH3CN in H2O (with 01TFA) over 40 minutes while

monitoring using a Waters 2420 ELS detector] yielded S60 (35 mg 72) as a white cottony substance

after lyophilization Retention time = 57 min 1H NMR (D2O) δ 477 (d J = 36 Hz 1H) 445-443 (d J

= 10 Hz 1H) 380-376 (dd J = 44 44 Hz 1H) 369-365 (dd J = 20 20 Hz 1H) 361-348 (m 5H)

339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38

2H) 204-200 (t J = 74 76 Hz 2H) 169-162 (m 2H) 13C NMR (D2O) δ 1824 1763 977 857

780 773 730 722 717 713 693 690 655 603 393 365 353 295 222

Conjugation of Sugar-Acids to BSA via EDC Coupling Sugar-acids were dissolved in H2O at

a final concentration of 150 mM EDC was dissolved in a 5050 mixture of DMFH2O at a final

concentration of 300 mM NHS was dissolved in DMF at a final concentration of 300 mM The NHS

ester was preformed by combining the carbohydrate EDC and NHS in an Eppendorf tube at a ratio of

211 and allowing the reaction to stand at room temperature with occasional gentle mixing After 1 hr

the reaction mixture was added to a solution of BSA (4 mgmL in 10 mM sodium borate 90 mM NaCl

pH 80) that had been pre-cooled to 4 degC to give a final ratio of carbohydrate to BSA of approximately

501 After 15 minutes the solution was warmed to room temperature and allowed to stand for 1 h

BSA-conjugates were then dialyzed extensively against water (SpectraPor 7 MWCO = 10000) BSA

conjugates were analysis by MALDI-TOF MS and the extent of conjugation was determined by

subtracting the average mass of BSA (66431) from the average mass of the BSA-conjugate and then

dividing by the molecular weight of the sugar-acid (minus 18) If necessary the ratio of acid to BSA was

altered to obtain a final ratio of sugarBSA between 161 and 241

Fabrication of the Microarrays

Glass microscope slides containing 16 wells and an epoxide modified surface (Nalge Nunc

International Rochester NY) were used to fabricate the microarrays An entire array was printed in each

well Printing was carried out at KamTek (Gaithersburg MD) Briefly samples (05 mgml with 5

glycerol in PBS buffer pH 72) were distributed in a 384 well plate (15 microLwell) and placed in the

chamber of the robotic microarray printer (Virtek CWP with a 48 pin head) Quill pins were dipped into

the samples (55 s) blotted twice and then printed in duplicate in each well of the slide (02 s dwell time)

S39

Pins were washed five times prior to printing the next sample Humidity was maintained at 65 The

temperature was kept at 16-18 ordmC Printing resulted in a 13 x 12 grid of spots in each well of the slide

with a spot to spot distance of 195 microm on the X-axis and 210 microm on the Y-axis Spots were

approximately 100 microm Once printed the slides were air dried for 24 hours then stored at minus20 ordmC until

used

Lectin Binding Assay and Analysis

The binding affinities of the lectins for various epitopes were evaluated using an ELISA-like

assay The detailed description of this protocol has been published previously[1] In summary the array

printed slides were initially incubated with blocking buffer (3 BSA in PBS 200 microLwell) for two hours

The binding buffers for the lectins were prepared according to the specification sheets in 1 BSA in PBS

at pH 72 Metals such as Ca++ (01 mM) and Mn++ (001 mM) were added when necessary Serial

dilutions of the lectins were then carried out on the 2 X 8 slides and were then incubated for another two

hours The slides were washed three times with PBS and then incubated for 1 hour with streptavidin-

HRP (diluted 15000 in PBS containing 3 BSA) The slides were washed again seven times with PBS

and then incubated with 01 cyanine 3- tyramide labeling reagent in PBS containing 1 BSA 001

H2O2 (diluted from a 30 solution) 0005 Tween 20 and 001 polyvinylpyrrolidone for 10 minutes

The wells were washed with PBS one more time and the detachable solution chamber was then peeled off

from the glass slides The detached slides were incubated in PBS for five minutes placed in a 50 mL

conical tube and then spin-dried in an Eppendorf 5810R centrifuge at 900 g for 5 min The slides were

scanned on a GenePix scanner (GenePix 4000B Microarray Scanner Molecular Devices Corporation

Union City CA) The fluorescence was quantified by using GenePix Pro 60 software with a GenePix

Array List file The mean values minus the background (typically around 200) for each of the two spots

for a particular sample were averaged The detection limit (DL) or the titer of a lectin for a particular

S40

epitope was defined as the lowest lectin concentration that gave a fluorescent signal of at least 1000 (~5

times the background fluorescence)

The unusual binding of RCA120 and BPL to the rha-α RCA120 and SNA to HSA and ACL to

Manβ4 was confirmed by ELISA with the pure BSA-conjugates ELISA results were consistent with the

microarray results indicating that binding was not an artifact or a result of mis-printing Further evidence

of recognition is in the next section

Lectin Inhibition assay

L-Rhamnose monohydrate (L-Rha) methyl-β-D-glucopyranoside (Glc-β) methyl-α-D-

galactopyranoside (Gal-α) and N-acetyl-D-galactosamine (GalNAc) and HSA were purchased from

Sigma Aldrich (Milwaukee WI)

Inhibition assays were performed for RCA120 BPL SNA and ACL on 96-well plates using the

biotinylated lectin conjugates For RCA120 lactose-BSA (50 ng well) was immobilized in wells of the

plate overnight at 4 ordmC T-BSA was immobilized for BPL while LSTc-BSA was used for SNA and Lex-

BSA was used for ACL The wells were then blocked with 200 microl of 3 BSA in PBS for two hours For

the inhibition studies RCA120 was used at 83 nM while BPL at 10 nM SNA at 133 nM and ACL at

14 microM The lectin incubation conditions were identical to the ELISA conditions and according to the

specification sheet in 03 BSA in PBS buffer Briefly in a separate BSA-blocked culture-treated plate

the lectins were incubated with various dilutions of the inhibitor for a total volume of 50 microl for two

hours Serial dilutions of the inhibitory free sugars L-Rha Glc-β Gal-α and GalNAc started at 1 M

Serial dilutions of HSA started at 76 microM and the BSA conjugates started around 7 microM After two hours of

incubation the solution was transferred to the ligand immobilized 96-well plate The plate was then

allowed to incubate for another two hours The wells were then washed three times with PBS buffer (200

microL) and were incubated with 11000 dilution of streptavidin-alkaline phosphatase (50 microL) for an hour

The wells were then washed again with PBS (200 microL) seven times and were incubated with 50 microL of 100

S41

microM methyl umbelliferryl phosphate in tris buffer at pH 90 After five minutes of incubation the plate

was then read using an FLX800 plate reader The fluorescence intensity was then normalized and curve

fitted with the logarithmic values of the concentrations using Origin 75 From the curve an IC50 value

was extrapolated

Table S1 Results from the Inhibition Assays

RCA120 (83 nM) BPL (10 nM) SNA (133 nM) ACL (14 microM) Epitope IC50 (mM) Epitope IC50 (mM) Epitope IC50 (mM) Epitope IC50 (mM)

L-Rha 168 L-Rha 119 BgB-BSA None Lex-BSA 0000012 Glc-β 110 galNAc 0195 T-BSA 000225 Glc-β-BSA None HSA 00018 Glc-β 62 Glc-β-BSA None Man4-BSA None Gal-α 132 LSTc-BSA 0000224 GalNAc 51 HSA 000763

References

[1] J Manimala Z Li A Jain S VedBrat J C Gildersleeve ChemBioChem 2005 6 2229

[2] R Roy E Katzenellenbogen H J Jennings Can J Chem 1984 62 270

[3] A M Wu FEBS Lett 2004 562 51

[4] R Paruszewski R Matusiak G Rostafinska-Suchar S Gumulka P Krzascik Pol J Chem

1987 61 127

[5] B Lou G V Reddy H Wang S Hanessian in Preparative Carbohydrate Chemistry (Ed S

Hanessian) Marcel Dekker Inc New York 1997 pp 389

[6] S Rio J-M Beau J C Jacquinet Carbohydr Res 1991 219 71

[7] A Marra J Esnault A Veyrieres P Sinay J Am Chem Soc 1992 114 6354

[8] M Christensen M Meldal K Bock J Klaus J Chem Soc Perkin Trans 1 1993 13 1453

[9] Z Szurmai L Janossy Carbohydr Res 1996 296 279

S42

[10] J S Debenham S D Debenham B Fraser-Reid Bioorg Med Chem 1996 4 1909

S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

High-Throughput Carbohydrate Microarray Analysis of 24 Lectins

Joseph C Manimala Timothy A Roach Zhitao Li and Jeffrey C Gildersleeve

Laboratory of Medicinal Chemistry National Cancer Institute 376 Boyles St Bldg 376 Rm 109

Frederick MD 21702

S1


























S2


























S3

















S4


OAcO

AcONHAc

OAc

OAcO

R1O

R1ONHAc

S

OR1

S2S3 R1 = Ac R2 = Me S4 R1 = H R2 = H

NH

OR2

O OHS

NH

OMe

O O

S1















(CDCl3) δ 1739 1728 1709 1708 1706 1704 845 749 716 671 619 518 495 384 355

333 303 235 211 209 208





S5








S6

O

OAc OAcOAc


NH

OR2

O OHSNH

OMe

O O

S1Br

O

OR1 OR1OR1

S












(CDCl3) δ 1734 1720 1704 1699 1697 833 733 720 702 670 514 388 352 330 300









S7


(d J = 68 Hz 1H) 13C NMR (D2O) δ 1738 859 749 747 717 696 506 394 345 325 290












1777 1758 856 748 739 713 692 392 347 327 292 205 156 HRMS calcd for

C13H24NO7NS 3381273 [M+H]+ found 3381272

S8

O

OH OHOH

S9 S10 R1 = Me S11 R1 = H

HSNH

OMe

O O

S1O N

MeO

NH

OR1

O O

O

OH OHOH

S












found 3521423










S9


1778 1758 860 715 701 675 672 388 347 327 295 206 152 HRMS calcd for

C13H24NO7S 3381273 [M+H]+ found 3381272

S10

OAcO

AcOOAc

S12

NH

OR2

O OHSNH

OMe

O O

S1 OR1O

R1O OR1

OAc


S





















186 (p 2H J = 72 Hz) 123 (d 3H J = 62 Hz)

S11













1779 1758 842 763 734 722 718 390 347 328 301 206 169 HRMS calcd for


S12

OHO

HOOH

O

OHO

HO

HOOH

S

OH

S16

NH

OR1

O O

HSNH

OMe

O O

S1

NMeO

S17 R1 = MeS18 R1 = H













344-331 (m 2H) 281-274 (m 1H) 264-257 (m 1H) 235-232 (t J = 73 2H) 222-218 (t J = 75

2H) 190-182 (m 2H) 13C NMR (D2O) δ 1762 1755 868 788 737 695 686 610 520 393

347 327 293 205






S13





(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677


S14


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69


























S2


























S3

















S4


OAcO

AcONHAc

OAc

OAcO

R1O

R1ONHAc

S

OR1

S2S3 R1 = Ac R2 = Me S4 R1 = H R2 = H

NH

OR2

O OHS

NH

OMe

O O

S1















(CDCl3) δ 1739 1728 1709 1708 1706 1704 845 749 716 671 619 518 495 384 355

333 303 235 211 209 208





S5








S6

O

OAc OAcOAc


NH

OR2

O OHSNH

OMe

O O

S1Br

O

OR1 OR1OR1

S












(CDCl3) δ 1734 1720 1704 1699 1697 833 733 720 702 670 514 388 352 330 300









S7


(d J = 68 Hz 1H) 13C NMR (D2O) δ 1738 859 749 747 717 696 506 394 345 325 290












1777 1758 856 748 739 713 692 392 347 327 292 205 156 HRMS calcd for

C13H24NO7NS 3381273 [M+H]+ found 3381272

S8

O

OH OHOH

S9 S10 R1 = Me S11 R1 = H

HSNH

OMe

O O

S1O N

MeO

NH

OR1

O O

O

OH OHOH

S












found 3521423










S9


1778 1758 860 715 701 675 672 388 347 327 295 206 152 HRMS calcd for

C13H24NO7S 3381273 [M+H]+ found 3381272

S10

OAcO

AcOOAc

S12

NH

OR2

O OHSNH

OMe

O O

S1 OR1O

R1O OR1

OAc


S





















186 (p 2H J = 72 Hz) 123 (d 3H J = 62 Hz)

S11













1779 1758 842 763 734 722 718 390 347 328 301 206 169 HRMS calcd for


S12

OHO

HOOH

O

OHO

HO

HOOH

S

OH

S16

NH

OR1

O O

HSNH

OMe

O O

S1

NMeO

S17 R1 = MeS18 R1 = H













344-331 (m 2H) 281-274 (m 1H) 264-257 (m 1H) 235-232 (t J = 73 2H) 222-218 (t J = 75

2H) 190-182 (m 2H) 13C NMR (D2O) δ 1762 1755 868 788 737 695 686 610 520 393

347 327 293 205






S13





(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677


S14


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69


























S3

















S4


OAcO

AcONHAc

OAc

OAcO

R1O

R1ONHAc

S

OR1

S2S3 R1 = Ac R2 = Me S4 R1 = H R2 = H

NH

OR2

O OHS

NH

OMe

O O

S1















(CDCl3) δ 1739 1728 1709 1708 1706 1704 845 749 716 671 619 518 495 384 355

333 303 235 211 209 208





S5








S6

O

OAc OAcOAc


NH

OR2

O OHSNH

OMe

O O

S1Br

O

OR1 OR1OR1

S












(CDCl3) δ 1734 1720 1704 1699 1697 833 733 720 702 670 514 388 352 330 300









S7


(d J = 68 Hz 1H) 13C NMR (D2O) δ 1738 859 749 747 717 696 506 394 345 325 290












1777 1758 856 748 739 713 692 392 347 327 292 205 156 HRMS calcd for

C13H24NO7NS 3381273 [M+H]+ found 3381272

S8

O

OH OHOH

S9 S10 R1 = Me S11 R1 = H

HSNH

OMe

O O

S1O N

MeO

NH

OR1

O O

O

OH OHOH

S












found 3521423










S9


1778 1758 860 715 701 675 672 388 347 327 295 206 152 HRMS calcd for

C13H24NO7S 3381273 [M+H]+ found 3381272

S10

OAcO

AcOOAc

S12

NH

OR2

O OHSNH

OMe

O O

S1 OR1O

R1O OR1

OAc


S





















186 (p 2H J = 72 Hz) 123 (d 3H J = 62 Hz)

S11













1779 1758 842 763 734 722 718 390 347 328 301 206 169 HRMS calcd for


S12

OHO

HOOH

O

OHO

HO

HOOH

S

OH

S16

NH

OR1

O O

HSNH

OMe

O O

S1

NMeO

S17 R1 = MeS18 R1 = H













344-331 (m 2H) 281-274 (m 1H) 264-257 (m 1H) 235-232 (t J = 73 2H) 222-218 (t J = 75

2H) 190-182 (m 2H) 13C NMR (D2O) δ 1762 1755 868 788 737 695 686 610 520 393

347 327 293 205






S13





(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677


S14


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

















S4


OAcO

AcONHAc

OAc

OAcO

R1O

R1ONHAc

S

OR1

S2S3 R1 = Ac R2 = Me S4 R1 = H R2 = H

NH

OR2

O OHS

NH

OMe

O O

S1















(CDCl3) δ 1739 1728 1709 1708 1706 1704 845 749 716 671 619 518 495 384 355

333 303 235 211 209 208





S5








S6

O

OAc OAcOAc


NH

OR2

O OHSNH

OMe

O O

S1Br

O

OR1 OR1OR1

S












(CDCl3) δ 1734 1720 1704 1699 1697 833 733 720 702 670 514 388 352 330 300









S7


(d J = 68 Hz 1H) 13C NMR (D2O) δ 1738 859 749 747 717 696 506 394 345 325 290












1777 1758 856 748 739 713 692 392 347 327 292 205 156 HRMS calcd for

C13H24NO7NS 3381273 [M+H]+ found 3381272

S8

O

OH OHOH

S9 S10 R1 = Me S11 R1 = H

HSNH

OMe

O O

S1O N

MeO

NH

OR1

O O

O

OH OHOH

S












found 3521423










S9


1778 1758 860 715 701 675 672 388 347 327 295 206 152 HRMS calcd for

C13H24NO7S 3381273 [M+H]+ found 3381272

S10

OAcO

AcOOAc

S12

NH

OR2

O OHSNH

OMe

O O

S1 OR1O

R1O OR1

OAc


S





















186 (p 2H J = 72 Hz) 123 (d 3H J = 62 Hz)

S11













1779 1758 842 763 734 722 718 390 347 328 301 206 169 HRMS calcd for


S12

OHO

HOOH

O

OHO

HO

HOOH

S

OH

S16

NH

OR1

O O

HSNH

OMe

O O

S1

NMeO

S17 R1 = MeS18 R1 = H













344-331 (m 2H) 281-274 (m 1H) 264-257 (m 1H) 235-232 (t J = 73 2H) 222-218 (t J = 75

2H) 190-182 (m 2H) 13C NMR (D2O) δ 1762 1755 868 788 737 695 686 610 520 393

347 327 293 205






S13





(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677


S14


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69


OAcO

AcONHAc

OAc

OAcO

R1O

R1ONHAc

S

OR1

S2S3 R1 = Ac R2 = Me S4 R1 = H R2 = H

NH

OR2

O OHS

NH

OMe

O O

S1















(CDCl3) δ 1739 1728 1709 1708 1706 1704 845 749 716 671 619 518 495 384 355

333 303 235 211 209 208





S5








S6

O

OAc OAcOAc


NH

OR2

O OHSNH

OMe

O O

S1Br

O

OR1 OR1OR1

S












(CDCl3) δ 1734 1720 1704 1699 1697 833 733 720 702 670 514 388 352 330 300









S7


(d J = 68 Hz 1H) 13C NMR (D2O) δ 1738 859 749 747 717 696 506 394 345 325 290












1777 1758 856 748 739 713 692 392 347 327 292 205 156 HRMS calcd for

C13H24NO7NS 3381273 [M+H]+ found 3381272

S8

O

OH OHOH

S9 S10 R1 = Me S11 R1 = H

HSNH

OMe

O O

S1O N

MeO

NH

OR1

O O

O

OH OHOH

S












found 3521423










S9


1778 1758 860 715 701 675 672 388 347 327 295 206 152 HRMS calcd for

C13H24NO7S 3381273 [M+H]+ found 3381272

S10

OAcO

AcOOAc

S12

NH

OR2

O OHSNH

OMe

O O

S1 OR1O

R1O OR1

OAc


S





















186 (p 2H J = 72 Hz) 123 (d 3H J = 62 Hz)

S11













1779 1758 842 763 734 722 718 390 347 328 301 206 169 HRMS calcd for


S12

OHO

HOOH

O

OHO

HO

HOOH

S

OH

S16

NH

OR1

O O

HSNH

OMe

O O

S1

NMeO

S17 R1 = MeS18 R1 = H













344-331 (m 2H) 281-274 (m 1H) 264-257 (m 1H) 235-232 (t J = 73 2H) 222-218 (t J = 75

2H) 190-182 (m 2H) 13C NMR (D2O) δ 1762 1755 868 788 737 695 686 610 520 393

347 327 293 205






S13





(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677


S14


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69








S6

O

OAc OAcOAc


NH

OR2

O OHSNH

OMe

O O

S1Br

O

OR1 OR1OR1

S












(CDCl3) δ 1734 1720 1704 1699 1697 833 733 720 702 670 514 388 352 330 300









S7


(d J = 68 Hz 1H) 13C NMR (D2O) δ 1738 859 749 747 717 696 506 394 345 325 290












1777 1758 856 748 739 713 692 392 347 327 292 205 156 HRMS calcd for

C13H24NO7NS 3381273 [M+H]+ found 3381272

S8

O

OH OHOH

S9 S10 R1 = Me S11 R1 = H

HSNH

OMe

O O

S1O N

MeO

NH

OR1

O O

O

OH OHOH

S












found 3521423










S9


1778 1758 860 715 701 675 672 388 347 327 295 206 152 HRMS calcd for

C13H24NO7S 3381273 [M+H]+ found 3381272

S10

OAcO

AcOOAc

S12

NH

OR2

O OHSNH

OMe

O O

S1 OR1O

R1O OR1

OAc


S





















186 (p 2H J = 72 Hz) 123 (d 3H J = 62 Hz)

S11













1779 1758 842 763 734 722 718 390 347 328 301 206 169 HRMS calcd for


S12

OHO

HOOH

O

OHO

HO

HOOH

S

OH

S16

NH

OR1

O O

HSNH

OMe

O O

S1

NMeO

S17 R1 = MeS18 R1 = H













344-331 (m 2H) 281-274 (m 1H) 264-257 (m 1H) 235-232 (t J = 73 2H) 222-218 (t J = 75

2H) 190-182 (m 2H) 13C NMR (D2O) δ 1762 1755 868 788 737 695 686 610 520 393

347 327 293 205






S13





(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677


S14


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

O

OAc OAcOAc


NH

OR2

O OHSNH

OMe

O O

S1Br

O

OR1 OR1OR1

S












(CDCl3) δ 1734 1720 1704 1699 1697 833 733 720 702 670 514 388 352 330 300









S7


(d J = 68 Hz 1H) 13C NMR (D2O) δ 1738 859 749 747 717 696 506 394 345 325 290












1777 1758 856 748 739 713 692 392 347 327 292 205 156 HRMS calcd for

C13H24NO7NS 3381273 [M+H]+ found 3381272

S8

O

OH OHOH

S9 S10 R1 = Me S11 R1 = H

HSNH

OMe

O O

S1O N

MeO

NH

OR1

O O

O

OH OHOH

S












found 3521423










S9


1778 1758 860 715 701 675 672 388 347 327 295 206 152 HRMS calcd for

C13H24NO7S 3381273 [M+H]+ found 3381272

S10

OAcO

AcOOAc

S12

NH

OR2

O OHSNH

OMe

O O

S1 OR1O

R1O OR1

OAc


S





















186 (p 2H J = 72 Hz) 123 (d 3H J = 62 Hz)

S11













1779 1758 842 763 734 722 718 390 347 328 301 206 169 HRMS calcd for


S12

OHO

HOOH

O

OHO

HO

HOOH

S

OH

S16

NH

OR1

O O

HSNH

OMe

O O

S1

NMeO

S17 R1 = MeS18 R1 = H













344-331 (m 2H) 281-274 (m 1H) 264-257 (m 1H) 235-232 (t J = 73 2H) 222-218 (t J = 75

2H) 190-182 (m 2H) 13C NMR (D2O) δ 1762 1755 868 788 737 695 686 610 520 393

347 327 293 205






S13





(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677


S14


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69


(d J = 68 Hz 1H) 13C NMR (D2O) δ 1738 859 749 747 717 696 506 394 345 325 290












1777 1758 856 748 739 713 692 392 347 327 292 205 156 HRMS calcd for

C13H24NO7NS 3381273 [M+H]+ found 3381272

S8

O

OH OHOH

S9 S10 R1 = Me S11 R1 = H

HSNH

OMe

O O

S1O N

MeO

NH

OR1

O O

O

OH OHOH

S












found 3521423










S9


1778 1758 860 715 701 675 672 388 347 327 295 206 152 HRMS calcd for

C13H24NO7S 3381273 [M+H]+ found 3381272

S10

OAcO

AcOOAc

S12

NH

OR2

O OHSNH

OMe

O O

S1 OR1O

R1O OR1

OAc


S





















186 (p 2H J = 72 Hz) 123 (d 3H J = 62 Hz)

S11













1779 1758 842 763 734 722 718 390 347 328 301 206 169 HRMS calcd for


S12

OHO

HOOH

O

OHO

HO

HOOH

S

OH

S16

NH

OR1

O O

HSNH

OMe

O O

S1

NMeO

S17 R1 = MeS18 R1 = H













344-331 (m 2H) 281-274 (m 1H) 264-257 (m 1H) 235-232 (t J = 73 2H) 222-218 (t J = 75

2H) 190-182 (m 2H) 13C NMR (D2O) δ 1762 1755 868 788 737 695 686 610 520 393

347 327 293 205






S13





(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677


S14


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

O

OH OHOH

S9 S10 R1 = Me S11 R1 = H

HSNH

OMe

O O

S1O N

MeO

NH

OR1

O O

O

OH OHOH

S












found 3521423










S9


1778 1758 860 715 701 675 672 388 347 327 295 206 152 HRMS calcd for

C13H24NO7S 3381273 [M+H]+ found 3381272

S10

OAcO

AcOOAc

S12

NH

OR2

O OHSNH

OMe

O O

S1 OR1O

R1O OR1

OAc


S





















186 (p 2H J = 72 Hz) 123 (d 3H J = 62 Hz)

S11













1779 1758 842 763 734 722 718 390 347 328 301 206 169 HRMS calcd for


S12

OHO

HOOH

O

OHO

HO

HOOH

S

OH

S16

NH

OR1

O O

HSNH

OMe

O O

S1

NMeO

S17 R1 = MeS18 R1 = H













344-331 (m 2H) 281-274 (m 1H) 264-257 (m 1H) 235-232 (t J = 73 2H) 222-218 (t J = 75

2H) 190-182 (m 2H) 13C NMR (D2O) δ 1762 1755 868 788 737 695 686 610 520 393

347 327 293 205






S13





(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677


S14


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69


1778 1758 860 715 701 675 672 388 347 327 295 206 152 HRMS calcd for

C13H24NO7S 3381273 [M+H]+ found 3381272

S10

OAcO

AcOOAc

S12

NH

OR2

O OHSNH

OMe

O O

S1 OR1O

R1O OR1

OAc


S





















186 (p 2H J = 72 Hz) 123 (d 3H J = 62 Hz)

S11













1779 1758 842 763 734 722 718 390 347 328 301 206 169 HRMS calcd for


S12

OHO

HOOH

O

OHO

HO

HOOH

S

OH

S16

NH

OR1

O O

HSNH

OMe

O O

S1

NMeO

S17 R1 = MeS18 R1 = H













344-331 (m 2H) 281-274 (m 1H) 264-257 (m 1H) 235-232 (t J = 73 2H) 222-218 (t J = 75

2H) 190-182 (m 2H) 13C NMR (D2O) δ 1762 1755 868 788 737 695 686 610 520 393

347 327 293 205






S13





(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677


S14


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

OAcO

AcOOAc

S12

NH

OR2

O OHSNH

OMe

O O

S1 OR1O

R1O OR1

OAc


S





















186 (p 2H J = 72 Hz) 123 (d 3H J = 62 Hz)

S11













1779 1758 842 763 734 722 718 390 347 328 301 206 169 HRMS calcd for


S12

OHO

HOOH

O

OHO

HO

HOOH

S

OH

S16

NH

OR1

O O

HSNH

OMe

O O

S1

NMeO

S17 R1 = MeS18 R1 = H













344-331 (m 2H) 281-274 (m 1H) 264-257 (m 1H) 235-232 (t J = 73 2H) 222-218 (t J = 75

2H) 190-182 (m 2H) 13C NMR (D2O) δ 1762 1755 868 788 737 695 686 610 520 393

347 327 293 205






S13





(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677


S14


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69













1779 1758 842 763 734 722 718 390 347 328 301 206 169 HRMS calcd for


S12

OHO

HOOH

O

OHO

HO

HOOH

S

OH

S16

NH

OR1

O O

HSNH

OMe

O O

S1

NMeO

S17 R1 = MeS18 R1 = H













344-331 (m 2H) 281-274 (m 1H) 264-257 (m 1H) 235-232 (t J = 73 2H) 222-218 (t J = 75

2H) 190-182 (m 2H) 13C NMR (D2O) δ 1762 1755 868 788 737 695 686 610 520 393

347 327 293 205






S13





(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677


S14


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

OHO

HOOH

O

OHO

HO

HOOH

S

OH

S16

NH

OR1

O O

HSNH

OMe

O O

S1

NMeO

S17 R1 = MeS18 R1 = H













344-331 (m 2H) 281-274 (m 1H) 264-257 (m 1H) 235-232 (t J = 73 2H) 222-218 (t J = 75

2H) 190-182 (m 2H) 13C NMR (D2O) δ 1762 1755 868 788 737 695 686 610 520 393

347 327 293 205






S13





(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677


S14


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69





(t J = 74 Hz 2H) 177-169 (m 2H) 13C NMR (D2O) δ 1779 1759 857 715 699 6901 677


S14


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69


OAcO

AcOOAc

OAc

OAcO

R1O

R1OOR1

S

OR1

S19

NH

OR2

O OHS

NH

OMe

O O

S1










= 68 Hz 1H) 367 (s 3H) 358-353 (m 1H) 346-341(m 1H) 295-290 (m 1H) 281-276 (m 1H)



839 747 716 672 669 616 514 388 352 329 304 207 205 2048 HRMS calcd for

C22H34NO12NS 5361801 [M+H]+ found 5361810







S15





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69





178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 858 788 737 695 686 610 520 393 347

327 293 205












S16


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24

OBzO

BzOBzO

OBz

S23

O

HN CCl3

+ OBzOBzO

OBz

R

OO

BzO

BzOBzO

OBz


OR1OR1O

OR1

S

OO

R1O

R1OR1O

OR1

NH

OR2

O O











= 120 64 Hz 1 H) 13C NMR (CDCl3) δ 1659 16555 16551 16540 16537 16532 16529 1335

13324 13321 1331 1329 1320 1300 1299 1298 1297 1296 1293 1291 1290 1289 12884

12877 1286 1285 1284 1282 1281 1018 860 719 717 714 702 695 688 680 673 617


S17






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69






4 H) 762-733 (m 17 H) 725-720 (m 4 H) 601 (dd J = 32 04 Hz 1 H) 586-579 (m 2 H) 568-



NMR (CDCl3) δ 1662 1658 1657 1656 1655 16541337 1336 1334 1332 1301 1300 1299

1297 1295 1292 1291 12894 12889 1287 1286 12842 12836 1031 921 7153 7145 709


10932940







803 (m 2 H) 800-798 (m 2 H) 796-794 (m 2 H) 791-789 (m 2 H) 778-775 (m 4 H) 764-721



68 Hz 1 H) 13C NMR (CDCl3) δ 1659 16551 16549 1654 1653 16522 16520 1337 13352

13349 1332 1330 13001 12997 1299 1298 12974 12965 1295 1293 1290 1289 1288

12873 12868 12865 12856 1284 1283 12822 12819 1018 944 904 728 718 713 696


12361980

S18







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69







4 H) 801-798 (m 2 H) 792-790 (m 4 H) 778-775 (m 4 H) 765-760 (m 2 H) 756-734 (m 14






13C NMR (CDCl3) δ 1745 1723 1659 1657 1656 16543 16535 16525 1651 1337 1336

1335 1334 1332 12983 12977 12969 12966 12962 12921 12919 1291 1289 1288 1287

12862 12858 12848 12845 12835 12825 1022 824 772 720 716 715 703 700 698 679


Found 12803593










S19




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69




H) 404-397 (m 2 H) 390 (m 1 H) 378-373 (m 2 H) 367-348 (m 6 H) 328 (m 2 H) 275-268


H) 13C NMR (D2O) δ 1824 1765 1033 850 750 726 720 716 708 707 686 684 666 609

385 366 354 302 224

S20


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69


HSNH

OMe

O O

S1

OBzOBzO

OBz

SPh

OH

S24S31

O

HN CCl3

+ OBzOBzO

OBz

R

O


OAcOAcO

OAcAcO

OAcOAcO

OAcAcO

OR1OR1O

R1OO

OR2OR2O

OR2OR2

SNH

OR3

O O








(CDCl3) δ 809-807 (m 2 H) 799-797 (m 2 H) 782-780 (m 2 H) 757-755 (m 3 H) 753-748 (m 3





(s 3 H) 13C NMR (CDCl3) δ1707 1700 1699 1697 16569 16564 16960 1339 1338 1335

1331 1324 1301 13004 12997 1296 1293 1291 12901 12898 1287 1285 981 865 722

S21


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69


C47H46O17NaS 9372348 Found 9372348






Found 8452239







798 (m 2 H) 784-782 (m 2 H) 766-761 (m 1 H) 757-751 (m 3 H) 746-737 (m 3 H) 728-724




NMR (CDCl3) δ 1705 1698 1696 1694 16539 16539 16535 16528 1597 1337 1333 1300

1298 1297 1288 1287 1286 1285 1283 975 948 906 772 720 697 694 690 689 685


Found 9881359





S22



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69



798 (m 2 H) 780 (m 2 H) 762 (m 1 H) 756-750 (m 3 H) 744-738 (m 3 H) 727-723 (m 2 H)

635 (m 1 H) 584-578 (m 3 H) 558 (s 1 H) 534-524 (m 3 H) 483 (d J = 12 Hz 1 H) 473 (m 1

H) 415 (dd J = 120 60 Hz 1 H) 406-396 (m 3 H) 364 (s 3 H) 367-355 (m 3 H) 301-295 (m 1



1654 1653 1337 1336 1332 12983 12979 1296 1291 1288 1287 1286 1285 1283 973

820 719 701 699 692 691 687 672 665 657 622 515 386 352 331 308 208 207 206














H) 384-379 (m 2 H) 373 (dd J = 120 16 Hz 1 H) 366-357 (m 5 H) 354-346 (m 2 H) 336-323


13C NMR (CDCl3) δ 1824 1764 994 851 726 715 712 710 705 698 669 666 656 608

387 366 354 303 223

S23

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

OAcO

AcOOAc

OAc

OAc

S19

HSNH

O CCl3

O

ORO

RORO

OR

S38 SNH

O CCl3

O


S39 R = AcS40 R = H

OO

RORO

O

SNH

O CCl3

O

Ph

S41 R = HS42 R = Ac

OHO

AcOAcO

OBz

SNH

O CCl3

O

S43

OAcO

AcOTCPN

OAc

Cl OO

AcOAcO

OBz

SNH

O CCl3

O

OAcO

AcOR

OAc


OO

R1OR1O

OR3

S

OR1O

R1OAcNH

OR1

NH

OR2

O O

S44












S24












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69












= 63 62 Hz 2H) 344-340 (m 2H) 297-291(m 1H) 281-276 (m 1H) 216 (s 3H) 207 (s 3H)


842 745 716 671 669 614 408 306 2162 2160 2073 2060 2050 HRMS calcd for












S25





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69





1374 1293 1283 1263 1065 1013 881 857 754 737 700 696 693 414 302 217 216












352-345 (m 1H) 343-335 (m 1H) 302-296 (m 1H) 281-274 (m 1H) 207 (s 6H) 191 (s 3H)

189 (s 3H) 13C NMR (CDCl3) δ 1705 1695 1540 1373 1292 1282 1261 1066 1009 879

828 734 727 697 690 662 409 293 2166 2160 2084 2083 HRMS calcd for







S26








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69








38 Hz 1H) 397-394 (t J = 62 Hz 1H) 345-340 (q 2H) 299-292 (m 2H) 275-268 (m 1H) 210


12931284 1064 881 837 762 672 669 628 411 301 216 214 208 207 HRMS calcd for
















S27



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69



3H) 191 (s 3H) 178 (s 3H) 13C NMR (CDCl3) δ 17035 17026 17024 1697 1689 1660 1635

1633 1540 1407 1404 1331 1306 1296 1293 1284 1270 1268 1066 980 878 821 761

7346 7339 707 669 661 651 635 609 517 416 279 2171 2167 2089 2065 2061 2051
















386-381 (m 2H) 353-344 (m 1H) 340-333 (m 1H) 327-319 (m 1H) 301-294 (m 1H) 252-





S28









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69









209-202 (q J = 74 72 Hz 2H)

















S29

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

366 (s 3H) 363-356 (m 1H) 354-348 (m 1H) 345-337 (m 1H) 297-290 (m 1H) 264-257 (m

1H) 240-237 (t J = 73 3H) 230-226 (t J = 73 3H) 2147 (s 3H) 2144 (s 3H) 206 (s 3H) 205


1695 1660 1331 1297 1295 1284 998 822 763 740 730 704 685 667 666 638 614

524 514 405 350 330 276 232 2070 2064 2061 2059 2056 2047 HRMS calcd for











3H) 350-347 (m 1H) 331-324 (m 3H) 276-262 (m 2H) 229-225 (t J = 74 Hz 2H) 216-212 (t


1026 858 778 760 747 737 708 696 677 609 604 525 520 393 347 327 292 205








S30


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69


433-431 (d J = 98 Hz 1H) 397-396 (d J = 28 Hz 1H) 376-371 (m 2H) 367-355 (m 7H) 350-

347 (m 1H) 332-319 (m 3H) 277-262 (m 2H) 226-222 (t J = 74 Hz 2H) 217-213 (t J = 73


858 778 760 747 737 708 696 677 609 604 525 393 347 331 292 223 207 HRMS


S31

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

OAcOAcO

OAcO

OAc

S50S51 R1 = Ac R2 = MeS52 R1 = H R2 = H

OAcO

OAcOAc

OAc HSNH

OMe

O O

OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1










(m 1 H) 366 (s 3 H) 362-359 (m 1H) 358-350 (m 1 H) 340-331 (m 1 H) 292-285 (m 1 H)


3 H) 203 (s 3 H) 202 (s 3 H) 201 (s 3 H) 199 (s 3 H) 196 (m 2 H)











S32





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69





H) 13C NMR (CDCl3) δ 1824 1764 1024 852 786 782 759 755 754 731 720 693 605


5381556

S33

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

OAcOAcO

AcOO

OAc

S53

OAcO

OAcOAc

OAcHS

NH

OMe

O O OR1OR1O

R1OO

R1O

OR1O

R1OS

R1O

NH

OR2

O OS1



















1H) 367 (s 3H) 362-360 (2bs 2H) 358-348 (m 1H) 340-332 (m 1H) 292-285 (m 1H) 276-



S34

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

anomer) δ 1736 1722 17051704 1703 1701 1696 1693 980 834 799 764 758 715 704

696 684 681 628 617 515 390 352 330 305 208 2075 2057 2051 HRMS calcd for

C34H49NO20NaS 8462461 [M+H]+ found 8462501









377-367 (d x 2 2H) 363-357 (m 3H) 353 (s 3H) 352-339 (m 4H) 331-316 (m 4H) 280-265


(D2O) δ 1763 1758 995 851 783 774 765 727 726 720 715 692 607 603 520 392 347









377-367 (d x 2 2H) 362-339 (m 8H) 331-316 (m 4H) 280-264 (2m 2H) 228-224 (t J = 73


S35

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

783 774 764 727 725 720 715 692 607 603 392 346 327 292 205 HRMS calcd for


S36

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

OAcOAcO

AcO

AcO

OAc

S57

OAcO

OAcOAc

OHS

NH

OMe

O O

S1


OR1OR1O

R1O

R1O

R1O

OR1O

R1OS

O

NH

OR2

O O

















352 (m 2H) 342-333 (m 1H) 293-286 (m 1H) 277-270 (m 1H) 239-236 (t J = 72 2H) 227-


(s 3H) 199-191 (m 2H) 13C NMR (D2O) δ 1735 1723 1705 17037 17035 17002 1694 1692

957 836 765 736 707 698 697 686 682 674 661 616 514 397 350 330 300 207

S37


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69


8462451











212 (t J = 74 Hz 2H) 178-170 (m 2H) 13C NMR (D2O) δ 1763 1758 977 857 780 773 730

722 717 713 693 690 654 603 521 392 347 327 296 205 HRMS calcd for










339-322 (m 6H) 317-311 (t J = 88 96 Hz 1H) 278-264 (m 2H) 211-207 (t J = 74 77 Hz

S38


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69


780 773 730 722 717 713 693 690 655 603 393 365 353 295 222





















S39





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69





used



















S40

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

























S41




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69




was extrapolated




References



[3] A M Wu FEBS Lett 2004 562 51


1987 61 127







S42


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69


S43

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S44

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

OH

O

HO

NH

Ac S

OH

NHO

H

OO

S4

S45

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH S

NHO

H

OO

(S8)

S46

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

NHO

H

OO

O

HO

OH

OH

SS8

S47

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

ppm (f1)

0010

2030

4050

6070

8090

O

OH

OH

OH

SNH

OH

OO

(S11)

S48

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

NHO

H

OO

O

OH

OH

OH

S

S11

S49

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

NHO

H

OO

OH

OH

OO

H

S

S15α

S50

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

NHO

H

OO

OH

OH

OO

H

S

S15α

S51

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

NHO

H

OO

OH

OH

OO

H S

S15β

S52

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

NHO

H

OO

OH

OH

OO

H S

S15β

S53

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

HO

SNH

OH

OO

(S18)

S54

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

OH

O

HO

HO

S

OH

NHO

H

OO

S18

S55

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

ppm (f1)

0050

100

O OH

OH

HO

HO

SNH

OH

OO

(S22)

S56

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

OH

O

HO

HO

S

OH

NHO

H

OO

S22

S57

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

S58

ppm (f1)

0050

100

0 100

200

300

400O

OH

OH

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

S59

ppm (f1)

050

100150

200

-500

0 500

1000

1500

2000

2500

OO

HO

H

HO

OH

OH

O

O

HO

OHS

NH

O

OH

O

S30

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

S60

ppm (f1)

0050

100

0 100

200

300

400

500

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

ppm (f1)

050

100150

200

-100

0 1000

2000

3000

4000

5000

6000

7000

SNH

O

OH

O

OH

O

OH

HO

OH

OH

O OH

O

OHS37

S61

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

ppm (f1)

0010

2030

4050

6070

8090

O OH

OH

HO

O OH

O

HO

OH

SN

HAc

NHO

H

OO

(S49)

S62

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

OO

HO

HO

OH

S

OH

O

HO

AcN

H

OH

NHO

H

OO

S49

S63

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

ppm (f1)

0050

100

0 50 100

150

200

250

300

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S64

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

ppm (f1)

050

100150

200

0 5000

OH

O

OH

HO

OH

OO

OH

HO

OH

SNH

O

OH

O

S52

S65

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

ppm (f1)

0010

2030

4050

6070

8090

OHOHO

OH

OH

OOHO

OH

OH

SNH

OO

OH

(S56)

S66

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

OH

OHO

HO

O

OH

OH

OH

OS

OH

NHO

H

OO

S56

S67

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

ppm (f1)

0010

2030

4050

6070

8090

OH

OHO

OH

OH

OH

OHO

OH

O

SNH

OO

OH

(S60)

S68

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

OH

OHO

HO

HO H

O

OH

OH

OS

O

NHO

H

OO

S60

S69

69451 weinheim, germany carbohydrate microarray analysis of 24 lectins joseph c. manimala, timothy...

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