zengwei lai,ab renwei zhang, qiang feng, and jianwei sunover anhydrous na 2 so 4, filtered and...

Supporting Information

3-Aminooxetanes: Versatile 1,3-Amphoteric Molecules

for Intermolecular Annulation Reactions

Zengwei Lai,ab Renwei Zhang,a Qiang Feng,a and Jianwei Sun a*

aDepartment of Chemistry, the Hong Kong University of Science and Technology,

Clear Water Bay, Kowloon, Hong Kong SAR, China

bState Key Laboratory of Drug Research, Shanghai Institute of Materia Medica,

Chinese Academy of Sciences, 555 Zuchongzhi Road, Shanghai 201203, China

Table of Contents

I. General Information .................................................................................... S-2

II. Substrate Preparation .................................................................................. S-3

III. [3+2] Annulation with Isothiocyanates .................................................. S-15

IV. [3+2] Annulation with Carbon Disulfide ............................................... S-22

V. [3+2] Annulation with Isocyanates .......................................................... S-28

VI. [3+2] Annulation with CO2 ....................................................................... S-34

VII. Product Structure Determination ............................................................ S-44

NMR Spectra

S-1

Electronic Supplementary Material (ESI) for Chemical Science.This journal is © The Royal Society of Chemistry 2020

I. General Information

All air or moisture sensitive reactions were conducted in oven-dried

glassware under nitrogen atmosphere using dry solvents. Flash column

chromatography was performed over silica gel (230-400 mesh) purchased

from Qindao Puke Co., China. Anhydrous dichloromethane and

tetrahydrofuran were purified by the Innovative® solvent purification system.

1H and 13C NMR spectra were collected on a Bruker AV 400 MHz NMR

spectrometer using residue solvent peaks as an internal standard (1H NMR:

CDCl3 at 7.26 ppm, acetone-d6 at 2.09 ppm, DMSO-d6 at 2.51 ppm, and CD3OD

at 3.34 ppm. 13C NMR: CDCl3 at 77.0 ppm, acetone-d6 at 206.0 ppm, DMSO-d6

at 39.8 ppm, and CD3OD at 48.8 ppm). Mass spectra were collected on an

Agilent GC/MS 5975C system, or a MALDI Micro MX mass spectrometer, or

an API QSTAR XL System.

S-2

II. Substrate Preparation

3-Aminooxatanes were synthesized according to the following procedures.

Siloxy alkynes used in this work are all known compounds.1

General Procedure A

A mixture of the oxetane (3 mmol) and the aldehyde (3.6 mmol) in MeOH (10

mL) was stirred at 50 oC overnight. The mixture was then cooled to 0 oC, to

which NaBH4 (125 mg, 3.3 mmol) was added slowly. Next, the reaction

mixture was allowed to warm to room temperature and stirred for 1 h before

it was quenched with saturated NH4Cl (10 mL). The mixture was extracted

with EtOAc (20 mL×3). The combined organic layers were washed with brine

(20 mL), dried with anhydrous Na2SO4, and concentrated in vacuo. The

residue was purified by flash column silica gel chromatography (eluent:

hexanes/EtOAc = 2:1) to afford the desired product 1.

General Procedure B

At room temperature, to a solution of oxetan-3-amine (0.7 mL, 10 mmol) and

the aldehyde or ketone (12 mmol, 1.2 equiv) in DCE (25 mL) were added

NaBH3CN (0.94 g, 15 mmol) and AcOH (0.7 mL, 12 mmol). The mixture was

stirred overnight, and an aqueous solution of NaOH (1M, 15 mL) was added

1 A. Wu, Q. Feng, H. H. Y. Sung, I. D. Williams, J. Sun, Angew. Chem., Int.

Ed., 2019, 58, 6776 – 6780.

S-3

to quench the reaction. The layers were separated, and the aqueous layer was

extracted with EtOAc (15 mL×3). The combined organic layers were dried

over anhydrous Na2SO4, filtered and concentrated under reduced pressure.

The residue was purified by silica gel column chromatography to afford the

secondary amine.

N-Benzyloxetan-3-amine (1b) was prepared as colorless oil according to the

General Procedure A (purification by flash column chromatography:

hexanes/EtOAc = 2:1).

1H NMR (400 MHz, CDCl3) δ 7.42 – 7.18 (m, 5H), 4.76 (t, J = 6.9 Hz, 2H), 4.40 (t,

J = 6.4 Hz, 2H), 4.08 – 3.91 (m, 1H), 3.73 (s, 2H), 1.90 (s, 1H).

13C NMR (100 MHz, CDCl3) δ 139.6, 128.4, 127.9, 127.1, 79.5, 53.0, 51.3.

IR (neat) 3421, 2953, 2872, 1664, 1375, 967, 848, 745, 702 cm-1.

HRMS (EI+) calcd for C10H14NO [M+H]+: 164.1075, found 164.1069.

N-(4-Fluorobenzyl)oxetan-3-amine (1c) was prepared as colorless oil

according to the General Procedure A (purification by flash column

chromatography: hexanes/EtOAc = 2:1).

1H NMR (400 MHz, CDCl3) δ 7.35 – 7.21 (m, 2H), 7.06 – 7.00 (m, 2H), 4.80 (t, J

= 6.9 Hz, 2H), 4.43 (t, J = 6.4 Hz, 2H), 4.09 – 3.95 (m, 1H), 3.73 (s, 2H), 1.83 (br s,

1H).

S-4

13C NMR (100 MHz, CDCl3) δ 162.1 (d, JC-F = 244.0 Hz), 135.4, 129.7 (d, JC-F = 8.0

Hz), 115.4 (d, JC-F = 22.0 Hz), 79.6, 53.1, 50.7.

IR (neat) 3421, 2957, 2875, 1604, 1510, 1221, 968, 828 cm-1.

HRMS (EI+) calcd for C10H13FNO [M+H]+: 182.0981, found 182.0947.

N-(4-Methoxybenzyl)oxetan-3-amine (1d) was prepared as colorless oil



1H NMR (400 MHz, CDCl3) δ 7.21 (d, J = 8.5 Hz, 2H), 6.86 (d, J = 8.6 Hz, 2H),

4.76 (t, J = 6.8 Hz, 2H), 4.39 (t, J = 6.3 Hz, 2H), 4.02-3.98 (m, 1H), 3.80 (s, 3H),

3.68 (s, 2H), 1.81 (br s, 1H).

13C NMR (100 MHz, CDCl3) δ 158.8, 131.7, 129.3, 113.9, 79.7, 55.3, 53.0, 50.9.

IR (neat) 3421, 2958, 1612, 1513, 1247, 1178, 1032, 965, 820 cm-1.

HRMS (EI+) calcd for C11H16NO2 [M+H]+: 194.1181, found 194.1182.

N-(Naphthalen-1-ylmethyl)oxetan-3-amine (1e) was prepared as colorless oil




7.84 – 7.73 (m, 1H), 7.54 (m, 2H), 7.45 – 7.42 (m, 2H), 4.77 (dd, J = 6.4, 6.6 Hz,

2H), 4.40 (dd, J = 6.4, 6.6 Hz, 2H), 4.20 (s, 2H), 4.15 – 4.04 (m, 1H), 2.03 (br s,

1H).

S-5

13C NMR (100 MHz, CDCl3) δ 135.2, 133.9, 131.6, 128.8, 128.2, 126.3, 126.2,

125.8, 125.4, 123.4, 79.7, 53.5, 49.1.

IR (neat) 3441, 2952, 2869, 1637, 1460, 1263, 969, 779 cm-1.


N-(Furan-2-ylmethyl)oxetan-3-amine (1f) was prepared as brown oil



1H NMR (400 MHz, CDCl3) δ 7.34 (s, 1H), 6.29 (s, 1H), 6.13 (d, J = 2.4 Hz, 1H),

4.72 (dd, J = 6.4, 6.6 Hz, 2H), 4.29 (t, J = 6.4, 6.6 Hz, 2H), 3.99 – 3.93(m, 1H), 3.74

(s, 2H), 2.02 (s, 1H).

13C NMR (100 MHz, CDCl3) δ 153.2, 142.0, 110.3, 107.1, 79.7, 53.1, 43.9.

IR (neat) 3425, 2358, 1637, 1148, 962 cm-1.

HRMS (EI+) calcd for C8H12NO2 [M+H]+: 154.0868, found 154.0866.

N-(Thiophen-3-ylmethyl)oxetan-3-amine (1g) was prepared as brown oil



1H NMR (400 MHz, CDCl3) δ 7.28 (dd, J = 4.8, 3.0 Hz, 1H), 7.14 – 7.07 (m, 1H),

7.02 (d, J = 4.9 Hz, 1H), 4.76 (t, J = 6.8 Hz, 2H), 4.39 (t, J = 6.4 Hz, 2H), 4.10 –

3.89 (m, 1H), 3.76 (s, 2 H), 1.94 (br s, 1H).

S-6

13C NMR (100 MHz, CDCl3) δ 140.6, 127.4, 126.1, 121.8, 79.6, 53.1, 46.2.

IR (neat) 3425, 2955, 2874, 1643, 1469, 965, 785 cm-1.

HRMS (EI+) calcd for C8H12NOS [M+H]+: 170.0640, found 170.0638.

N-(Cyclohexylmethyl)oxetan-3-amine (1h) was prepared as colorless oil



1H NMR (400 MHz, CDCl3) δ 4.77 (t, J = 6.7 Hz, 2H), 4.39 (t, J = 6.2 Hz, 2H),

3.89 (m, 1H), 2.33 (d, J = 6.6 Hz, 2H), 1.72 – 1.62 (m, 6H), 1.38 – 1.28 (m, 1H),

1.26 – 1.00 (m, 3H), 0.99 – 0.69 (m, 2H).

13C NMR (100 MHz, CDCl3) δ 79.6, 53.8, 53.6, 38.2, 31.3, 26.5, 25.9.

IR (neat) 3429, 2924, 2855, 1642, 1454, 1144, 968 cm-1.

HRMS (EI+) calcd for C10H20NO [M+H]+:170.1545, found 170.1546.

N-Benzyl-3-phenyloxetan-3-amine (1i) was prepared as colorless oil



1H NMR (400 MHz, CDCl3) δ 7.52 – 7.50 (m, 2H), 7.48 – 7.44 (m, 2H), 7.38 –

7.34 (m, 5H), 7.31 – 7.26 (m, 1H), 5.02 (d, J = 6.4 Hz, 2H), 4.82 (d, J = 6.4 Hz, 2H),

3.59 (s, 2H), 2.11 (br s, 1H).

13C NMR (100 MHz, CDCl3) δ 142.0, 139.9, 128.6, 128.5, 128.1, 127.4, 127.1,

126.2, 82.4, 63.5, 47.9.

S-7

IR (neat) 3445, 2949, 2871, 2357, 1636, 1455, 980, 700 cm-1.


N-(4-Bromobenzyl)oxetan-3-amine (1j) was prepared according to the

General Procedure A.


4.76 (t, J = 6.7 Hz, 2H), 4.39 (t, J = 6.2 Hz, 2H), 4.03 – 3.90 (m, 1H), 3.68 (s, 2H).

13C NMR (100 MHz, CDCl3) δ 138.6, 131.5, 129.7, 121.0, 79.5, 53.0, 50.6.

IR (thin film) 3048, 2952, 2868, 1481, 1266, 970 cm-1.

HRMS (CI+) Calcd for C10H13BrNO [M+H]+: 242.0181, Found: 242.0187.

N-(4-(Trifluoromethyl)benzyl)oxetan-3-amine (1k) was prepared according

to the General Procedure A.


4.79 (t, J = 6.6 Hz, 2H), 4.42 (t, J = 6.0 Hz, 2H), 4.06 – 3.91 (m, 1H), 3.80 (s, 2H).

13C NMR (100 MHz, CDCl3) δ 143.8, 129.5 (q, J = 34.0 Hz), 128.3, 125.4 (q, J =

4.0 Hz), 124.1 (q, J = 271.0 Hz), 79.5, 53.1, 50.8.

IR (thin film) 3052, 2954, 2870, 1322, 1116, 970 cm-1.

HRMS (CI+) Calcd for C11H13F3NO [M+H]+: 232.0949, Found: 232.0954.

S-8

N-(Thiophen-2-ylmethyl)oxetan-3-amine (1l) was prepared according to the


1H NMR (400 MHz, CDCl3) δ 7.21 (dd, J = 5.1, 1.2 Hz, 1H), 6.93 (dd, J = 5.0, 3.5

Hz, 1H), 6.89 (dd, J = 3.3, 0.9 Hz, 1H), 4.76 (t, J = 6.9 Hz, 2H), 4.39 (t, J = 6.4 Hz,

2H), 4.08 – 3.98 (m, 1H), 3.94 (s, 2H).

13C NMR (100 MHz, CDCl3) δ 143.1, 126.7, 125.1, 124.7, 79.5, 52.9, 45.9.

IR (thin film) 3050, 2952, 2868, 1466, 1267, 969 cm-1.

HRMS (CI+) Calcd for C8H12NOS [M+H]+: 170.0636, Found: 170.0640.

N-(Pyridin-2-ylmethyl)oxetan-3-amine (1m) was prepared according to the


1H NMR (400 MHz, CDCl3) δ 8.63 – 8.45 (m, 1H), 7.62 (td, J = 7.7, 1.8 Hz, 1H),

7.35 – 7.20 (m, 1H), 7.23 – 7.03 (m, 1H), 4.73 (t, J = 6.9 Hz, 2H), 4.41 (t, J = 6.5 Hz,

2H), 4.10 – 3.91 (m, 1H), 3.84 (s, 2H), 2.34 (s, 1H)

13C NMR (100 MHz, CDCl3) δ 159.1, 149.3, 136.6, 122.2 (2C), 79.5, 53.3, 52.7.

IR (thin film) 3052, 2952, 2870, 1590, 1472, 967 cm-1.

HRMS (CI+) Calcd for C9H13N2O [M+H]+: 165.1028, Found: 165.1026.

S-9

N-Cinnamyloxetan-3-amine (1n) was prepared according to the General

Procedure A.

1H NMR (400 MHz, CDCl3) δ 7.43 – 7.27 (m, 4H), 7.27 – 7.19 (m, 1H), 6.51 (d, J

= 15.8 Hz, 1H), 6.21 (dt, J = 15.8, 6.4 Hz, 1H), 4.82 (t, J = 6.9 Hz, 2H), 4.46 (t, J =

6.5 Hz, 2H), 4.11 – 3.92 (m, 1H), 3.36 (dd, J = 6.4, 1.3 Hz, 2H).

13C NMR (100 MHz, CDCl3) δ 136.7, 131.7, 128.5, 127.6, 127.5, 126.2, 79.8, 53.1,

49.3.

IR (thin film) 3045, 2953, 2869, 1456, 1266, 968 cm-1.

HRMS (CI+) Calcd for C12H16NO [M+H]+: 190.1232, Found: 190.1233.

N-Phenethyloxetan-3-amine (1o) was prepared according to the General

Procedure B.


= 6.8 Hz, 2H), 4.37 (t, J = 6.4 Hz, 2H), 4.03 – 3.85 (m, 1H), 2.91 – 2.61 (m, 4H).

13C NMR (100 MHz, CDCl3) δ 139.3, 128.43, 128.39, 126.2, 79.4, 53.3, 48.1, 36.4.

IR (thin film) 3047, 2950, 2868, 1459, 1267, 969 cm-1.


N-Cyclohexyloxetan-3-amine (1p) was prepared according to the General

Procedure B.


4.13 – 3.93 (m, 1H), 2.47 – 2.31 (m, 1H), 1.81 – 1.63 (m, 4H), 1.61 – 1.55 (m, 1H),

S-10

1.33 – 1.10 (m, 3H), 1.08 – 0.89 (m, 2H).

13C NMR (100 MHz, CDCl3) δ 80.8, 55.6, 51.5, 34.0, 25.8, 24.9.

IR (thin film) 2928, 2857, 1453, 1266, 969 cm-1.


N-Benzyl-3-(2-((tert-butyldimethylsilyl)oxy)ethyl)oxetan-3-amine (1q). A

miture of S1q (1.4 g, 10 mmol, 1.0 equiv) and BnNH2 (1.2 mL, 11 mmol, 1.1

equiv) was stirred (without solvent) at 60 oC for 3 h to afford S2q. Next, dry

THF (20 mL) was added to dissolve the crude S2q. The mixture was cooled to

0 oC and LiAlH4 (312 mg, 8 mmol, 0.8 equiv) was added in portions. Then the

mixture was allowed to stir at room temperature for 1.5 h before

Na2SO4•10H2O was added to quench the reaction. The mixture was filtered

and washed with EtOAc (10 mL×3). The filtrate was concentrated under

reduced pressure. The residue was dissolved in DCM (20 mL), to which

imidazole (817 mg, 12 mmol, 1.2 equiv) was added. The mixture was cooled to

0 oC, and TBSCl (1.3 g, 8.8 mmol, 0.88 equiv) was added in portions. The

reaction mixture was stirred overnight at room temperature, and then water

(30 mL) was added to quench the reaction. The layers were separated, and the

aqueous layer was extracted with DCM (15 mL×3). The combined organic

layers were dried over anhydrous Na2SO4, and concentrated under reduced

pressure. The residue was purified by silica gel column chromatography

(eluent: 20% Et2O in hexanes) to afford the pure 1q as a pale yellow oil (2.1 g,

65% for 3 steps).


= 6.5 Hz, 2H), 4.53 (d, J = 6.6 Hz, 2H), 3.87 – 3.72 (m, 4H), 2.15 (t, J = 6.2 Hz,

2H), 0.86 (s, 9H), 0.04 (s, 6H).

S-11

13C NMR (100 MHz, CDCl3) δ 140.3, 128.5, 128.1, 127.1, 81.6, 59.7, 59.3, 47.3,

38.0, 25.9, 18.2, –5.5.

IR (thin film) 3055, 2938, 2862, 1464, 1258, 1092 cm-1.

HRMS (CI+) Calcd for C18H32NO2Si [M+H]+: 322.2202, Found: 322.2210.

N,N'-(1,3-Phenylenebis(methylene))bis(oxetan-3-amine) (1r) was prepared

according to the General Procedure A.

1H NMR (400 MHz, CDCl3) δ 7.35 – 7.22 (m, 2H), 7.17 (d, J = 7.5 Hz, 2H), 4.75

(t, J = 6.8 Hz, 4H), 4.39 (t, J = 6.3 Hz, 4H), 4.07 – 3.88 (m, 2H), 3.70 (s, 4H).

13C NMR (100 MHz, CDCl3) δ 139.9, 128.7, 127.8, 127.0, 79.6, 53.1, 51.2.

IR (thin film) 3045, 2948, 2865, 1471, 1172, 966 cm-1.

HRMS (CI+) Calcd for C14H21N2O2 [M+H]+: 249.1603, Found: 249.1600.

N-Butyloxetan-3-amine (1s) was prepared according to the General

Procedure B.


4.01 – 3.91 (m, 1H), 2.56 (t, J = 8.0 Hz, 2H), 1.49 – 1.42 (m, 2H), 1.41 – 1.29 (m,

2H), 0.92 (t, J = 7.2 Hz, 3H).

13C NMR (100 MHz, CDCl3) δ 79.8, 53.5, 46.8, 32.4, 20.3, 13.9.

IR (thin film) 2956, 2870, 2330, 1465, 1131, 964 cm-1.

HRMS (CI+) Calcd for C13H16NO3 [M+H]+: 130.1232, Found:130.1236.

S-12

(R)-N-(1-Phenylethyl)oxetan-3-amine (1t) was prepared according to the



= 6.7 Hz, 1H), 4.51 (t, J = 6.8 Hz, 1H), 4.44 (t, J = 6.3 Hz, 1H), 4.20 (t, J = 6.4 Hz,

1H), 3.87 (p, J = 6.7 Hz, 1H), 3.72 (q, J = 6.6 Hz, 1H), 1.80 (s, 1H), 1.37 (d, J = 6.6

Hz, 3H).

13C NMR (100 MHz, CDCl3) δ 144.8, 128.5, 127.2, 126.4, 80.1, 80.0, 56.5, 51.8,

23.8.

IR (thin film) 3029, 2963, 2869, 1265, 970 cm-1.


2-(4-(Oxetan-3-ylamino)butyl)isoindoline-1,3-dione (1u). A 100-mL flask was

charged with S1u (2.2 g, 7.8 mmol, 1.3 equiv), K2CO3 (1.7 g, 12 mmol, 2.0

equiv) and KI (2.0 g, 12 mmol, 2.0 equiv), to which MeCN (30 mL) and

oxetan-3-amine (0.42 mL, 6.0 mmol, 1.0 equiv) were sequentially added. The

mixture was stirred at 80 oC for 24 h, and then water (30 mL) was added. The

mixture was extracted with EtOAc (20 mL×3). The combined organic layers

were dried over anhydrous Na2SO4, and concentrated under reduced pressure.

The residue was purified by silica gel column chromatography (eluent: 5%

MeOH in DCM) to afford pure 1u as a pale yellow solid (612 mg, 37%).

S-13


= 6.7 Hz, 2H), 4.37 (t, J = 6.2 Hz, 2H), 3.90 (p, J = 6.4 Hz, 1H), 3.66 (t, J = 7.1 Hz,

2H), 2.55 (t, J = 7.2 Hz, 2H), 1.74 – 1.64 (m, 2H), 1.54 – 1.38 (m, 2H).

13C NMR (100 MHz, CDCl3) δ 168.3, 133.8, 131.9, 123.1, 79.6, 53.4, 46.4, 37.5,

27.4, 26.2.

IR (thin film) 3055, 2946, 2867, 1707, 1440, 1267, 969 cm-1.


Oxetane 1v is a known compound. It was prepared according to literature

procedure.2

2 B. O. Beasley, A. Alli-Balogun, G. J. Clarkson, M. Shipman, Tetrahedron

Lett., 2014, 55, 541–543.

S-14

III. [3+2] Annulation with Isothiocyanates

General Procedure C

To a stirred solution of 3-aminooxetane (0.3 mmol) in DCM (3 mL) was added

isothiocyanate (0.33 mmol) at room temperature. The reaction was stirred for

~3 h at the same temperature before it was concentrated under reduced

pressure and purified by silica gel flash chromatography to afford the desired

product.

(Z)-(3-Benzyl-2-(phenylimino)thiazolidin-4-yl)methanol (3a) was prepared

as colorless oil according to the General Procedure C (purification by flash

column chromatography: hexanes/EtOAc = 3:1, 86.7 mg, 97% yield).


= 15.5 Hz, 1H), 4.56 (d, J = 15.5 Hz, 1H), 4.05 – 3.72 (m, 3H), 3.67 (dd, J = 11.6,

3.5 Hz, 1H), 3.26 (dd, J = 12.0, 8.0 Hz, 1H), 3.20 (dd, J = 11.2, 9.4 Hz, 1H).

13C NMR (100 MHz, CDCl3) δ 161.3, 149.7, 137.0, 128.9, 128.82, 127.8, 127.7,

123.9, 122.5, 62.4, 60.9, 49.1, 29.0.

IR (neat) 3366, 2933, 2358, 1618, 1489, 1221, 1062, 696 cm-1.

HRMS (EI+) calcd for C17H19N2OS [M+H]+: 299.1218, found 299.1216.

S-15

(Z)-(3-Benzyl-2-((2-fluorophenyl)imino)thiazolidin-4-yl)methanol (3b) was

prepared as white solid according to the General Procedure C (purification by

flash column chromatography: hexanes/EtOAc = 3:1, 93.9 mg, 99% yield).


6.94 (m, 4H), 5.15 (d, J = 15.4 Hz, 1H), 4.46 (d, J = 15.4 Hz, 1H), 3.83 – 3.76 (m,

2H), 3.62 (d, J = 8.5 Hz, 1H), 3.27 – 3.00 (m, 2H), 2.33 (br s, 1H).

13C NMR (100 MHz, CDCl3) δ 161.9, 156.2, 153.7, 139.4 (d, JC-F = 12.2 Hz), 137.2,

128.8, 127.8, 127.6, 124.2, 124.1, 115.8 (d, JC-F = 20.2 Hz), 62.1, 60.9, 48.6, 28.9.

IR (neat) 3394, 2358, 1605, 1491, 1230, 1044, 750 cm-1.

HRMS (EI+) calcd for C17H18FN2OS [M+H]+: 317.1124, found 317.1110.

(Z)-(3-Benzyl-2-((3-methoxyphenyl)imino)thiazolidin-4-yl)methanol (3c)

was prepared as white solid according to the General Procedure C

(purification by flash column chromatography: hexanes/EtOAc = 3:1, 97.4 mg,

99% yield).

1H NMR (400 MHz, CDCl3) δ 7.44-7.24 (m, 5H), 7.20 (t, J = 8.0 Hz, 1H), 6.70 –

6.36 (m, 3H), 5.10 (d, J = 15.5 Hz, 1H), 4.40 (d, J = 15.5 Hz, 1H), 3.79 (s, 3H), 3.76

– 3.66 (m, 2H), 3.59 (d, J = 8.0 Hz, 1H), 3.11 (d, J = 4.9 Hz, 2H), 2.64 (br s, 1H).

13C NMR (100 MHz, CDCl3) δ 160.0, 152.8, 137.3, 129.5 (2C), 128.7, 127.6, 127.5,

114.5, 109.0, 107.7, 61.7, 60.8, 55.1, 48.5, 28.9.

S-16

IR (neat) 3382, 2942, 2358, 1582, 1481, 1273, 1043, 947, 778 cm-1.

HRMS (EI+) calcd for C18H21N2O2S [M+H]+: 329.1324, found 329.1322.

(Z)-N-(3-Benzyl-4-(hydroxymethyl)thiazolidin-2-ylidene)benzamide (3d)

was prepared as colorless oil according to the General Procedure C


92% yield).

1H NMR (400 MHz, CDCl3) δ 8.25 (d, J = 7.8 Hz, 2H), 7.49 (t, J = 7.1 Hz, 1H),

7.40 (t, J = 7.5 Hz, 2H), 7.33 – 7.29 (m, 5H), 5.51 (d, J = 15.0 Hz, 1H), 4.59 (d, J =

15.0 Hz, 1H), 3.98 – 3.87 (m, 1H), 3.83 (dd, J = 11.3, 8.6 Hz, 1H), 3.75 (dd, J =

11.6, 7.8 Hz, 1H), 3.27 – 3.10 (m, 2H).

13C NMR (100 MHz, CDCl3) δ 176.1, 172.7, 136.5, 136.4, 132.0, 129.6, 128.9,

128.0, 128.0, 127.8, 60.8, 60.6, 45.0, 29.6.

IR (neat) 3701, 2924, 1566, 1402, 1318, 1063, 720 cm-1.


(Z)-(3-Benzyl-2-(benzylimino)thiazolidin-4-yl)methanol (3e) was prepared

as colorless oil according to the General Procedure C (purification by flash


S-17

1H NMR (400 MHz, CDCl3) δ 7.47 – 7.10 (m, 10H), 5.08 (d, J = 15.5 Hz, 1H),

4.61 – 4.41 (m, 2H), 4.31 (d, J = 15.5 Hz, 1H), 3.72 – 3.57 (m, 2H), 3.49 (dd, J =

10.7, 2.5 Hz, 1H), 3.35 (br s, 1H), 3.25 – 3.04 (m, 2H).

13C NMR (100 MHz, CDCl3) δ 160.4, 140.9, 137.7, 128.6, 128.1, 127.6, 127.4,

127.3, 126.4, 61.5, 60.5, 58.2, 48.5, 28.9.

IR (neat) 3407, 2358, 1622, 1522, 1445, 1043, 699 cm-1.

HRMS (EI+) calcd for C18H20N2OS [M]+: 312.1296, found 312.1293.

(Z)-(3-(Naphthalen-1-ylmethyl)-2-(phenylimino)thiazolidin-4-yl)methanol

(3f) was prepared as white solid according to the General Procedure C


98% yield).


7.83 (d, J = 7.9 Hz, 1H), 7.63 – 7.48 (m, 2H), 7.48 – 7.37 (m, 2H), 7.33 (t, J = 7.7

Hz, 2H), 7.15 – 6.97 (m, 3H), 5.68 (d, J = 15.3 Hz, 1H), 4.67 (d, J = 15.3 Hz, 1H),

3.71 – 3.43 (m, 3H), 3.03 (br s, 1H), 2.94 (d, J = 4.5 Hz, 2H).

13C NMR (100 MHz, CDCl3) δ 159.2, 151.6, 133.8, 132.5, 131.5, 128.9, 128.7,

128.5, 126.5, 126.4, 126.0, 125.1, 123.7, 123.3, 122.2, 60.8, 60.5, 46.9, 28.8.

IR (neat) 3394, 2357, 1616, 1482, 1209, 1057, 778 cm-1.


S-18

(Z)-(3-(Furan-2-ylmethyl)-2-(phenylimino)thiazolidin-4-yl)methanol (3g)



99% yield).

1H NMR (400 MHz, CDCl3) δ 7.40 (s, 1H), 7.31 (t, J = 7.7 Hz, 2H), 7.08 (t, J = 7.3

Hz, 1H), 6.98 (d, J = 8.1 Hz, 2H), 6.38 (s, 2H), 5.04 (d, J = 15.8 Hz, 1H), 4.44 (d, J

= 15.8 Hz, 1H), 3.93 – 3.76 (m, 2H), 3.70 (dd, J = 10.9, 2.9 Hz, 1H), 3.31 – 3.07 (m,

2H), 2.99 (br s, 1H).

13C NMR (100 MHz, CDCl3) δ 159.8, 151.4, 150.6, 142.1, 128.8, 123.3, 122.0,

110.5, 108.7, 62.0, 60.8, 41.5, 28.8.

IR (neat) 3390, 2358, 1618, 1490, 1215, 1062, 739 cm-1.


(Z)-(2-(Phenylimino)-3-(thiophen-3-ylmethyl)thiazolidin-4-yl)methanol (3h)



99% yield).

1H NMR (400 MHz, CDCl3) δ 7.31 (dd, J = 10.0, 5.2 Hz, 3H), 7.19 (s, 1H), 7.12

(d, J = 4.9 Hz, 1H), 7.08 (t, J = 7.3 Hz, 1H), 6.99 (d, J = 7.9 Hz, 2H), 5.05 (d, J =

S-19

15.4 Hz, 1H), 4.38 (d, J = 15.4 Hz, 1H), 3.71 – 3.68 (m, 2H), 3.60 – 3.56 (m, 1H),

3.10 – 3.02 (m, 3H).

13C NMR (100 MHz, CDCl3) δ 160.1, 151.4, 137.9, 128.8, 127.5, 126.3, 123.3,

122.6, 122.1, 61.7, 60.8, 43.8, 28.8.

IR (neat) 3379, 2937, 2358, 1616, 1437, 1215, 1058, 771 cm-1.

HRMS (EI+) calcd for C15H17N2OS2 [M+H]+: 305.0782, found 305.0789.

(Z)-(3-(Cyclohexylmethyl)-2-(phenylimino)thiazolidin-4-yl)methanol (3i)

was prepared as white solid according to the General Procedure C


99% yield).


6.93 (d, J = 8.1 Hz, 2H), 3.86 – 3.77 (m, 2H), 3.75 – 3.60 (m, 2H), 3.27 (br s, 1H),

3.21 (dd, J = 10.9, 7.1 Hz, 1H), 3.11 (dd, J = 11.0, 3.1 Hz, 1H), 2.91 (dd, J = 13.9,

6.4 Hz, 1H), 1.79 – 1.72 (m, 6H), 1.32 – 1.16 (m, 3H), 1.07 – 0.98(m, 2H).

13C NMR (100 MHz, CDCl3) δ 159.5, 151.9, 128.8, 123.1, 122.2, 62.6, 60.4, 50.8,

36.1, 30.9, 30.5, 29.1, 26.4, 25.9, 25.8.

IR (neat) 3382, 2924, 2358, 1617, 1446, 1217, 1058, 770, 695 cm-1.


S-20

(Z)-N-(3-Benzyl-4-(hydroxymethyl)-4-phenylthiazolidin-2-ylidene)benzami

de (3j) was prepared as colorless oil according to the General Procedure C


90% yield).

1H NMR (400 MHz, CDCl3) δ 8.34 (d, J = 7.7 Hz, 2H), 7.67 – 7.32 (m, 11H), 7.29

(d, J = 6.2 Hz, 2H), 5.89 (d, J = 15.3 Hz, 1H), 4.09 – 3.99 (m, 3H), 3.88 (d, J = 11.3

Hz, 1H), 3.13 (d, J = 11.3 Hz, 1H), 1.71 (br s, 1H).

13C NMR (100 MHz, CDCl3) δ 176.1, 174.9, 139.3, 138.0, 136.6, 132.0, 129.7,

129.3 (2C), 128.6, 128.2, 128.1, 127.6, 125.9, 73.0, 63.5, 49.2, 37.8.

IR (neat) 3442, 2361, 1632, 1507, 1391, 1070, 783 cm-1.


S-21

IV. [3+2] Annulation with Carbon Disulfide

General Procedure D

To a stirred solution of the 3-aminooxetane (0.4 mmol) in DCM (2 mL) was

added CS2 (0.6 mmol) at room temperature. The reaction mixture was

continued to stir for 36 h at room temperature and it was concentrated under

reduced pressure and purified by silica gel chromatography to afford the

desired product.

4-(Hydroxymethyl)thiazolidine-2-thione (4a) was prepared as colorless oil

according to the General Procedure D (purification by flash column

chromatography: hexanes/EtOAc = 2:1, 57.4 mg, 97% yield).

1H NMR (400 MHz, MeOD) δ 4.35 – 4.28 (m, 1H), 3.73 – 3.59 (m, 3H), 3.42 (dd,

J = 11.3, 6.1 Hz, 1H).

13C NMR (100 MHz, MeOD) δ 202.3, 66.8, 62.9, 35.6.

IR (neat) 3419, 1633, 1498, 1294, 1048, 982, 782 cm-1.

HRMS (EI+) calcd for C4H8NOS2 [M+H]+: 150.0047, found 150.0040.

S-22

3-Benzyl-4-(hydroxymethyl)thiazolidine-2-thione (4b) was prepared as

colorless oil according to the General Procedure D (purification by flash



(d, J = 15.1 Hz, 1H), 4.23 – 4.17 (m, 1H), 3.88 – 3.83 (m, 1H), 3.74 – 3.70 (m, 1H),

3.37 – 3.32 (m, 1H), 3.27 – 3.23 (m, 1H), 2.76 (br s, 1H).

13C NMR (100 MHz, CDCl3) δ 198.0, 135.1, 128.9, 128.1, 127.7, 67.5, 60.48, 50.9,

29.9.

IR (neat) 3337, 2941, 1450, 1302, 1225, 1029, 913, 700 cm-1.


3-(4-Fluorobenzyl)-4-(hydroxymethyl)thiazolidine-2-thione (4c) was

prepared as white solid according to the General Procedure D (purification by


1H NMR (400 MHz, CDCl3) δ 7.32 (dd, J = 8.0, 5.5 Hz, 2H), 7.03 (t, J = 8.5 Hz,

2H), 5.63 (d, J = 15.0 Hz, 1H), 4.49 (d, J = 15.0 Hz, 1H), 4.21 (dd, J = 8.6, 4.5 Hz,

1H), 3.87 (dd, J = 11.5, 5.5 Hz, 1H), 3.76 (dd, J = 11.5, 4.2 Hz, 1H), 3.46 – 3.31 (m,

1H), 3.25 (dd, J = 11.3, 4.4 Hz, 1H), 2.43 (br s, 1H).

13C NMR (100 MHz, CDCl3) δ 198.14, 162.4 (d, JC-F = 245.7 Hz), 131.0 (d, JC-F =

3.2 Hz), 129.7 (d, JC-F = 8.1 Hz), 115.8 (d, JC-F = 21.5 Hz), 67.44, 60.77, 50.29, 29.93.

S-23

IR (neat) 3393, 2933, 1604, 1509, 1462, 1223, 1160, 1037, 833 cm-1.

HRMS (EI+) calcd for C11H13FNOS2 [M+H]+: 258.0423, found 258.0418.

4-(Hydroxymethyl)-3-(4-methoxybenzyl)thiazolidine-2-thione (4d) was




5.60 (d, J = 14.8 Hz, 1H), 4.44 (d, J = 14.8 Hz, 1H), 4.23 – 4.20 (m, 1H), 3.88 (dd, J

= 11.5, 5.5 Hz, 1H), 3.79 (s, 3H), 3.74 (dd, J = 11.6, 3.6 Hz, 1H), 3.40 – 3.30 (m,

1H), 3.26 (dd, J = 11.2, 4.3 Hz, 1H), 2.72 (br s, 1H).

13C NMR (100 MHz, CDCl3) δ 197.6, 159.3, 129.2, 127.1, 114.2, 67.4, 60.4, 55.2,

50.4, 29.8.

IR (neat) 3419, 2933, 1612, 1522, 1462, 1299, 1248, 1176, 1030, 921, 733 cm-1.

HRMS (EI+) calcd for C12H15NO2S2 [M]+: 269.0544, found 269.0536.

4-(Hydroxymethyl)-3-(naphthalen-1-ylmethyl)thiazolidine-2-thione (4e)

was prepared as white solid according to the General Procedure D


58% yield).

1H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 8.1 Hz, 1H), 7.93 – 7.79 (m, 2H), 7.63 –

7.42 (m, 4H), 6.22 (d, J = 15.2 Hz, 1H), 4.76 (d, J = 15.2 Hz, 1H), 4.01 (dd, J = 6.8,

S-24

4.4 Hz, 1H), 3.93 – 3.69 (m, 2H), 3.26 (dd, J = 11.3, 8.4 Hz, 1H), 3.11 (dd, J = 11.4,

2.1 Hz, 1H), 1.98 (s, 1H).

13C NMR (100 MHz, CDCl3) δ 197.0, 133.9, 131.4, 130.8, 129.3, 128.8, 127.4,

127.2, 126.4, 125.3, 123.5, 66.8, 60.8, 50.1, 30.0.

IR (neat) 3684, 1845, 1693, 1456, 1296, 1178, 1052, 782 cm-1.

HRMS (EI+) calcd for C15H15NOS2 [M]+: 289.0595, found 289.0604.

3-(Furan-2-ylmethyl)-4-(hydroxymethyl)thiazolidine-2-thione (4f) was




6.37 – 6.24 (m, 1H), 5.47 (d, J = 15.5 Hz, 1H), 4.57 (d, J = 15.5 Hz, 1H), 4.32 –

4.27 (m, 1H), 3.94 (dd, J = 11.7, 5.5 Hz, 1H), 3.78 (dd, J = 11.7, 4.1 Hz, 1H), 3.37

(dd, J = 11.2, 8.6 Hz, 1H), 3.26 (dd, J = 11.2, 4.7 Hz, 1H), 2.81 (br s, 1H).

13C NMR (100 MHz, CDCl3) δ 197.7, 148.2, 142.6, 110.6, 109.9, 68.0, 60.5, 43.9,

29.8.

IR (neat) 3420, 2944, 1632, 1501, 1168, 1015, 736 cm-1.

HRMS (EI+) calcd for C9H11NO2S2 [M]+: 229.0231, found 229.0229.

S-25

4-(Hydroxymethyl)-3-(thiophen-3-ylmethyl)thiazolidine-2-thione (4g) was



1H NMR (400 MHz, CDCl3) δ 7.37 – 7.27 (m, 2H), 7.10 (dd, J = 4.8, 1.0 Hz, 1H),

5.52 (d, J = 15.0 Hz, 1H), 4.61 (d, J = 15.0 Hz, 1H), 4.27 – 4.21 (m, 1H), 3.89 (dd, J

= 11.6, 5.5 Hz, 1H), 3.75 (dd, J = 11.6, 4.2 Hz, 1H), 3.35 (dd, J = 11.2, 8.6 Hz, 1H),

3.25 (dd, J = 11.3, 4.9 Hz, 1H), 2.52 (br s, 1H).

13C NMR (100 MHz, CDCl3) δ 197.7, 135.7, 127.2, 126.9, 123.8, 67.7, 60.7, 46.3,

29.9.

IR (neat) 3358, 2939, 1461, 1244, 1172, 1055, 910, 710 cm-1.

HRMS (EI+) calcd for C9H11NOS3 [M]+: 245.0003, found 244.9995.

3-(Cyclohexylmethyl)-4-(hydroxymethyl)thiazolidine-2-thione (4h) was



1H NMR (400 MHz, CDCl3) δ 4.40-4.29 (m, 1H), 4.24 (dd, J = 13.6, 8.3 Hz, 1H),

3.84 (dd, J = 11.2, 6.6 Hz, 1H), 3.77 (dd, J = 11.3, 4.2 Hz, 1H), 3.47 (dd, J = 11.2,

8.4 Hz, 1H), 3.25 (dd, J = 11.3, 2.7 Hz, 1H), 3.03 (dd, J = 13.6, 6.8 Hz, 1H), 2.94

(br s, 1H), 1.95 – 1.77 (m, 1H), 1.65 (dd, J = 22.5, 15.0 Hz, 5H), 1.35–1.10 (m, 3H),

1.10–0.81 (m, 2H).

S-26

13C NMR (100 MHz, CDCl3) δ 196.7, 68.8, 59.9, 53.5, 36.0, 30.8, 30.2, 30.2, 26.1,

25.6, 25.5.

IR (neat) 3388, 2924, 1468, 1305, 1177, 954 cm-1.


S-27

V. [3+2] Annulation with Isocyanates

General Procedure E

At room temperature, a solution of 3-aminooxetane 1 (0.3 mmol) and

isocyanate 5 (0.3 mmol) in toluene (2 mL) was stirred for about 30 min. Next,

FeCl3 (0.48 mg, 3 μmol) was added to the solution. The reaction mixture was

then warmed to 80 oC and stirred at the same temperature for about 3 h. Upon

completion, the reaction mixture was cooled to room temperature and

concentrated under reduced pressure. The residue was purified by silica gel

flash chromatography to afford the desired product.

(Z)-(3-Benzyl-2-(phenylimino)oxazolidin-4-yl)methanol (6a) was prepared

as white solid according to the General Procedure E (purification by flash

column chromatography: hexanes/EtOAc = 2:1, 69 mg, 82% yield).

1H NMR (400 MHz, CDCl3) δ 7.43 – 7.27 (m, 7H), 7.21 (s, 1H), 7.19 (s, 1H), 7.04

(t, J = 7.2 Hz, 1H), 5.01 (d, J = 15.4 Hz, 1H), 4.38 – 4.18 (m, 3H), 3.70 – 3.50 (m,

2H), 3.39 (d, J = 12.1 Hz, 1H).

13C NMR (100 MHz, CDCl3) δ 154.7, 146.9, 136.6, 128.7, 128.6, 128.1, 127.7,

123.6, 122.4, 67.0, 59.6, 56.7, 46.5.

IR (neat) 3429, 2357, 1654, 1439, 1249, 1031, 699 cm-1.

HRMS (EI+) calcd for C17H19N2O2 [M+H]+: 283.1447, found 283.1437.

S-28

(Z)-(3-Benzyl-2-((4-chlorophenyl)imino)oxazolidin-4-yl)methanol (6b) was

prepared as white solid according to the General Procedure E (purification by

flash column chromatography: hexanes/EtOAc = 3:1→1:1, 79 mg, 83% yield).


(d, J = 8.4 Hz, 2H), 4.99 (d, J = 15.3 Hz, 1H), 4.49 – 4.27 (m, 2H), 4.21 (d, J = 15.3

Hz, 1H), 3.95 (br s, 1H), 3.75 – 3.54 (m, 2H), 3.41 (d, J = 10.5 Hz, 1H).

13C NMR (100 MHz, CDCl3) δ 154.9, 145.6, 136.3, 128.8, 128.5, 128.0, 127.8,

127.3, 124.9, 67.1, 59.6, 56.7, 46.5.

IR (neat) 3415, 2357, 2074, 1658, 1484, 1246, 1088, 706 cm-1.

HRMS (EI+) calcd for C17H18ClN2O2 [M+H]+: 317.1057, found 317.1069.

(Z)-(3-Benzyl-2-((3-methoxyphenyl)imino)oxazolidin-4-yl)methanol (6c)

was prepared as colorless oil according to the General Procedure E

(purification by flash column chromatography: hexanes/EtOAc = 2:1→1:1 , 85

mg, 91% yield).

1H NMR (400 MHz, CDCl3) δ 7.44 – 7.27 (m, 5H), 7.21 (t, J = 8.0 Hz, 1H), 6.82

(d, J = 8.0 Hz, 1H), 6.78 (s, 1H), 6.61 (d, J = 8.1 Hz, 1H), 5.00 (d, J = 15.4 Hz, 1H),

4.34 – 4.20 (m, 3H), 3.80 (br s, 1H), 3.80 (s, 3H), 3.64 – 3.57 (m, 2H), 3.39 (d, J =

12.1 Hz, 1H).

S-29

13C NMR (100 MHz, CDCl3) δ 159.9, 154.8, 148.2, 136.4, 129.1, 128.7, 128.0,

127.7, 116.2, 109.4, 108.0, 67.1, 59.6, 56.6, 55.1, 46.4.

IR (neat) 3422, 2357, 2076, 1661, 1480, 1259, 1037, 700 cm-1.


(Z)-(3-Benzyl-2-(naphthalen-1-ylimino)oxazolidin-4-yl)methanol (6d) was

prepared as yellow solid according to the General Procedure E (purification

by flash column chromatography: hexanes/EtOAc = 2:1→1:1, 91 mg, 91%

yield).


7.56 (d, J = 8.0 Hz, 1H), 7.49 – 7.35 (m, 8H), 7.29 (d, J = 4.9 Hz, 1H), 5.06 (d, J =

15.4 Hz, 1H), 4.61 (d, J = 15.3 Hz, 1H), 4.30 – 4.28 (m, 2H), 3.71 – 3.68 (m, 2H),

3.49 (d, J = 10.9 Hz, 1H), 2.58 (br s, 1H).

13C NMR (100 MHz, CDCl3) δ 154.1, 143.4, 137.1, 134.4, 129.5, 128.9, 128.0,

127.8, 127.7, 125.8, 125.6, 124.9, 124.1, 122.4, 118.0, 67.0, 60.4, 57.3, 47.4.

IR (neat) 3430, 2357, 1652, 1261, 1018, 704 cm-1.


(Z)-(3-(Furan-2-ylmethyl)-2-(phenylimino)oxazolidin-4-yl)methanol (6e)


S-30

(purification by flash column chromatography: hexanes/EtOAc = 2:1→1:1, 59

mg, 73% yield).

1H NMR (400 MHz, CDCl3) δ 7.39 (s, 1H), 7.30 (t, J = 7.7 Hz, 2H), 7.16 (d, J = 7.8

Hz, 2H), 7.03 (t, J = 7.3 Hz, 1H), 6.36 (s, 2H), 4.90 (d, J = 15.9 Hz, 1H), 4.45 –

4.24 (m, 3H), 3.84 (br s, 1H), 3.77 – 3.62 (m, 2H), 3.50 (d, J = 10.6 Hz, 1H).

13C NMR (100 MHz, CDCl3) δ 154.2, 150.1, 146.7, 142.4, 128.6, 123.5, 122.5,

110.5, 109.0, 67.0, 59.6, 57.6, 39.9.

IR (neat) 3414, 2357, 2072, 1662, 1486, 1246, 1025, 749 cm-1.


(Z)-(2-(Phenylimino)-3-(thiophen-3-ylmethyl)oxazolidin-4-yl)methanol (6f)

was prepared as brown oil according to the General Procedure E (purification

by flash column chromatography: hexanes/EtOAc = 2:1→1:1, 62 mg, 74%

yield).

1H NMR (400 MHz, CDCl3) δ 7.31 – 7.28 (m, 3H), 7.19 (s, 2H), 7.17 (s, 1H), 7.13

(d, J = 4.8 Hz, 1H), 7.03 (t, J = 7.2 Hz, 1H), 4.96 (d, J = 15.3 Hz, 1H), 4.40 – 4.14

(m, 3H), 3.75 (br s, 1H), 3.67 (dd, J = 12.3, 3.0 Hz, 1H), 3.61 (t, J = 7.6 Hz, 1H),

3.44 (dd, J = 12.3, 1.8 Hz, 1H).

13C NMR (100 MHz, CDCl3) δ 154.5, 146.5, 137.1, 128.6, 127.7, 126.6, 123.6,

123.5, 122.6, 67.1, 59.7, 56.9, 41.8.

IR (neat) 3420, 2356, 2075, 1655, 1245, 1032, 695 cm-1.


S-31

(Z)-(3-(Cyclohexylmethyl)-2-(phenylimino)oxazolidin-4-yl)methanol (6g)



76% yield).


(t, J = 7.3 Hz, 1H), 4.41 – 4.32 (m, 2H), 3.73 (d, J = 2.4 Hz, 1H), 3.68 – 3.52 (m,

2H), 3.45 (d, J = 12.2 Hz, 1H), 2.86 (dd, J = 14.3, 5.7 Hz, 1H), 1.77 – 1.68 (m, 6H),

1.28 – 1.21 (m, 3H), 1.03 (d, J = 10.1 Hz, 2H).

13C NMR (100 MHz, CDCl3) δ 154.7, 146.9, 128.5, 123.7, 122.2, 67.1, 59.8, 57.8,

48.1, 35.6, 30.9, 30.4, 26.4, 25.8, 25.7.

IR (neat) 3424, 2925, 2075, 1655, 1253, 1034, 695 cm-1.


(Z)-(3-Benzyl-4-phenyl-2-(phenylimino)oxazolidin-4-yl)methanol (6h) was

prepared as colorless oil according to the General Procedure E (purification

by flash column chromatography: hexanes/EtOAc = 3:1, 76.3 mg, 71% yield).


= 7.2 Hz, 1H), 5.21 (d, J = 15.6 Hz, 1H), 4.65 (d, J = 8.2 Hz, 1H), 4.26 (d, J = 8.2

Hz, 1H), 3.92 (AB, JAB = 12.4 Hz, 1H), 3.85 (BA, JBA = 12.0 Hz, 1H), 3.79 (d, J =

15.6 Hz, 1H).

S-32

13C NMR (100 MHz, CDCl3) δ 154.1, 147.3, 139.9, 139.1, 129.3, 129.1, 128.6,

128.5, 127.9, 127.9, 125.8, 123.6, 122.2, 74.5, 68.2, 62.2, 45.5.

IR (neat) 3393, 2358, 1664, 1486, 1242, 1056, 698 cm-1.


S-33

VI. [3+2] Annulation with CO2

General Procedure F

A 10-mL Schlenk flask was purged by evacuating and refilling with CO2

balloon for three times. A solution of 3-aminooxetane 1 (0.5 mmol) and DBU

(7.5 μL, 0.05 mmol, 10 mol%) or TBD (14 mg, 0.05 mmol, 10 mol%) in MeCN

(0.5 mL) was added to the flask. Then the reaction was stirred at 80 oC for 12 h,

and the mixture was directly purified by silica gel column chromatography to

afford the desired product 7.

3-Benzyl-4-(hydroxymethyl)oxazolidin-2-one (7a) was prepared as white

solid from 1b (98 mg) according to the General Procedure F (purification by

flash column chromatography: 5% MeOH in DCM) in 85% yield (106 mg).


– 4.20 (m, 3H), 3.83 – 3.60 (m, 2H), 3.51 (d, J = 11.8 Hz, 1H).

13C NMR (100 MHz, CDCl3) δ 159.2, 135.9, 128.9, 128.0 (2C), 64.5, 60.2, 55.7,

46.2.

IR (thin film) 3398, 3059, 2928, 1722, 1430, 1253, 1091 cm-1.

HRMS (CI+) Calcd for C11H14NO3 [M+H]+: 208.0974, Found: 208.0978.

S-34

4-(Hydroxymethyl)-3-(4-methoxybenzyl)oxazolidin-2-one (7b) was prepared

as colorless oil from 1d (116 mg) according to the General Procedure F

(purification by flash column chromatography: 3% MeOH in DCM) in 86%

yield (122 mg).


4.63 (d, J = 15.1 Hz, 1H), 4.33 – 4.22 (m, 2H), 4.19 (d, J = 15.1 Hz, 1H), 3.78 (s,

3H), 3.74 (dd, J = 11.9, 3.6 Hz, 1H), 3.71 – 3.63 (m, 1H), 3.51 (dd, J = 11.9, 2.7 Hz,

1H), 2.69 (s, 1H).

13C NMR (100 MHz, CDCl3) δ 159.3, 159.1, 129.4, 127.9, 114.2, 64.5, 60.3, 55.7,

55.2, 45.7.

IR (thin film) 3415, 3056, 2930, 1723, 1437, 1243, 1032, 729 cm-1.

HRMS (CI+) Calcd For C12H16NO4 [M+H]+: 238.1077, Found: 238.1079.

3-(4-Bromobenzyl)-4-(hydroxymethyl)oxazolidin-2-one (7c) was prepared as

colorless oil from 1j (128 mg) according to the General Procedure F


yield (146 mg).


4.65 (d, J = 15.4 Hz, 1H), 4.31 (t, J = 8.8 Hz, 1H), 4.27 – 4.14 (m, 2H), 3.83 – 3.64

(m, 2H), 3.63 – 3.45 (m, 1H), 2.90 (s, 1H).

13C NMR (100 MHz, CDCl3) δ 159.0, 135.0, 132.0, 129.8, 122.0, 64.5, 60.6, 55.8,

S-35

45.7.

IR (thin film) 3406, 3056, 2924, 1723, 1436, 1254, 1078, 728 cm-1.

HRMS (CI+) Calcd for C11H13BrNO3 [M+H]+: 286.0079, Found: 286.0084.

4-(Hydroxymethyl)-3-(4-(trifluoromethyl)benzyl)oxazolidin-2-one (7d) was

prepared as colorless oil from 1k (116 mg) according to the General Procedure

F (purification by flash column chromatography: 3% MeOH in DCM) in 92%

yield (127 mg).


4.77 (d, J = 15.6 Hz, 1H), 4.40 – 4.18 (m, 3H), 3.82 – 3.65 (m, 2H), 3.56 (dd, J =

11.7, 3.2 Hz, 1H), 2.84 (s, 1H).

13C NMR (100 MHz, CDCl3) δ 159.1, 140.1, 130.3 (q, J = 32.0 Hz), 128.3, 125.8 (q,

J = 4.0 Hz), 123.9 (q, J = 271.0 Hz), 64.6, 60.6, 55.8, 45.8.

IR (thin film) 3417, 3058, 2927, 1727, 1323, 1118, 730 cm-1.

HRMS (CI+) Calcd for C12H13F3NO3 [M+H]+: 276.0848, Found: 276.0851.

4-(Hydroxymethyl)-3-(thiophen-2-ylmethyl)oxazolidin-2-one (7e) was

prepared as colorless oil from 1l (101 mg) according to the General Procedure


yield (112 mg).

S-36


6.98 (dd, J = 5.0, 3.6 Hz, 1H), 4.88 (d, J = 15.7 Hz, 1H), 4.49 (d, J = 15.7 Hz, 1H),

4.38 – 4.13 (m, 2H), 3.89 – 3.75 (m, 2H), 3.61 (dd, J = 13.0, 4.2 Hz, 1H), 2.77 (s,

1H).

13C NMR (100 MHz, CDCl3) δ 158.7, 138.1, 127.2, 127.1, 125.9, 64.6, 60.5, 55.6,

40.9.

IR (thin film) 3431, 3058, 2926, 1729, 1433, 1260, 733 cm-1.

HRMS (CI+) Calcd for C9H12NO3S [M]+: 214.0538, Found: 214.0537.

4-(Hydroxymethyl)-3-(pyridin-2-ylmethyl)oxazolidin-2-one (7f) was

prepared as colorless oil from 1m (99 mg) according to the General Procedure


yield (114 mg).


7.37 (d, J = 7.8 Hz, 1H), 7.30 – 7.19 (m, 1H), 6.91 (s, 1H), 4.73 (d, J = 16.0 Hz, 1H),

4.39 (t, J = 8.9 Hz, 1H), 4.30 (t, J = 7.9 Hz, 1H), 4.23 (d, J = 16.0 Hz, 1H), 4.01 –

3.89 (m, 1H), 3.82 (d, J = 13.1 Hz, 1H), 3.54 (dd, J = 13.1, 3.1 Hz, 1H).

13C NMR (100 MHz, CDCl3) δ 158.6, 156.2, 148.7, 137.7, 123.3, 123.0, 64.2, 60.5,

59.7, 47.9.

IR (thin film) 3415, 3059, 2921, 1734, 1434, 1264, 1087, 910, 727 cm-1.


S-37

3-Cinnamyl-4-(hydroxymethyl)oxazolidin-2-one (7g) was prepared as

colorless oil from 1n (95 mg) according to the General Procedure F


yield (105 mg).


7.28 – 7.20 (m, 1H), 6.58 (d, J = 15.9 Hz, 1H), 6.29 – 5.97 (m, 1H), 4.35 (t, J = 8.8

Hz, 1H), 4.31 – 4.21 (m, 2H), 3.98 – 3.76 (m, 3H), 3.62 (d, J = 11.6 Hz, 1H), 3.18

(s, 1H).

13C NMR (100 MHz, CDCl3) δ 158.7, 136.0, 134.0, 128.6, 128.0, 126.5, 123.2, 64.6,

60.6, 56.0, 44.5.

IR (thin film) 3396, 3056, 2924, 1724, 1437, 1256, 1090 cm-1.


4-(Hydroxymethyl)-3-phenethyloxazolidin-2-one (7h) was prepared as

colorless oil from 1o (106 mg) according to the General Procedure F (TBD as

base, purification by flash column chromatography: 3% MeOH in DCM) in 95%

yield (126 mg).

1H NMR (400 MHz, CDCl3) δ 7.35 – 7.26 (m, 2H), 7.22 (t, J = 6.4 Hz, 3H), 4.30 –

4.18 (m, 1H), 4.18 – 4.09 (m, 1H), 3.73 – 3.56 (m, 3H), 3.49 (dd, J = 11.3, 2.8 Hz,

1H), 3.42 – 3.29 (m, 1H), 3.11 (s, 1H), 2.96 – 2.80 (m, 2H).

13C NMR (100 MHz, CDCl3) δ 158.8, 138.4, 128.7, 128.6, 126.6, 64.5, 60.8, 56.7,

43.7, 33.8.

S-38

IR (thin film) 3408, 3030, 2930, 1721, 1431, 1259, 1035 cm-1.

HRMS (CI+) Calcd for: C12H16NO3 [M+H]+: 222.1130, Found: 222.1140.

3-Cyclohexyl-4-(hydroxymethyl)oxazolidin-2-one (7i) was prepared as white

solid from 1p (93 mg) according to the General Procedure F (TBD as base,

DMF as solvent at 100 oC (purification by flash column chromatography: 3%

MeOH in DCM) in 89% yield (106 mg).


3.55 (m, 2H), 3.48 (tt, J = 12.1, 3.7 Hz, 1H), 3.18 (s, 1H), 1.89 (d, J = 11.9 Hz, 1H),

1.84 – 1.70 (m, 3H), 1.70 – 1.53 (m, 2H), 1.51 – 1.36 (m, 1H), 1.37 – 1.20 (m, 2H),

1.20 – 0.97 (m, 1H).

13C NMR (100 MHz, CDCl3) δ 158.4, 65.4, 62.7, 55.5, 54.0, 31.8, 30.0, 25.70, 25.69,

25.2.

IR (thin film) 3401, 2933, 2859, 1715, 1424, 1237, 1047 cm-1.


3-Butyl-4-(hydroxymethyl)oxazolidin-2-one (7j) was prepared as colorless oil

from 1s (90 mg) according to the General Procedure F (TBD as base,

purification by flash column chromatography: 3% MeOH in DCM) in 50%

yield (61 mg).

1H NMR (400 MHz, CDCl3) δ 4.34 (t, J = 8.8 Hz, 1H), 4.25 (dd, J = 8.7, 5.6 Hz,

1H), 3.89 – 3.83 (m, 1H), 3.79 (dd, J = 11.8, 4.1 Hz, 1H), 3.64 (dd, J = 11.8, 3.2 Hz,

S-39

1H), 3.52 – 3.40 (m, 1H), 3.13 – 3.03 (m, 1H), 1.62 – 1.45 (m, 2H), 1.37 – 1.27 (m,

2H), 0.93 (t, J = 7.3 Hz, 3H).

13C NMR (100 MHz, CDCl3) δ 158.8, 64.5, 60.8, 56.0, 41.8, 29.4, 19.9, 13.7.

IR (thin film) 3403, 2929, 2871, 1716, 1430, 1250, 1040 cm-1.

HRMS (CI+) Calcd for C8H16NO3 [M+H+]: 174.1130, Found: 174.1133.

3-Benzyl-4-(2-((tert-butyldimethylsilyl)oxy)ethyl)-4-(hydroxymethyl)oxazoli

din-2-one (7k) was prepared as white solid from 1q (128 mg) according to the

General Procedure (purification by flash column chromatography: 50%

EtOAc in hexanes) in 78% yield (114 mg).

1H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 7.2 Hz, 2H), 7.36 – 7.23 (m, 3H), 4.58

(d, J = 15.7 Hz, 1H), 4.32 (d, J = 15.7 Hz, 1H), 4.22 (q, J = 8.8 Hz, 2H), 3.62 (t, J =

5.6 Hz, 2H), 3.55 – 3.42 (m, 2H), 2.53 (t, J = 6.5 Hz, 1H), 1.91 – 1.70 (m, 2H), 0.86

(s, 9H), 0.03 (s, 6H).

13C NMR (100 MHz, CDCl3) δ 158.9, 138.3, 128.9, 127.83, 127.79, 69.3, 65.0, 64.2,

58.3, 44.6, 36.0, 25.8, 18.1, -5.67.

IR (thin film) 3424, 3060, 2934, 1723, 1416, 1066, 729 cm-1.

HRMS (CI+) Calcd for C19H32NO4Si [M+H]+: 366.2101, Found: 366.2084.

4-(Hydroxymethyl)-3-((R)-1-phenylethyl)oxazolidin-2-one (7l) was prepared

as yellow oil from 1t (89 mg) according to the General Procedure F with TBD

S-40

as catalyst and DMF as solvent at 100 oC. The product was obtained by flash

column chromatography (5% MeOH in DCM) as an inseparable mixture of

diastereomers in 83% yield (92 mg, 1.3:1 dr).

Major diastereomer:

1H NMR (400 MHz, CDCl3) δ 7.37 – 7.28 (m, 5H), 5.12 (q, J = 7.2 Hz, 1H), 4.24 –

4.13 (m, 2H), 3.61 – 3.45 (m, 2H), 3.18 – 3.17 (m, 1H), 2.84 (s, 1H), 1.67 (d, J = 7.2

Hz, 3H).

13C NMR (100 MHz, CDCl3) δ 158.7, 139.1, 128.8, 128.0, 127.2, 65.2, 62.4, 55.4,

52.7, 18.4.

Minor diastereomer:

1H NMR (400 MHz, CDCl3) δ 7.44 – 4.42 (m, 2H), 7.37 – 7.28 (m, 3H), 5.18 (q, J

= 7.2 Hz, 1H), 4.29 (t, J = 8.8 Hz, 1H), 4.24 – 4.13 (m, 1H), 3.97 – 3.87 (m, 1H),

3.61 – 3.56 (m, 1H), 3.18 – 3.17 (m, 1H), 1.75 (s, 1H), 1.64 (d, J = 7.3 Hz, 3H).

13C NMR (100 MHz, CDCl3) δ 158.9, 141.2, 128.8, 128.1, 126.7, 64.8, 61.2, 54.8,

51.1, 15.7.

IR (thin film) 3052, 2954, 2871, 1665, 1511, 1252 cm-1.


3,3'-(1,3-Phenylenebis(methylene))bis(4-(hydroxymethyl)oxazolidin-2-one)

(7m) was prepared as white solid from 1r (74 mg) according to the General

Procedure F (purification by flash column chromatography: 5% MeOH in

DCM) as an inseparable mixture of diastereomers in 71% yield (71 mg, 1.2:1

dr).

Major diastereomer:

S-41

1H NMR (400 MHz, acetone-d6) δ 7.44 – 7.36 (m, 2H), 7.32 (d, J = 7.8 Hz, 2H),

4.72 (dd, J = 15.5, 2.4 Hz, 2H), 4.43 – 4.32 (m, 3H), 4.30 (d, J = 3.5 Hz, 1H), 4.26

(s, 1H), 4.22 (dd, J = 8.6, 5.6 Hz, 2H), 3.89 – 3.71 (m, 4H), 3.61 (d, J = 9.9 Hz, 2H),

3.04 (s, 1H).

13C NMR (100 MHz, acetone-d6) δ 159.4, 138.5, 129.9, 128.4, 128.0, 65.3, 61.1,

56.7, 46.5.

IR (thin film) 3409, 3057, 2924, 1716, 1425, 1251, 1086, 727 cm-1.


2-(4-(4-(Hydroxymethyl)-2-oxooxazolidin-3-yl)butyl)isoindoline-1,3-dione

(7n) was prepared as white solid from 1u (110 mg) according to the General

Procedure F (with TBD as base). The product was obtained in 72% yield (92

mg) by direct filtration of the reaction mixture followed by washing with

DCM.

1H NMR (400 MHz, DMSO-d6) δ 8.01 – 7.70 (m, 4H), 5.11 – 4.89 (m, 1H), 4.26 (t,

J = 7.7 Hz, 1H), 4.17 – 3.98 (m, 1H), 3.85 – 3.70 (m, 1H), 3.64 – 3.53 (m, 3H), 3.34

– 3.21 (m, 1H), 3.15 – 3.01 (m, 1H), 1.72 – 1.30 (m, 4H).

13C NMR (100 MHz, DMSO-d6) δ 168.5, 158.3, 134.8, 132.1, 123.5, 64.6, 60.0,

56.0, 41.3, 37.5, 25.7, 24.7.

IR (thin film) 3360, 2938, 2869, 1708, 1393 1261,1032 cm-1.


S-42

11b-(Hydroxymethyl)-1,5,6,11b-tetrahydrooxazolo[3',4':1,2]pyrido[3,4-b]indo

l-3(11H)-one (7o) was prepared as pale yellow solid from 1v (107 mg)

according to the General Procedure F (TBD as base, DMF as solvent at 100 oC.

Purification by flash column chromatography: 5% MeOH in DCM) in 85%

yield (110 mg).

1H NMR (400 MHz, CD3OD) δ 7.37 (d, J = 7.9 Hz, 1H), 7.26 (d, J = 8.1 Hz, 1H),

7.06 (t, J = 7.6 Hz, 1H), 6.96 (t, J = 7.5 Hz, 1H), 4.68 (d, J = 8.4 Hz, 1H), 4.30 (d, J

= 8.4 Hz, 1H), 4.04 (dd, J = 13.8, 6.2 Hz, 1H), 3.82 (d, J = 12.2 Hz, 1H), 3.73 (d, J

= 12.2 Hz, 1H), 3.39 – 3.23 (m, 3H), 2.90 – 2.77 (m, 1H), 2.67 (dd, J = 15.6, 4.8 Hz,

1H).

13C NMR (100 MHz, CD3OD) δ 160.8, 138.3, 132.8, 127.9, 123.3, 120.4, 119.3,

112.4, 109.5, 71.2, 64.6, 63.8, 38.6, 21.3.

IR (thin film) 3297, 3056, 2974, 2932, 1719, 1415, 1258, 1032 cm-1.


S-43

VII. Product Structure Determination

The structures of the products 3b and 6a were determined by X-ray

crystallography. The X-ray data have been deposited at the Cambridge

Crystallographic Data Center (CCDC 1987318 for 3b; 1987319 for 6a). The

structures of other products were assumed by analogy.

Table S1. Crystal data and structure refinement for 3b.

Identification code 3b

Empirical formula C17H17FN2OS

Formula weight 316.38

Temperature/K 100.15

Crystal system triclinic

Space group P-1

a/Å 9.7070(3)

b/Å 12.3991(6)

c/Å 13.7578(6)

α/° 110.620(4)

β/° 90.804(3)

γ/° 101.885(3)

Volume/Å3 1509.77(12)

Z 4

S-44

ρcalcg/cm3 1.392

μ/mm-1 2.029

F(000) 664.0

Crystal size/mm3 0.25 × 0.22 × 0.2

Radiation CuKα (λ = 1.54184)

2Θ range for data collection/° 8.342 to 134.994

Index ranges -11 ≤ h ≤ 11, -14 ≤ k ≤ 14, -12 ≤ l ≤ 16

Reflections collected 8240

Independent reflections 5347 [Rint = 0.0147, Rsigma = 0.0198]

Data/restraints/parameters 5347/0/399

Goodness-of-fit on F2 1.023

Final R indexes [I>=2σ (I)] R1 = 0.0276, wR2 = 0.0695

Final R indexes [all data] R1 = 0.0287, wR2 = 0.0705

Largest diff. peak/hole / e Å-3 0.34/-0.21

Table S2. Fractional Atomic Coordinates (×104) and Equivalent Isotropic

Displacement Parameters (Å2×103) for 3b. Ueq is defined as 1/3 of the trace of the

orthogonalised UIJ tensor.

Atom x y z U(eq)

S1 7919.3(3) 7142.1(3) 4245.8(2) 17.77(8)

F1 4109.8(8) 5736.0(6) 2496.0(6) 24.28(17)

O1 7674.0(9) 4146.9(7) 5286.6(7) 19.63(18)

N1 5134.7(10) 6972.9(9) 4560.7(8) 16.6(2)

N2 6526.5(10) 6282.9(9) 5510.3(8) 15.2(2)

C1 6331.9(12) 6786.8(10) 4801.0(9) 14.7(2)

C3 8006.0(12) 6302.2(10) 5781.2(9) 16.7(2)

C4 8757.5(13) 6293.0(11) 4814.7(10) 19.2(2)

C5 8166.7(13) 5266.2(11) 6091.2(10) 18.6(2)

C10 5478.7(12) 6214.1(10) 6249.2(9) 15.5(2)

C11 5700.0(12) 7298.6(10) 7242.2(9) 15.2(2)

C12 6529.0(13) 8388.1(11) 7323.0(10) 18.5(2)

C13 6708.9(13) 9349.3(11) 8257.8(10) 21.7(3)

C14 6032.6(14) 9239.7(11) 9110.6(10) 22.8(3)

C15 5171.0(13) 8162.3(12) 9025.5(10) 20.9(3)

C16 5020.3(12) 7194.6(11) 8101.4(10) 17.5(2)

C21 5124.3(12) 7550.7(11) 3838.2(9) 16.7(2)

C22 4586.8(13) 6929.8(11) 2805.8(10) 18.2(2)

C23 4506.1(13) 7450.9(12) 2077.7(10) 22.8(3)

C24 4981.0(15) 8668.7(13) 2397.2(11) 26.8(3)

C25 5496.7(15) 9327.7(12) 3430.1(11) 26.5(3)

S-45

C26 5568.8(13) 8773.7(11) 4142.8(10) 22.0(3)

S1A 1895.9(3) 2853.1(3) 697.6(2) 18.76(8)

F1A -1378.5(9) 4107.5(7) 2446.4(6) 25.95(17)

O1A 3046.9(9) 5835.1(7) -364.6(7) 20.01(18)

N1A -833.9(11) 2984.0(9) 420.9(8) 17.6(2)

N2A 825.8(10) 3679.7(9) -563.4(8) 16.1(2)

C1A 437.8(13) 3180.3(10) 157.5(9) 15.5(2)

C3A 2281.0(13) 3678.9(11) -850.7(9) 17.4(2)

C4A 3113.7(13) 3702.7(11) 105.4(10) 19.8(3)

C5A 2929.1(13) 4717.3(11) -1170.5(9) 19.0(2)

C10A -247.2(13) 3714.5(10) -1301.8(9) 16.8(2)

C11A -578.0(12) 2638.2(10) -2308.2(9) 15.9(2)

C12A -339.1(13) 1545.7(11) -2376.7(10) 20.0(3)

C13A -671.5(14) 583.7(11) -3310.4(11) 23.7(3)

C14A -1267.7(14) 690.4(12) -4184.5(10) 24.3(3)

C15A -1535.5(13) 1772.3(12) -4116.8(10) 22.8(3)

C16A -1179.0(12) 2739.5(11) -3187.9(10) 18.6(2)

C21A -1077.7(12) 2375.1(11) 1122.2(9) 17.7(2)

C22A -1391.4(13) 2937.9(11) 2133.9(10) 19.0(2)

C23A -1705.9(13) 2379.7(12) 2836.2(10) 23.4(3)

C24A -1709.6(14) 1184.5(13) 2515.6(11) 27.3(3)

C25A -1414.4(15) 583.2(12) 1509.8(12) 28.1(3)

C26A -1098.8(14) 1172.8(12) 821.8(10) 22.9(3)

Table S3. Anisotropic Displacement Parameters (Å2×103) for 3b. The Anisotropic

displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].

Atom U11 U22 U33 U23 U13 U12

S1 14.74(14) 21.13(15) 20.96(15) 11.28(12) 5.19(11) 4.92(11)

F1 30.4(4) 19.0(4) 19.7(4) 5.3(3) 2.5(3) 0.5(3)

O1 15.3(4) 18.8(4) 24.9(4) 8.3(4) 3.2(3) 3.2(3)

N1 14.9(5) 17.8(5) 17.9(5) 7.8(4) 1.5(4) 3.2(4)

N2 13.2(5) 17.2(5) 15.6(5) 6.2(4) 1.7(4) 3.6(4)

C1 15.2(6) 12.2(5) 14.3(5) 2.8(4) 2.4(4) 1.4(4)

C3 12.2(5) 18.8(6) 18.5(6) 6.7(5) 0.1(4) 2.8(4)

C4 15.1(6) 22.6(6) 22.9(6) 11.0(5) 3.7(5) 5.9(5)

C5 15.4(6) 21.5(6) 20.2(6) 9.1(5) -0.1(4) 4.1(5)

C10 13.4(5) 16.4(6) 17.0(6) 7.3(5) 2.0(4) 1.8(4)

C11 13.1(5) 17.6(6) 17.5(6) 7.7(5) 1.2(4) 6.6(4)

C12 17.6(6) 19.0(6) 20.7(6) 8.8(5) 3.7(5) 5.1(5)

S-46

C13 19.2(6) 16.6(6) 27.7(7) 5.8(5) 2.7(5) 4.2(5)

C14 20.6(6) 21.9(6) 22.0(6) 1.1(5) 2.5(5) 9.0(5)

C15 18.5(6) 28.1(7) 19.5(6) 9.4(5) 6.0(5) 10.7(5)

C16 14.6(6) 19.8(6) 21.2(6) 10.2(5) 2.8(5) 5.1(5)

C21 12.0(5) 21.1(6) 20.2(6) 10.0(5) 4.2(4) 5.5(5)

C22 14.4(6) 19.1(6) 21.9(6) 8.1(5) 4.7(5) 4.2(5)

C23 19.2(6) 33.0(7) 20.6(6) 13.3(5) 4.4(5) 9.0(5)

C24 27.1(7) 33.5(7) 31.9(7) 22.2(6) 11.1(6) 14.0(6)

C25 28.8(7) 20.6(6) 35.0(8) 14.5(6) 9.8(6) 7.6(5)

C26 19.8(6) 20.9(6) 24.4(6) 7.7(5) 3.6(5) 3.8(5)

S1A 15.59(15) 23.56(16) 21.51(15) 12.58(12) 1.25(11) 6.05(11)

F1A 34.1(4) 23.4(4) 21.2(4) 6.5(3) 1.9(3) 11.1(3)

O1A 17.8(4) 19.5(4) 23.4(4) 7.5(4) 0.8(3) 6.4(3)

N1A 17.0(5) 19.9(5) 18.4(5) 8.9(4) 2.8(4) 6.1(4)

N2A 14.6(5) 19.1(5) 16.4(5) 7.7(4) 2.2(4) 5.5(4)

C1A 17.6(6) 13.8(5) 14.6(5) 3.8(4) -0.1(4) 5.1(4)

C3A 15.6(6) 19.0(6) 18.6(6) 6.7(5) 3.1(5) 6.1(5)

C4A 15.9(6) 23.7(6) 23.2(6) 12.0(5) 2.7(5) 5.3(5)

C5A 18.2(6) 21.3(6) 19.3(6) 8.3(5) 4.8(5) 6.3(5)

C10A 17.2(6) 18.5(6) 17.4(6) 8.2(5) 2.0(4) 7.1(5)

C11A 11.2(5) 18.8(6) 18.4(6) 8.2(5) 3.6(4) 2.3(4)

C12A 18.7(6) 20.6(6) 22.8(6) 10.3(5) 1.7(5) 4.4(5)

C13A 20.3(6) 17.4(6) 31.9(7) 7.8(5) 4.2(5) 3.3(5)

C14A 17.3(6) 24.0(6) 22.8(6) 0.7(5) 1.6(5) -0.4(5)

C15A 16.8(6) 30.8(7) 19.4(6) 9.0(5) 0.5(5) 2.5(5)

C16A 14.5(6) 22.2(6) 21.6(6) 10.7(5) 3.4(5) 4.5(5)

C21A 12.0(5) 22.6(6) 20.6(6) 10.6(5) 0.6(4) 3.4(5)

C22A 15.1(6) 20.6(6) 21.4(6) 7.8(5) -0.6(5) 4.5(5)

C23A 17.8(6) 34.6(7) 21.6(6) 14.3(5) 3.0(5) 6.6(5)

C24A 22.1(7) 34.3(7) 33.3(7) 23.0(6) 3.3(5) 3.9(6)

C25A 28.0(7) 22.4(7) 37.4(8) 15.8(6) 1.3(6) 4.3(5)

C26A 22.4(6) 22.0(6) 24.8(6) 8.5(5) 3.3(5) 5.8(5)

Table S4. Bond Lengths for 3b.

Atom Atom Length/Å Atom Atom Length/Å

S1 C1 1.7727(12) S1A C1A 1.7718(12)

S1 C4 1.8163(12) S1A C4A 1.8137(12)

F1 C22 1.3619(14) F1A C22A 1.3569(15)

O1 C5 1.4177(15) O1A C5A 1.4184(15)

S-47

N1 C1 1.2910(16) N1A C1A 1.2904(16)

N1 C21 1.4162(15) N1A C21A 1.4153(16)

N2 C1 1.3604(15) N2A C1A 1.3624(16)

N2 C3 1.4719(15) N2A C3A 1.4722(15)

N2 C10 1.4594(15) N2A C10A 1.4624(15)

C3 C4 1.5232(16) C3A C4A 1.5223(17)

C3 C5 1.5240(16) C3A C5A 1.5233(17)

C10 C11 1.5164(16) C10A C11A 1.5201(16)

C11 C12 1.3888(17) C11A C12A 1.3921(17)

C11 C16 1.3941(17) C11A C16A 1.3921(17)

C12 C13 1.3905(18) C12A C13A 1.3884(19)

C13 C14 1.3869(19) C13A C14A 1.387(2)

C14 C15 1.3873(19) C14A C15A 1.390(2)

C15 C16 1.3876(18) C15A C16A 1.3887(18)

C21 C22 1.3878(18) C21A C22A 1.3900(18)

C21 C26 1.3925(18) C21A C26A 1.3953(18)

C22 C23 1.3789(18) C22A C23A 1.3777(18)

C23 C24 1.388(2) C23A C24A 1.389(2)

C24 C25 1.390(2) C24A C25A 1.388(2)

C25 C26 1.3895(19) C25A C26A 1.3883(19)

Table S5. Bond Angles for 3b.

Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚

C1 S1 C4 90.70(6) C1A S1A C4A 90.78(6)

C1 N1 C21 116.85(10) C1A N1A C21A 116.63(10)

C1 N2 C3 115.34(10) C1A N2A C3A 115.10(10)

C1 N2 C10 119.91(10) C1A N2A C10A 120.09(10)

C10 N2 C3 119.75(9) C10A N2A C3A 119.58(10)

N1 C1 S1 124.50(9) N1A C1A S1A 124.36(9)

N1 C1 N2 123.92(11) N1A C1A N2A 123.95(11)

N2 C1 S1 111.58(8) N2A C1A S1A 111.69(9)

N2 C3 C4 105.19(9) N2A C3A C4A 105.44(9)

N2 C3 C5 113.29(10) N2A C3A C5A 113.05(10)

C4 C3 C5 111.39(10) C4A C3A C5A 111.47(10)

C3 C4 S1 105.90(8) C3A C4A S1A 105.97(8)

O1 C5 C3 113.66(10) O1A C5A C3A 113.50(10)

N2 C10 C11 114.48(10) N2A C10A C11A 114.41(10)

C12 C11 C10 122.79(11) C12A C11A C10A 122.50(11)

C12 C11 C16 118.99(11) C12A C11A C16A 118.68(11)

S-48

C16 C11 C10 118.21(11) C16A C11A C10A 118.79(11)

C11 C12 C13 120.30(12) C13A C12A C11A 120.48(12)

C14 C13 C12 120.42(12) C14A C13A C12A 120.57(12)

C13 C14 C15 119.53(12) C13A C14A C15A 119.29(12)

C14 C15 C16 120.07(12) C16A C15A C14A 120.08(12)

C15 C16 C11 120.65(11) C15A C16A C11A 120.87(12)

C22 C21 N1 121.34(11) C22A C21A N1A 121.11(11)

C22 C21 C26 116.85(11) C22A C21A C26A 116.62(11)

C26 C21 N1 121.69(11) C26A C21A N1A 122.17(11)

F1 C22 C21 117.95(11) F1A C22A C21A 117.84(11)

F1 C22 C23 118.20(11) F1A C22A C23A 118.30(11)

C23 C22 C21 123.85(12) C23A C22A C21A 123.86(12)

C22 C23 C24 118.12(12) C22A C23A C24A 118.13(12)

C23 C24 C25 119.90(12) C25A C24A C23A 120.05(12)

C26 C25 C24 120.48(12) C24A C25A C26A 120.37(13)

C25 C26 C21 120.77(12) C25A C26A C21A 120.97(12)

Table S6. Hydrogen Bonds for 3b.

D H A d(D-H)/Å d(H-A)/Å d(D-A)/Å D-H-A/°

O1 H1 N11 0.84 2.01 2.8403(13) 172.7

O1A H1A N1A2 0.84 2.02 2.8522(13) 169.5

11-X,1-Y,1-Z; 2-X,1-Y,-Z

Table S7. Torsion Angles for 3b.

A B C D Angle/˚ A B C D Angle/˚

F1 C22 C23 C24 179.43(11) F1A C22A C23A C24A -179.61(11)

N1 C21 C22 F1 -2.16(17) N1A C21A C22A F1A -3.62(17)

N1 C21 C22 C23 177.74(11) N1A C21A C22A C23A 176.74(11)

N1 C21 C26 C25 -177.39(11) N1A C21A C26A C25A -176.56(12)

N2 C3 C4 S1 34.46(11) N2A C3A C4A S1A 34.10(11)

N2 C3 C5 O1 61.62(13) N2A C3A C5A O1A 61.70(13)

N2 C10 C11 C12 18.72(16) N2A C10A C11A C12A 23.80(16)

N2 C10 C11 C16 -162.33(10) N2A C10A C11A C16A -158.03(10)

C1 S1 C4 C3 -26.64(8) C1A S1A C4A C3A -26.32(9)

C1 N1 C21 C22 103.47(13) C1A N1A C21A C22A 111.94(13)

C1 N1 C21 C26 -80.61(14) C1A N1A C21A C26A -71.89(15)

S-49

C1 N2 C3 C4 -28.69(13) C1A N2A C3A C4A -28.32(13)

C1 N2 C3 C5 -150.58(10) C1A N2A C3A C5A -150.34(10)

C1 N2 C10 C11 -86.98(13) C1A N2A C10A C11A -89.30(13)

C3 N2 C1 S1 8.74(12) C3A N2A C1A S1A 8.59(12)

C3 N2 C1 N1 -171.70(11) C3A N2A C1A N1A -172.15(11)

C3 N2 C10 C11 66.85(13) C3A N2A C10A C11A 63.91(14)

C4 S1 C1 N1 -168.22(11) C4A S1A C1A N1A -168.05(11)

C4 S1 C1 N2 11.33(9) C4A S1A C1A N2A 11.21(9)

C4 C3 C5 O1 -56.74(13) C4A C3A C5A O1A -56.87(13)

C5 C3 C4 S1 157.57(8) C5A C3A C4A S1A 157.13(8)

C10 N2 C1 S1 163.68(8) C10A N2A C1A S1A 162.95(8)

C10 N2 C1 N1 -16.77(17) C10A N2A C1A N1A -17.80(17)

C10 N2 C3 C4 176.33(10) C10A N2A C3A C4A 177.19(10)

C10 N2 C3 C5 54.44(14) C10A N2A C3A C5A 55.17(14)

C10 C11 C12 C13 -179.19(11) C10A C11A C12A C13A 179.33(11)

C10 C11 C16 C15 -179.18(11) C10A C11A C16A C15A -178.22(11)

C11 C12 C13 C14 -1.75(19) C11A C12A C13A C14A -1.07(19)

C12 C11 C16 C15 -0.19(18) C12A C11A C16A C15A 0.02(18)

C12 C13 C14 C15 -0.08(19) C12A C13A C14A C15A -0.22(19)

C13 C14 C15 C16 1.76(19) C13A C14A C15A C16A 1.39(19)

C14 C15 C16 C11 -1.63(18) C14A C15A C16A C11A -1.30(19)

C16 C11 C12 C13 1.87(18) C16A C11A C12A C13A 1.16(18)

C21 N1 C1 S1 -3.03(15) C21A N1A C1A S1A -5.61(15)

C21 N1 C1 N2 177.47(10) C21A N1A C1A N2A 175.23(11)

C21 C22 C23 C24 -0.47(19) C21A C22A C23A C24A 0.02(19)

C22 C21 C26 C25 -1.30(18) C22A C21A C26A C25A -0.22(19)

C22 C23 C24 C25 -1.05(19) C22A C23A C24A C25A -0.6(2)

C23 C24 C25 C26 1.4(2) C23A C24A C25A C26A 0.7(2)

C24 C25 C26 C21 -0.1(2) C24A C25A C26A C21A -0.3(2)

C26 C21 C22 F1 -178.27(10) C26A C21A C22A F1A 180.00(10)

C26 C21 C22 C23 1.63(18) C26A C21A C22A C23A 0.37(18)

Table S8. Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement

Parameters (Å2×103) for 3b.

Atom x y z U(eq)

H1 6826 3876 5348 29

H3 8422 7058 6372 20

H4A 8652 5473 4315 23

H4B 9778 6660 5007 23

S-50

H5A 9178 5360 6299 22

H5B 7639 5290 6706 22

H10A 5495 5516 6438 19

H10B 4529 6088 5900 19

H12 6975 8477 6737 22

H13 7299 10086 8313 26

H14 6158 9898 9749 27

H15 4684 8087 9600 25

H16 4448 6454 8054 21

H23 4136 6989 1377 27

H24 4954 9051 1911 32

H25 5802 10163 3651 32

H26 5926 9235 4846 26

H1A 2328 6095 -420 30

H3A 2279 2925 -1442 21

H4AA 3459 4526 599 24

H4AB 3936 3343 -99 24

H5AA 3882 4639 -1390 23

H5AB 2341 4682 -1779 23

H10C 78 4429 -1477 20

H10D -1130 3790 -957 20

H12A 54 1458 -1780 24

H13A -489 -154 -3351 28

H14A -1491 31 -4823 29

H15A -1963 1850 -4707 27

H16A -1347 3480 -3152 22

H23A -1914 2801 3521 28

H24A -1914 778 2985 33

H25A -1428 -237 1291 34

H26A -894 751 136 28

Table S9. Crystal data and structure refinement for 6a.

Identification code 6a

Empirical formula C17H18N2O2

Formula weight 282.33

Temperature/K 100.15

Crystal system monoclinic

S-51

Space group P21/n

a/Å 10.7941(3)

b/Å 9.6492(3)

c/Å 14.6149(4)

α/° 90

β/° 109.529(3)

γ/° 90

Volume/Å3 1434.64(8)

Z 4

ρcalcg/cm3 1.307

μ/mm-1 0.695

F(000) 600.0

Crystal size/mm3 0.15 × 0.12 × 0.06

Radiation CuKα (λ = 1.54184)

2Θ range for data collection/° 8.914 to 134.99

Index ranges -12 ≤ h ≤ 12, -11 ≤ k ≤ 8, -17 ≤ l ≤ 17

Reflections collected 7689

Independent reflections 2573 [Rint = 0.0271, Rsigma = 0.0274]

Data/restraints/parameters 2573/0/191

Goodness-of-fit on F2 1.024

Final R indexes [I>=2σ (I)] R1 = 0.0336, wR2 = 0.0844

Final R indexes [all data] R1 = 0.0420, wR2 = 0.0902

Largest diff. peak/hole / e Å-3 0.17/-0.19

Table S10. Fractional Atomic Coordinates (×104) and Equivalent Isotropic

Displacement Parameters (Å2×103) for 6a. Ueq is defined as 1/3 of the trace of the

orthogonalised UIJ tensor.

Atom x y z U(eq)

O1 1227.5(8) 5125.7(9) 2281.6(6) 22.7(2)

O2 935.4(10) 2060.9(10) 720.7(7) 30.2(2)

N1 325.3(10) 6850.3(11) 1130.2(7) 20.5(2)

N2 1621.2(10) 5038.4(11) 882.7(7) 20.6(2)

C1 1010.6(11) 5742.0(13) 1412.8(8) 19.1(3)

C3 2464.4(12) 3932.2(13) 1455.4(9) 22.0(3)

C4 2052.0(13) 3916.0(14) 2358.9(9) 25.8(3)

C5 2236.6(13) 2544.5(14) 932.1(9) 25.6(3)

C10 1835.7(12) 5630.2(13) 25.7(9) 21.4(3)

C11 2926.8(12) 6693.9(13) 278.1(8) 21.2(3)

C12 4239.2(13) 6285.3(14) 601.9(10) 27.6(3)

C13 5237.6(14) 7263.1(16) 875.7(10) 33.2(3)

S-52

C14 4937.2(15) 8662.3(16) 811.1(10) 33.1(3)

C15 3638.9(15) 9077.7(15) 469.6(10) 32.0(3)

C16 2636.6(14) 8103.0(14) 203.0(9) 25.4(3)

C21 -322.1(11) 7521.7(13) 1705.8(9) 21.1(3)

C22 -761.9(12) 6885.1(14) 2402.5(9) 24.3(3)

C23 -1388.4(13) 7657.6(15) 2920.9(10) 27.7(3)

C24 -1605.3(13) 9061.2(15) 2751.3(10) 28.8(3)

C25 -1192.4(13) 9700.2(15) 2053.5(10) 29.1(3)

C26 -560.9(13) 8940.1(14) 1532.8(9) 25.1(3)

Table S11. Anisotropic Displacement Parameters (Å2×103) for 6a. The Anisotropic

displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].

Atom U11 U22 U33 U23 U13 U12

O1 24.7(5) 25.0(5) 17.8(4) 1.9(3) 6.4(3) 5.8(4)

O2 35.4(5) 26.6(5) 23.5(5) 4.0(4) 2.9(4) -3.1(4)

N1 19.7(5) 21.1(5) 19.6(5) -0.8(4) 4.9(4) 0.3(4)

N2 22.9(5) 20.8(5) 18.5(5) 1.7(4) 7.4(4) 2.8(4)

C1 17.5(6) 21.7(6) 16.6(5) -1.3(5) 3.6(5) -3.4(5)

C3 20.0(6) 25.0(7) 19.1(6) 2.2(5) 4.0(5) 3.5(5)

C4 29.0(7) 25.8(7) 22.4(6) 3.1(5) 8.3(5) 8.1(5)

C5 28.3(7) 25.6(7) 21.2(6) 2.1(5) 6.0(5) 7.8(5)

C10 24.7(6) 22.3(6) 17.0(6) 0.7(5) 6.6(5) 1.3(5)

C11 26.2(6) 23.5(6) 15.1(5) 1.5(5) 8.7(5) 1.0(5)

C12 27.6(7) 26.0(7) 29.5(7) 6.5(5) 9.8(5) 2.0(5)

C13 25.5(7) 40.5(8) 31.6(7) 9.4(6) 6.9(6) -2.5(6)

C14 39.2(8) 35.6(8) 26.0(7) -2.5(6) 12.8(6) -14.9(6)

C15 50.2(9) 22.0(7) 32.2(7) -1.5(5) 25.0(7) -3.4(6)

C16 31.2(7) 25.1(7) 24.5(6) 2.9(5) 15.3(5) 3.5(5)

C21 15.7(6) 25.4(7) 18.8(6) -3.9(5) 1.3(5) -0.3(5)

C22 19.4(6) 24.5(7) 28.2(7) -2.9(5) 6.9(5) -2.4(5)

C23 22.2(6) 34.0(7) 28.0(7) -3.5(6) 9.9(5) -2.5(5)

C24 22.5(6) 34.1(8) 27.8(7) -8.6(6) 5.7(5) 4.3(5)

C25 28.3(7) 27.5(7) 26.4(7) -2.7(5) 2.5(6) 8.0(5)

C26 25.2(6) 26.3(7) 20.2(6) 1.1(5) 3.0(5) 3.2(5)

Table S12. Bond Lengths for 6a.

Atom Atom Length/Å Atom Atom Length/Å

S-53

O1 C1 1.3497(15) C11 C16 1.3914(18)

O1 C4 1.4492(15) C12 C13 1.387(2)

O2 C5 1.4127(17) C13 C14 1.384(2)

N1 C1 1.2873(16) C14 C15 1.381(2)

N1 C21 1.4173(16) C15 C16 1.387(2)

N2 C1 1.3554(16) C21 C22 1.4011(18)

N2 C3 1.4693(15) C21 C26 1.4000(19)

N2 C10 1.4636(15) C22 C23 1.3890(19)

C3 C4 1.5280(17) C23 C24 1.383(2)

C3 C5 1.5207(18) C24 C25 1.387(2)

C10 C11 1.5121(17) C25 C26 1.3886(19)

C11 C12 1.3921(18)

Table S13. Bond Angles for 6a.

Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚

C1 O1 C4 109.70(9) C16 C11 C10 120.51(11)

C1 N1 C21 122.26(11) C16 C11 C12 118.70(12)

C1 N2 C3 111.42(10) C13 C12 C11 120.64(13)

C1 N2 C10 122.69(10) C14 C13 C12 120.14(13)

C10 N2 C3 121.73(10) C15 C14 C13 119.62(13)

O1 C1 N2 110.64(10) C14 C15 C16 120.44(13)

N1 C1 O1 124.62(11) C15 C16 C11 120.42(13)

N1 C1 N2 124.74(11) C22 C21 N1 125.81(12)

N2 C3 C4 101.29(10) C26 C21 N1 115.93(11)

N2 C3 C5 112.82(10) C26 C21 C22 118.24(12)

C5 C3 C4 112.38(11) C23 C22 C21 120.41(13)

O1 C4 C3 105.85(10) C24 C23 C22 120.80(13)

O2 C5 C3 112.50(11) C23 C24 C25 119.38(12)

N2 C10 C11 112.91(10) C24 C25 C26 120.36(13)

C12 C11 C10 120.79(12) C25 C26 C21 120.79(13)

Table S14. Hydrogen Bonds for 6a.

D H A d(D-H)/Å d(H-A)/Å d(D-A)/Å D-H-A/°

O2 H2 N11 0.84 1.97 2.7950(13) 166.5

1-X,1-Y,-Z

S-54

Table S15. Torsion Angles for 6a.

A B C D Angle/˚ A B C D Angle/˚

N1 C21 C22 C23 -179.87(11) C10 N2 C1 N1 15.01(18)

N1 C21 C26 C25 179.82(11) C10 N2 C3 C4 167.91(11)

N2 C3 C4 O1 -9.54(13) C10 N2 C3 C5 -71.74(15)

N2 C3 C5 O2 -60.89(14) C10 C11 C12 C13 -176.98(12)

N2 C10 C11 C12 77.85(15) C10 C11 C16 C15 177.56(11)

N2 C10 C11 C16 -101.28(13) C11 C12 C13 C14 -1.3(2)

C1 O1 C4 C3 6.18(13) C12 C11 C16 C15 -1.59(18)

C1 N1 C21 C22 -26.87(18) C12 C13 C14 C15 -0.2(2)

C1 N1 C21 C26 154.79(12) C13 C14 C15 C16 0.8(2)

C1 N2 C3 C4 10.31(13) C14 C15 C16 C11 0.1(2)

C1 N2 C3 C5 130.66(11) C16 C11 C12 C13 2.17(19)

C1 N2 C10 C11 74.93(14) C21 N1 C1 O1 -2.27(18)

C3 N2 C1 O1 -7.21(14) C21 N1 C1 N2 178.22(11)

C3 N2 C1 N1 172.36(11) C21 C22 C23 C24 0.86(19)

C3 N2 C10 C11 -80.14(14) C22 C21 C26 C25 1.35(18)

C4 O1 C1 N1 -179.23(12) C22 C23 C24 C25 0.1(2)

C4 O1 C1 N2 0.34(13) C23 C24 C25 C26 -0.3(2)

C4 C3 C5 O2 52.88(14) C24 C25 C26 C21 -0.4(2)

C5 C3 C4 O1 -130.20(11) C26 C21 C22 C23 -1.56(18)

C10 N2 C1 O1 -164.56(11)

Table S16. Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement

Parameters (Å2×103) for 6a.

Atom x y z U(eq)

H2 453 2415 198 45

H3 3410 4204 1635 26

H4A 1557 3059 2380 31

H4B 2833 3964 2955 31

H5A 2430 2638 319 31

H5B 2853 1852 1341 31

H10A 1011 6070 -390 26

H10B 2053 4874 -353 26

H12 4453 5327 636 33

H13 6130 6972 1108 40

H14 5620 9333 1001 40

S-55

H15 3430 10037 417 38

H16 1746 8400 -32 31

H22 -631 5919 2521 29

H23 -1671 7216 3398 33

H24 -2033 9583 3109 35

H25 -1342 10663 1931 35

H26 -288 9388 1054 30

S-56

9 8 7 6 5 4 3 2 1 ppm

1.895

3.735

3.983

3.999

4.015

4.377

4.393

4.409

4.745

4.762

4.779

7.277

7.284

7.294

7.304

7.310

7.327

7.333

7.341

7.344

7.362

1.15

2.04

1.00

2.15

2.04

5.46

Current Data ParametersNAME bn-2EXPNO 1PROCNO 1

F2 - Acquisition ParametersDate_ 20141130Time 0.19INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zg30TD 65536SOLVENT CDCl3NS 6DS 2SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 19.7DW 62.400 usecDE 6.50 usecTE 297.7 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 400.1324710 MHzNUC1 1HP1 14.30 usecPLW1 9.10000038 W

F2 - Processing parametersSI 65536SF 400.1300000 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

S-57

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

51.320

52.971

76.681

76.999

77.318

79.530

127.091

127.943

128.365

139.572

Current Data ParametersNAME lzw2101-CEXPNO 1PROCNO 1

F2 - Acquisition ParametersDate_ 20150402Time 11.23INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 25DS 2SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 196.92DW 20.800 usecDE 6.50 usecTE 297.2 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 100.6228298 MHzNUC1 13CP1 9.70 usecPLW1 46.98899841 W

======== CHANNEL f2 ========SFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 90.00 usecPLW2 11.99499989 WPLW12 0.34213999 WPLW13 0.27713001 W


S-58

lenovo

图章

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

1.827

3.732

3.982

3.997

3.999

4.014

4.030

4.031

4.047

4.410

4.426

4.442

4.780

4.797

4.815

7.012

7.033

7.055

7.269

7.284

7.291

7.304

1.31

2.02

0.99

2.00

2.03

1.96

2.23

Current Data ParametersNAME lzw2002BEXPNO 1PROCNO 1

F2 - Acquisition ParametersDate_ 20150131Time 21.55INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 65536SOLVENT CDCl3NS 5DS 2SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 88.84DW 62.400 usecDE 6.50 usecTE 297.4 KD1 1.00000000 secTD0 1



S-59

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

50.680

53.087

76.685

77.003

77.320

79.636

115.240

115.452

129.616

129.695

135.356

135.387

160.869

163.308






S-60

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

1.812

3.676

3.798

3.961

3.977

3.994

4.010

4.026

4.374

4.390

4.405

4.744

4.761

4.778

6.848

6.870

7.194

7.216

7.259

1.36

2.02

3.05

1.02

2.00

2.05

1.98

1.95

Current Data ParametersNAME lzw2024AEXPNO 1PROCNO 1




S-61

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

50.903

53.047

55.259

76.685

77.002

77.320

79.757

113.921

129.296

131.732

158.867






S-62

lenovo

图章

10 9 8 7 6 5 4 3 2 1 ppm2.032

4.087

4.103

4.120

4.135

4.196

4.380

4.396

4.412

4.754

4.771

4.787

7.259

7.418

7.431

7.492

7.510

7.530

7.544

7.564

7.581

7.787

7.799

7.810

7.872

7.892

8.104

8.125

1.22

1.00

1.97

1.97

2.00

1.98

2.01

1.04

0.98

0.97

Current Data ParametersNAME lzw2002A-HEXPNO 1PROCNO 1




S-63

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

49.141

53.449

76.682

77.000

77.318

79.662

123.411

125.363

125.763

126.196

126.291

128.146

128.808

131.601

133.874

135.200






S-64

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm2.021

3.735

3.929

3.945

3.961

3.977

3.993

4.277

4.292

4.308

4.699

4.716

4.733

6.127

6.133

6.284

7.259

7.338

1.37

2.09

1.03

2.09

2.09

0.99

1.00

0.99





S-65

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

43.939

53.130

76.682

77.000

77.318

79.650

107.056

110.265

141.972

153.208

Current Data ParametersNAME lzw2125A-CEXPNO 1PROCNO 1





S-66

lenovo

图章

10 9 8 7 6 5 4 3 2 1 ppm1.935

3.758

3.961

3.978

3.994

4.011

4.026

4.370

4.386

4.402

4.743

4.760

4.777

7.018

7.030

7.107

7.109

7.113

7.260

7.273

7.280

7.285

7.293

1.30

2.02

1.00

2.04

2.04

0.97

0.94

0.95





S-67

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

46.228

53.081

76.681

76.999

77.317

79.556

121.807

126.062

127.386

140.579

Current Data ParametersNAME lzw2125B-CEXPNO 1PROCNO 1





S-68

lenovo

图章

10 9 8 7 6 5 4 3 2 1 0 ppm

1.097

1.128

1.155

1.185

1.216

1.247

1.295

1.304

1.313

1.322

1.331

1.339

1.348

1.358

1.688

1.718

2.324

2.341

3.857

3.873

3.889

3.905

3.921

4.372

4.388

4.403

4.756

4.773

4.790

7.260

2.37

3.68

1.15

6.66

2.06

1.00

2.06

2.07

Current Data ParametersNAME lzw2002D-HEXPNO 1PROCNO 1




S-69

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

25.87

26.47

31.29

38.16

53.66

53.77

76.68

77.00

77.32

79.63

Current Data ParametersNAME lzw2002D-CEXPNO 1PROCNO 1





S-70

lenovo

图章

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

3.592

4.811

4.827

5.011

5.027

7.283

7.290

7.301

7.339

7.350

7.375

7.439

7.458

7.477

7.502

7.520

1.17

2.01

2.01

2.00

1.19

4.86

2.02

2.00

Current Data ParametersNAME lzw2138-HEXPNO 3PROCNO 1




S-71

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

47.881

63.553

76.688

77.005

77.323

82.413

126.192

127.143

127.369

128.125

128.459

128.638

139.891

142.009






S-72

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm1.818

3.676

3.712

3.931

3.948

3.964

3.980

3.995

4.372

4.388

4.403

4.742

4.759

4.776

7.159

7.177

7.260

7.426

7.443

2.03

0.99

2.00

2.01

1.96

1.94

Current Data ParametersNAME zrw-1506-1EXPNO 1PROCNO 1




S-73

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

50.64

53.01

76.68

77.00

77.32

79.53

120.98

129.72

131.52

138.64






S-74

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm1.826

3.798

3.976

3.992

4.008

4.406

4.411

4.421

4.437

4.772

4.788

4.805

7.260

7.417

7.436

7.570

7.590

2.00

1.01

1.99

2.00

1.98

1.98





S-75

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

50.76

53.11

76.68

77.00

77.32

79.51

122.77

125.39

125.42

125.46

128.25

129.38

129.70

143.76






S-76

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm1.974

3.936

3.990

4.006

4.023

4.038

4.055

4.378

4.394

4.410

4.745

4.762

4.779

6.889

6.891

6.898

6.900

6.921

6.930

6.934

6.942

7.201

7.204

7.214

7.217

7.260

1.21

2.00

1.00

2.00

2.00

0.97

0.98

0.95

PC 1.00GB 0LB 0.30 HzSSB 0WDW EMSF 400.1300096 MHzSI 65536P1 14.30 usecNUC1 1HSFO1 400.1324710 MHz======== CHANNEL f1 ========

TD0 1D1 1.00000000 secTE 295.5 KDE 6.50 usecDW 62.400 usecRG 54.81AQ 4.0894966 secFIDRES 0.122266 HzSWH 8012.820 HzDS 0NS 8SOLVENT CDCl3TD 65536PULPROG zg30PROBHD 5 mm DUL 13C−1INSTRUM spectTime 20.09Date_ 20180903PROCNO 1EXPNO 1NAME zrw−−1489

S-77

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

45.85

52.87

76.68

77.00

77.31

79.51

124.71

125.08

126.67

143.13

PC 1.40GB 0LB 1.00 HzSSB 0WDW EMSF 100.6127824 MHzSI 32768P1 9.60 usecNUC1 13CSFO1 100.6228298 MHz======== CHANNEL f1 ========

TD0 1D11 0.03000000 secD1 2.00000000 secTE 296.0 KDE 6.50 usecDW 20.800 usecRG 196.92AQ 1.3631988 secFIDRES 0.366798 HzSWH 24038.461 HzDS 0NS 96SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm DUL 13C−1INSTRUM spectTime 20.15Date_ 20180903PROCNO 1EXPNO 2NAME zrw−−1489

S-78

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm2.343

3.835

3.989

4.005

4.006

4.022

4.038

4.055

4.398

4.414

4.430

4.717

4.734

4.751

7.137

7.138

7.151

7.155

7.157

7.168

7.169

7.236

7.255

7.260

7.599

7.603

7.618

7.622

7.637

7.642

8.520

8.521

8.532

1.21

1.98

1.00

1.97

2.03

0.99

1.08

1.00

0.98





S-79

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

52.66

53.33

76.68

77.00

77.32

79.50

122.16

136.57

149.31

159.05


F2 - Acquisition ParametersDate_ 20180905Time 21.23INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zgpg30TD 65536SOLVENT CDCl3NS 48DS 0SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 196.92DW 20.800 usecDE 6.50 usecTE 296.4 KD1 2.00000000 secD11 0.03000000 secTD0 1




S-80

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

1.700

3.352

3.355

3.368

3.371

3.982

3.998

3.999

4.015

4.030

4.032

4.047

4.444

4.461

4.477

4.804

4.821

4.838

6.175

6.191

6.207

6.215

6.231

6.247

6.491

6.531

7.209

7.213

7.216

7.224

7.230

7.236

7.244

7.248

7.252

7.260

7.290

7.293

7.305

7.309

2.01

1.00

2.03

2.04

1.00

1.00

1.00

4.05


TD0 1D1 1.00000000 secTE 297.0 KDE 6.50 usecDW 62.400 usecRG 34.77AQ 4.0894966 secFIDRES 0.122266 HzSWH 8012.820 HzDS 0NS 4SOLVENT CDCl3TD 65536PULPROG zg30PROBHD 5 mm DUL 13C−1INSTRUM spectTime 23.25Date_ 20180827PROCNO 1EXPNO 1NAME zrw−1479

S-81

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

49.32

53.05

76.68

77.00

77.32

79.75

126.17

127.47

127.61

128.49

131.65

136.71


TD0 1D11 0.03000000 secD1 2.00000000 secTE 297.5 KDE 6.50 usecDW 20.800 usecRG 196.92AQ 1.3631988 secFIDRES 0.366798 HzSWH 24038.461 HzDS 0NS 96SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm DUL 13C−1INSTRUM spectTime 23.28Date_ 20180827PROCNO 1EXPNO 2NAME zrw−1479

S-82

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

1.722

2.737

2.744

2.750

2.760

2.774

2.791

2.794

2.801

2.806

2.816

2.822

2.829

3.910

3.926

3.928

3.943

3.958

3.960

3.975

4.096

4.339

4.352

4.369

4.384

4.751

4.768

4.785

4.806

7.176

7.187

7.192

7.196

7.206

7.211

7.221

7.224

7.227

7.260

7.273

7.277

7.292

7.296

7.306

4.01

1.00

2.11

2.13

2.95

2.08


TD0 1D1 1.00000000 secTE 295.7 KDE 6.50 usecDW 62.400 usecRG 22.47AQ 4.0894966 secFIDRES 0.122266 HzSWH 8012.820 HzDS 0NS 2SOLVENT CDCl3TD 65536PULPROG zg30PROBHD 5 mm DUL 13C−1INSTRUM spectTime 12.55Date_ 20180905PROCNO 1EXPNO 1NAME zrw−1486−distill

S-83

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

36.43

48.13

53.28

76.68

77.00

77.32

79.36

126.18

128.39

128.43

139.30


TD0 1D11 0.03000000 secD1 2.00000000 secTE 296.0 KDE 6.50 usecDW 20.800 usecRG 196.92AQ 1.3631988 secFIDRES 0.366798 HzSWH 24038.461 HzDS 0NS 20SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm DUL 13C−1INSTRUM spectTime 12.56Date_ 20180905PROCNO 1EXPNO 2NAME zrw−1486−distill

S-84

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.976

0.999

1.027

1.057

1.063

1.098

1.120

1.128

1.135

1.151

1.158

1.169

1.176

1.200

1.207

1.231

1.262

1.574

1.593

1.597

1.602

1.605

1.683

1.691

1.721

1.739

1.754

2.057

2.354

2.363

2.372

2.381

2.389

2.398

2.407

2.415

4.032

4.049

4.066

4.083

4.386

4.403

4.419

4.784

4.802

4.819

5.282

7.260

2.09

3.15

0.96

4.10

0.96

1.01

1.95

2.00

Current Data ParametersNAME zrw-1470EXPNO 1PROCNO 1




S-85

lenovo

图章

190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

24.92

25.83

34.00

51.50

55.54

76.68

77.00

77.32

80.81






S-86

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

0.045

0.861

2.130

2.146

2.161

3.781

3.797

3.812

4.523

4.539

4.600

4.616

7.256

7.260

7.273

7.307

7.322

7.326

7.328

7.344

7.349

6.01

9.12

2.04

1.39

4.00

1.99

1.98

1.17

4.02


TD0 1D1 1.00000000 secTE 297.4 KDE 6.50 usecDW 62.400 usecRG 82.92AQ 4.0894966 secFIDRES 0.122266 HzSWH 8012.820 HzDS 0NS 5SOLVENT CDCl3TD 65536PULPROG zg30PROBHD 5 mm DUL 13C−1INSTRUM spectTime 22.08Date_ 20180901PROCNO 1EXPNO 1NAME zrw−1491−crude(2)

S-87

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

−5.47

18.14

25.85

37.95

47.30

59.30

59.70

76.68

77.00

77.32

81.64

127.08

128.05

128.48

140.31


TD0 1D11 0.03000000 secD1 2.00000000 secTE 297.8 KDE 6.50 usecDW 20.800 usecRG 196.92AQ 1.3631988 secFIDRES 0.366798 HzSWH 24038.461 HzDS 0NS 61SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm DUL 13C−1INSTRUM spectTime 22.11Date_ 20180901PROCNO 1EXPNO 2NAME zrw−1491−crude(2)

S-88

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm1.898

3.965

3.982

3.998

4.014

4.369

4.385

4.401

4.736

4.753

4.770

7.163

7.182

7.235

7.248

7.266

7.285

4.02

2.00

4.02

4.02

1.99

2.17





S-89

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

51.22

53.07

76.69

77.00

77.32

79.54

126.99

127.76

128.64

139.93






S-90

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.327

1.335

1.346

1.364

1.370

1.381

1.398

1.410

1.415

1.428

1.432

1.451

1.679

2.497

2.507

2.515

2.525

2.531

2.543

3.904

3.913

3.915

3.919

3.930

3.946

4.386

4.397

4.402

4.412

4.428

4.768

4.778

4.784

4.795

4.801

4.812

7.260

3.08

2.09

2.09

2.01

1.00

2.00

2.00

Current Data ParametersNAME zrw--1573EXPNO 1PROCNO 1




S-91

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

13.83

20.30

32.36

46.82

53.53

76.68

77.00

77.32

79.73

Current Data ParametersNAME zrw--1573EXPNO 2PROCNO 1





S-92

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

1.357

1.374

3.697

3.714

3.730

3.747

3.854

3.871

3.888

3.904

4.182

4.198

4.214

4.426

4.442

4.458

4.497

4.514

4.531

4.739

4.755

4.772

7.226

7.244

7.255

7.263

7.272

7.296

7.314

7.333

3.05

1.02

1.00

0.99

1.00

1.00

1.02

1.01

3.01

2.08


TD0 1D1 1.00000000 secTE 295.3 KDE 6.50 usecDW 62.400 usecRG 31.55AQ 4.0894966 secFIDRES 0.122266 HzSWH 8012.820 HzDS 0NS 8SOLVENT CDCl3TD 65536PULPROG zg30PROBHD 5 mm PABBO BB/INSTRUM spectTime 19.08Date_ 20180918PROCNO 1EXPNO 1NAME zrw−1536

S-93

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm23.76

51.79

56.46

76.68

77.00

77.32

80.01

80.08

126.44

127.23

128.47

144.77


TD0 1D11 0.03000000 secD1 2.00000000 secTE 296.1 KDE 6.50 usecDW 20.800 usecRG 196.92AQ 1.3631988 secFIDRES 0.366798 HzSWH 24038.461 HzDS 0NS 48SOLVENT CDCl3TD 65536PULPROG zgpg30PROBHD 5 mm PABBO BB/INSTRUM spectTime 19.11Date_ 20180918PROCNO 1EXPNO 2NAME zrw−1536

S-94

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.422

1.440

1.459

1.478

1.496

1.608

1.651

1.670

1.689

1.708

1.726

2.535

2.554

2.571

3.643

3.660

3.678

3.868

3.884

3.900

3.916

3.932

4.358

4.373

4.389

4.743

4.760

4.777

5.264

7.260

7.654

7.663

7.670

7.676

7.684

7.694

7.772

7.782

7.790

7.796

7.803

2.05

2.11

1.99

2.06

1.00

1.99

1.99

2.02

1.99





S-95

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

26.17

27.37

37.50

46.42

53.38

76.68

77.00

77.32

79.62

123.07

131.93

133.83

168.29






S-96

lenovo

图章

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

3.174

3.193

3.202

3.221

3.241

3.253

3.269

3.281

3.656

3.665

3.685

3.694

3.832

3.845

3.861

3.874

3.886

3.898

3.907

3.914

3.917

3.926

4.537

4.576

5.381

5.420

7.088

7.107

7.109

7.131

7.149

7.260

7.285

7.304

7.314

7.323

7.332

7.353

7.361

7.367

7.380

2.02

1.10

4.04

1.00

0.98

2.95

7.03





S-97

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm29.040

49.132

60.911

62.421

76.684

77.001

77.319

122.511

123.918

127.701

127.844

128.823

128.935

136.972

149.692

161.320






S-98

lenovo

图章

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm2.357

3.176

3.189

3.200

3.214

3.633

3.655

3.782

3.796

3.810

3.821

3.838

4.465

4.503

5.159

5.197

7.014

7.032

7.049

7.071

7.090

7.099

7.117

7.284

7.301

7.318

7.334

7.364

7.384

7.404

7.425

1.29

2.01

1.02

2.01

1.00

1.00

3.99

1.01

4.00





S-99

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm28.865

48.604

60.890

62.131

76.684

77.002

77.319

115.738

115.940

124.136

124.169

127.585

127.758

128.764

137.201

139.302

139.424

153.739

156.166

161.903






S-100

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

2.645

3.105

3.117

3.577

3.597

3.687

3.702

3.727

3.746

3.794

4.383

4.422

5.078

5.117

6.555

6.580

6.600

6.618

6.639

7.177

7.197

7.217

7.260

7.288

7.306

7.337

7.352

7.372

1.10

2.02

1.05

2.09

3.00

1.01

1.00

0.97

1.98

0.99

5.11

Current Data ParametersNAME lzw1120DEXPNO 3PROCNO 1




S-101

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm28.856

48.530

55.137

60.759

61.663

76.684

77.002

77.320

107.677

109.016

114.486

127.453

127.612

128.669

129.496

137.320

152.787

160.034

Current Data ParametersNAME lzw1120DEXPNO 4PROCNO 1





S-102

lenovo

图章

10 9 8 7 6 5 4 3 2 1 ppm3.190

3.199

3.210

3.730

3.741

3.758

3.769

3.811

3.825

3.838

3.853

3.885

3.898

3.915

3.928

4.570

4.608

5.492

5.530

7.260

7.293

7.328

7.382

7.401

7.419

7.470

7.487

7.505

8.237

8.256

0.55

2.08

1.00

1.04

1.03

1.02

1.00

5.01

2.04

1.07

1.97

Current Data ParametersNAME lzw1179EXPNO 3PROCNO 1




S-103

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm29.547

49.960

60.626

60.844

76.686

77.004

77.322

127.831

127.951

128.031

128.932

129.638

132.002

136.399

136.457

172.696

176.132






S-104

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

3.117

3.134

3.145

3.161

3.173

3.187

3.200

3.348

3.476

3.482

3.502

3.509

3.594

3.608

3.621

3.635

3.665

4.289

4.328

4.458

4.496

4.508

4.546

5.058

5.097

7.253

7.278

7.297

7.313

7.332

7.351

7.369

2.04

1.28

1.08

2.05

1.09

2.08

1.00

10.5

9

Current Data ParametersNAME lzw2135B-HEXPNO 1PROCNO 1




S-105

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm28.871

48.461

58.225

60.473

61.518

76.684

77.002

77.320

126.407

127.258

127.374

127.620

128.133

128.560

137.711

140.919

160.370






S-106

lenovo

图章

10 9 8 7 6 5 4 3 2 1 ppm

2.931

2.942

3.026

3.574

3.578

3.594

3.603

3.611

3.631

3.639

4.651

4.690

5.662

5.700

7.047

7.068

7.077

7.096

7.115

7.259

7.307

7.326

7.345

7.377

7.394

7.408

7.427

7.445

7.517

7.534

7.549

7.568

7.582

7.584

7.814

7.834

7.887

7.906

8.168

8.189

2.06

1.21

3.09

1.01

1.00

3.10

2.11

2.02

2.16

1.08

1.02

1.01





S-107

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm28.831

46.915

60.520

60.835

76.681

76.999

77.317

122.172

123.275

123.711

125.137

125.975

126.348

126.458

128.479

128.647

128.849

131.450

132.448

133.800

151.562

159.203






S-108

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

2.991

3.101

3.119

3.129

3.145

3.158

3.172

3.186

3.681

3.688

3.708

3.716

3.782

3.797

3.804

3.813

3.818

3.827

3.841

3.856

3.869

3.883

4.420

4.460

5.020

5.059

6.378

6.973

6.993

7.066

7.084

7.102

7.293

7.312

7.331

7.404

1.16

2.05

1.02

2.02

1.00

1.00

1.96

2.00

1.02

2.09

0.98





S-109

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm28.779

41.544

60.786

61.992

76.684

77.002

77.320

108.646

110.500

122.013

123.269

128.802

142.079

150.637

151.387

159.794






S-110

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

3.025

3.041

3.053

3.067

3.075

3.101

3.555

3.570

3.589

3.604

3.682

3.697

3.714

4.365

4.404

5.029

5.067

6.976

6.996

7.064

7.083

7.101

7.119

7.131

7.186

7.260

7.292

7.311

7.323

7.330

3.21

1.02

2.04

1.01

1.00

2.02

2.03

1.00

3.02





S-111

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm28.795

43.749

60.789

61.659

76.684

77.002

77.320

122.048

122.623

123.276

126.311

127.461

128.838

137.857

151.426

160.115






S-112

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

1.293

1.719

1.764

1.787

2.889

2.906

2.924

2.940

3.096

3.104

3.123

3.131

3.185

3.203

3.213

3.231

3.267

3.650

3.661

3.678

3.691

3.710

3.719

3.737

3.773

3.793

3.808

3.829

3.838

3.847

3.856

3.873

6.922

6.942

7.040

7.059

7.077

7.269

7.288

7.307

2.02

3.14

5.99

1.00

1.05

2.04

1.97

1.97

1.95

0.99

2.04

Current Data ParametersNAME lzw2137C-HEXPNO 1PROCNO 1




S-113

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm28.831

46.915

60.520

60.835

76.681

76.999

77.317

122.172

123.275

123.711

125.137

125.975

126.348

126.458

128.479

128.647

128.849

131.450

132.448

133.800

151.562

159.203






S-114

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

1.710

3.112

3.140

3.861

3.889

3.986

4.025

4.055

4.087

5.873

5.911

7.281

7.296

7.370

7.387

7.402

7.418

7.434

7.452

7.479

7.497

7.525

8.326

8.345

0.73

1.03

1.05

2.96

1.00

2.31

10.9

9

1.93





S-115

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm37.828

49.164

63.484

72.957

76.679

76.997

77.315

125.844

127.566

128.060

128.211

128.606

129.334

129.737

131.995

136.591

137.985

139.249

174.873

176.108






S-116

lenovo

图章

6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

3.306

3.310

3.399

3.414

3.427

3.442

3.605

3.622

3.634

3.644

3.648

3.671

3.685

3.699

3.713

4.282

4.297

4.304

4.311

4.318

4.326

4.333

4.347

1.03

3.09

1.00


F2 - Acquisition ParametersDate_ 20151201Time 20.52INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 65536SOLVENT MeODNS 7DS 0SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 45.67DW 62.400 usecDE 6.50 usecTE 296.5 KD1 1.00000000 secTD0 1



S-117

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

35.548

48.358

48.571

48.785

48.999

49.211

49.423

49.636

62.925

66.805

202.281


F2 - Acquisition ParametersDate_ 20151201Time 20.54INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 65536SOLVENT MeODNS 30DS 0SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 196.92DW 20.800 usecDE 6.50 usecTE 297.2 KD1 2.00000000 secD11 0.03000000 secTD0 1




S-118

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

2.763

3.227

3.238

3.255

3.267

3.317

3.339

3.345

3.367

3.704

3.714

3.733

3.743

3.808

3.833

3.847

3.862

3.876

4.169

4.181

4.192

4.204

4.215

4.227

4.473

4.510

5.644

5.682

7.294

7.303

7.319

7.324

7.337

7.342

7.359

1.05

1.01

1.00

1.01

0.99

1.00

1.07

1.00

5.21





S-119

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm29.862

50.936

60.481

67.531

76.683

77.002

77.319

127.713

128.069

128.876

135.064

197.997






S-120

lenovo

图章

0.00.00.50.51.01.01.51.52.02.02.52.53.03.03.53.54.04.04.54.55.05.05.55.56.06.06.56.57.07.07.57.58.08.08.58.59.09.0f1 (ppm)f1 (ppm)

lzw4100B-H

1.17

1.17

0.99

0.99

1.02

1.02

0.99

0.99

1.01

1.01

1.01

1.01

1.00

1.00

1.00

1.00

1.97

1.97

1.98

1.98

2.4289

3.2296

3.2407

3.2578

3.2689

3.3420

3.3635

3.3915

3.7730

3.7835

3.8521

3.8657

4.1999

4.2102

4.4686

4.5061

5.6145

5.6520

7.0075

7.0287

7.0499

7.3033

7.3171

7.3231

7.3371

S-121

lenovo

图章

-10-1000101020203030404050506060707080809090100100110110120120130130140140150150160160170170180180190190200200210210f1 (ppm)f1 (ppm)

lzw4100B-C

29.9272

50.2877

60.7691

67.4410

76.6815

76.9998

77.3178

115.7426

115.9572

129.6285

129.7092

131.0052

161.1924

163.6489

198.1357

S-122

lenovo

图章

10 9 8 7 6 5 4 3 2 1 ppm

2.721

3.240

3.250

3.268

3.278

3.321

3.342

3.370

3.721

3.730

3.750

3.759

3.790

3.856

3.869

3.884

3.898

4.198

4.208

4.218

4.228

4.423

4.460

5.581

5.618

6.863

6.884

7.267

7.288

1.07

1.00

0.99

4.01

1.07

1.01

1.01

1.00

2.01

2.07





S-123

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm29.854

50.427

55.219

60.425

67.429

76.683

77.001

77.319

114.226

127.075

129.237

159.304

197.619

Current Data ParametersNAME lzw4100C-CEXPNO 1PROCNO 1





S-124

lenovo

图章

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

3.089

3.095

3.118

3.123

3.238

3.259

3.266

3.287

3.782

3.797

3.809

3.822

3.837

3.849

4.006

4.012

4.019

4.744

4.782

6.203

6.241

7.259

7.451

7.460

7.467

7.516

7.533

7.554

7.574

7.590

7.847

7.854

7.863

7.870

7.884

7.903

7.983

8.003

1.03

1.06

2.22

1.00

1.05

1.00

4.34

2.31

1.00





S-125

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm30.037

50.122

60.780

66.776

76.678

76.996

77.313

123.470

125.263

126.355

127.177

127.372

128.856

129.311

130.837

131.427

133.905

197.039






S-126

lenovo

图章

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

2.812

3.236

3.248

3.264

3.276

3.349

3.371

3.377

3.399

3.762

3.772

3.791

3.801

3.921

3.935

3.950

3.964

4.265

4.277

4.287

4.299

4.310

4.322

4.552

4.591

5.449

5.488

6.320

6.327

6.332

6.391

6.398

7.354

7.357

1.12

1.00

1.04

1.02

1.04

1.01

1.01

1.00

1.96

0.96





S-127

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm29.872

43.913

60.515

68.021

76.682

77.000

77.318

109.954

110.595

142.655

148.235

197.760

Current Data ParametersNAME lzw4110C-CEXPNO 1PROCNO 1





S-128

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

2.521

3.226

3.238

3.254

3.266

3.321

3.342

3.349

3.370

3.726

3.737

3.755

3.766

3.862

3.876

3.891

3.905

4.208

4.221

4.231

4.243

4.254

4.266

4.585

4.622

5.503

5.540

7.095

7.097

7.107

7.109

7.258

7.290

7.301

7.308

7.313

7.320

1.17

1.01

1.01

1.01

1.01

1.00

1.00

1.00

0.98

1.92

Current Data ParametersNAME lzw4110D-HEXPNO 1PROCNO 1




S-129

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm29.902

46.366

60.733

67.756

76.683

77.001

77.319

123.772

126.878

127.254

135.664

197.699

Current Data ParametersNAME lzw4110D-CEXPNO 1PROCNO 1





S-130

lenovo

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.143

1.167

1.202

1.233

1.602

1.631

1.649

1.695

1.831

1.849

1.858

1.868

2.942

3.000

3.017

3.034

3.051

3.229

3.236

3.257

3.264

3.447

3.468

3.475

3.496

3.749

3.760

3.777

3.788

3.818

3.834

3.846

3.862

4.211

4.232

4.245

4.266

4.326

7.259

2.07

3.08

5.10

1.08

1.07

1.06

1.00

1.00

1.03

0.96

1.01

0.97





S-131

Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

25.482

25.599

26.066

30.200

30.245

30.862

35.997

53.502

59.913

68.821

76.683

77.001

77.318

196.702






S-132

Administrator

图章

10 9 8 7 6 5 4 3 2 1 ppm3.371

3.401

3.554

3.562

3.575

3.601

3.609

3.632

3.640

4.209

4.248

4.277

4.298

4.320

4.336

4.357

4.995

5.033

7.019

7.037

7.055

7.199

7.218

7.260

7.289

7.308

7.320

7.332

7.346

7.367

1.09

2.37

3.16

1.00

1.06

2.06

7.50





S-133

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

46.513

56.716

59.600

67.000

76.688

77.006

77.323

122.387

123.633

127.732

128.117

128.595

128.729

136.569

146.910

154.693






S-134

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

3.396

3.422

3.611

3.628

3.638

3.954

4.192

4.230

4.294

4.315

4.338

4.344

4.360

4.380

4.967

5.005

7.148

7.169

7.255

7.277

7.313

7.330

7.344

7.357

7.373

7.390

1.08

2.06

0.83

1.09

2.11

1.00

2.02

2.06

5.33





S-135

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

46.468

56.664

59.581

67.110

76.681

77.000

77.317

124.920

127.267

127.830

128.008

128.516

128.778

136.282

145.552

154.867






S-136

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm3.373

3.403

3.568

3.590

3.599

3.607

3.630

3.638

3.803

4.196

4.234

4.251

4.272

4.294

4.305

4.321

4.341

4.983

5.022

6.603

6.623

6.782

6.809

6.829

7.189

7.209

7.229

7.283

7.294

7.314

7.327

7.341

7.361

1.04

2.09

3.16

0.69

1.17

2.12

1.00

1.02

0.97

1.02

1.03

5.10





S-137

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

46.406

55.091

56.613

59.590

67.085

76.681

76.999

77.317

107.967

109.435

116.228

127.667

128.039

128.668

129.107

136.439

148.203

154.762

159.917






S-138

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

2.578

3.471

3.499

3.679

3.710

4.289

4.308

4.588

4.626

5.038

5.076

7.281

7.293

7.347

7.362

7.380

7.401

7.418

7.434

7.451

7.476

7.493

7.549

7.569

7.816

7.835

8.232

8.251

1.52

1.04

1.98

2.06

1.03

1.00

1.40

7.81

1.13

1.03

0.95





S-139

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

47.380

57.339

60.381

67.010

76.681

76.999

77.316

117.979

122.370

124.107

124.875

125.578

125.816

127.732

127.822

128.004

128.896

129.493

134.344

137.063

143.389

154.136






S-140

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

3.485

3.512

3.680

3.702

3.721

3.750

3.758

3.836

4.303

4.324

4.339

4.358

4.377

4.877

4.917

6.360

7.016

7.034

7.053

7.151

7.170

7.277

7.296

7.315

7.394

1.04

2.16

0.96

3.01

1.00

1.95

0.99

1.95

2.12

1.00





S-141

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm39.932

57.553

59.619

66.996

76.683

77.000

77.319

109.024

110.535

122.503

123.540

128.563

142.382

146.652

150.102

154.146






S-142

lenovo

图章

10 9 8 7 6 5 4 3 2 1 ppm

3.444

3.448

3.474

3.479

3.612

3.633

3.650

3.678

3.686

3.709

3.717

3.771

4.281

4.302

4.324

4.330

4.340

4.347

4.368

4.963

5.001

7.036

7.054

7.072

7.152

7.164

7.195

7.215

7.283

7.298

7.318

7.334

1.02

1.10

1.14

1.06

3.00

1.00

1.04

1.02

2.90

3.19





S-143

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm41.752

56.937

59.711

67.077

76.685

77.003

77.321

122.579

123.467

123.571

126.563

127.674

128.635

137.055

146.520

154.505






S-144

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

1.014

1.039

1.228

1.281

1.676

1.699

1.742

1.767

2.830

2.844

2.866

2.880

3.436

3.467

3.557

3.579

3.599

3.608

3.630

3.638

3.724

3.730

4.324

4.345

4.366

4.378

4.391

4.412

6.982

7.000

7.018

7.121

7.141

7.251

7.270

7.282

7.289

2.09

3.49

6.04

1.00

1.07

1.98

1.06

2.22

1.02

1.92

2.12





S-145

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

25.692

25.791

26.354

30.397

30.939

35.562

48.101

57.797

59.776

67.075

76.687

77.004

77.323

122.201

123.660

128.471

146.877

154.734






S-146

lenovo

图章

10 9 8 7 6 5 4 3 2 1 ppm

3.775

3.814

3.837

3.868

3.910

3.941

4.253

4.273

4.642

4.663

5.190

5.229

7.040

7.058

7.076

7.250

7.270

7.288

7.308

7.323

7.342

7.363

7.382

7.398

7.415

7.433

7.458

7.478

7.493

7.510

1.02

2.00

1.01

1.02

1.00

1.03

10.5

64.

05





S-147

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

45.538

62.183

68.156

74.535

76.684

77.002

77.319

122.240

123.641

125.842

127.882

127.923

128.468

128.554

129.090

129.317

139.075

139.846

147.288

154.069






S-148

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

3.179

3.500

3.530

3.695

3.700

3.727

3.758

4.215

4.254

4.265

4.280

4.300

4.321

4.697

4.735

7.261

7.288

7.303

7.323

7.339

7.357

0.91

1.02

2.03

2.99

1.00

4.98





S-149

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

46.15

55.70

60.21

64.53

76.68

77.00

77.32

127.99

128.86

135.89

159.15






S-150

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

2.693

3.495

3.502

3.525

3.531

3.665

3.672

3.679

3.687

3.694

3.702

3.709

3.721

3.730

3.751

3.760

3.781

4.170

4.208

4.225

4.247

4.261

4.282

4.304

4.612

4.650

6.847

6.868

7.213

7.234

7.260

1.25

0.97

1.00

1.00

2.97

0.99

2.01

1.00

1.98

1.97





S-151

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

45.67

55.23

55.69

60.32

64.46

76.68

77.00

77.32

114.22

127.93

129.40

159.07

159.30






S-152

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

2.899

3.532

3.555

3.561

3.667

3.676

3.683

3.690

3.699

3.706

3.717

3.745

3.753

4.190

4.229

4.239

4.246

4.261

4.292

4.314

4.336

4.633

4.671

7.174

7.195

7.260

7.455

7.476

0.92

0.99

1.99

2.00

1.02

1.00

1.97

1.94





S-153

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

45.72

55.74

60.61

64.54

76.68

77.00

77.32

121.99

129.78

132.00

135.02

159.04






S-154

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

2.835

3.545

3.553

3.574

3.582

3.684

3.693

3.700

3.707

3.715

3.723

3.730

3.741

3.749

3.770

3.779

4.243

4.257

4.265

4.279

4.288

4.318

4.327

4.340

4.362

4.755

4.794

7.260

7.415

7.436

7.587

7.607

1.17

0.98

1.99

2.98

1.00

1.97

1.97





S-155

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

45.80

55.80

60.61

64.64

76.68

77.00

77.31

119.84

122.55

125.25

125.74

125.77

125.81

125.85

127.96

128.29

129.76

130.09

130.41

130.73

140.07

159.14






S-156

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm2.773

3.592

3.603

3.625

3.635

3.813

3.820

3.829

3.852

3.861

4.252

4.266

4.273

4.288

4.307

4.328

4.350

4.472

4.511

4.860

4.899

6.969

6.977

6.981

6.990

7.040

7.048

7.269

7.284

1.26

0.98

1.97

1.98

1.02

1.00

0.96

0.98

1.04





S-157

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm40.87

55.62

60.51

64.57

76.68

77.00

77.32

125.93

127.04

127.18

138.12

158.67






S-158

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm3.518

3.526

3.551

3.559

3.806

3.839

3.935

3.954

3.958

3.968

3.976

4.207

4.247

4.276

4.297

4.316

4.372

4.394

4.416

4.713

4.753

6.908

7.229

7.247

7.260

7.357

7.376

7.693

7.712

7.731

8.473

8.485

0.98

0.98

1.01

0.96

1.01

1.04

1.00

0.87

1.08

1.00

0.98

0.97





S-159

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

47.86

59.68

60.53

64.18

76.68

77.00

77.32

123.01

123.28

137.70

148.69

156.21

158.61






S-160

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

3.178

3.606

3.635

3.800

3.809

3.830

3.839

3.859

3.879

3.887

3.896

3.909

3.918

4.242

4.245

4.258

4.273

4.280

4.294

4.324

4.346

4.368

6.112

6.126

6.132

6.145

6.152

6.166

6.171

6.185

6.561

6.601

7.232

7.243

7.250

7.256

7.261

7.268

7.294

7.313

7.331

0.92

1.00

3.01

2.00

1.03

0.99

0.99

1.06

1.97

2.04





S-161

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

44.54

55.97

60.55

64.60

76.68

77.00

77.32

123.14

126.45

128.03

128.61

133.99

135.97

158.74






S-162

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

2.849

2.865

2.882

2.901

2.918

2.935

2.952

3.111

3.312

3.328

3.331

3.347

3.363

3.366

3.383

3.476

3.483

3.504

3.511

3.587

3.596

3.609

3.618

3.624

3.634

3.653

3.662

3.673

3.691

4.134

4.148

4.155

4.169

4.193

4.204

4.215

4.236

7.201

7.220

7.233

7.260

7.273

7.290

7.310

2.03

0.88

1.01

1.00

2.98

0.98

1.00

2.89

1.97





S-163

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm33.74

43.72

56.71

60.77

64.49

76.68

77.00

77.32

126.63

128.61

128.67

138.37

158.82






S-164

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.077

1.085

1.100

1.109

1.117

1.141

1.257

1.265

1.273

1.289

1.297

1.305

1.321

1.329

1.338

1.376

1.407

1.415

1.437

1.446

1.606

1.616

1.637

1.646

1.666

1.676

1.728

1.756

1.790

1.796

1.830

1.872

1.902

3.179

3.449

3.470

3.479

3.489

3.509

3.652

3.690

3.717

3.865

3.873

3.882

3.891

4.260

4.276

1.02

1.99

1.05

2.03

3.04

1.00

0.97

1.00

1.99

1.00

1.99





S-165

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

25.21

25.68

25.70

30.03

31.84

54.00

55.45

62.68

65.41

76.68

77.00

77.32

158.40






S-166

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.883

0.901

0.919

1.268

1.275

1.289

1.307

1.311

1.325

1.330

1.467

1.482

1.501

1.514

1.522

1.535

3.032

3.040

3.054

3.067

3.075

3.088

3.380

3.401

3.415

3.419

3.434

3.436

3.455

3.582

3.590

3.612

3.620

3.713

3.723

3.742

3.753

3.824

3.834

3.844

3.856

4.208

4.222

4.230

4.244

4.288

4.310

4.332

3.08

2.14

2.09

1.05

1.18

1.14

1.07

1.04

1.02

1.00





S-167

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

13.59

19.77

29.26

41.66

55.97

60.55

64.63

76.68

77.00

77.32

158.90






S-168

lenovo

图章

9 8 7 6 5 4 3 2 1 0 ppm

0.029

0.864

1.734

1.748

1.756

1.771

1.786

1.803

1.818

1.826

1.841

1.854

2.509

2.525

2.541

3.452

3.457

3.471

3.602

3.616

3.630

4.187

4.209

4.229

4.251

4.299

4.338

4.562

4.601

7.260

7.275

7.293

7.308

7.327

7.345

7.373

7.391

6.03

9.11

2.08

0.99

2.04

2.02

2.03

1.00

0.99

3.12

2.00





S-169

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

-5.69

-5.68

18.05

25.76

35.97

44.64

58.25

64.23

64.98

69.30

76.68

77.00

77.32

127.79

127.83

128.85

138.29

158.90






S-170

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

1.642

1.660

1.668

1.686

2.827

3.166

3.177

3.492

3.501

3.513

3.522

3.535

3.557

3.585

3.599

3.613

3.914

3.923

3.934

3.946

4.155

4.176

4.184

4.198

4.207

4.221

4.229

4.242

4.274

4.296

4.318

5.092

5.110

5.128

5.146

5.171

5.189

5.207

5.225

7.280

7.297

7.314

7.336

7.348

7.356

7.372

7.421

7.440

6.90

1.03

1.23

2.00

1.35

2.50

1.00

3.52

1.04

1.30

1.03

2.68

6.95

2.05





S-171

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

15.65

18.40

51.07

54.83

55.42

61.16

62.37

64.82

65.17

76.68

77.00

77.32

126.68

127.17

127.94

128.05

128.75

128.83

139.07

141.22

158.73

158.89






S-172

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

2.078

2.084

2.089

2.095

2.100

3.039

3.600

3.625

3.779

3.797

4.201

4.215

4.223

4.236

4.264

4.299

4.308

4.338

4.346

4.368

4.389

4.694

4.700

4.732

4.738

7.312

7.331

7.372

7.389

7.409

1.18

1.95

3.93

2.02

1.25

0.98

3.06

2.00

1.91

1.92


F2 - Acquisition ParametersDate_ 20180915Time 21.34INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 65536SOLVENT AcetoneNS 8DS 0SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 70.97DW 62.400 usecDE 6.50 usecTE 297.9 KD1 1.00000000 secTD0 1



S-173

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

29.34

29.53

29.73

29.92

30.11

30.30

30.50

46.50

46.52

56.63

56.68

61.14

65.32

128.00

128.01

128.39

128.41

129.88

138.45

159.42

206.48


F2 - Acquisition ParametersDate_ 20180915Time 21.46INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 65536SOLVENT AcetoneNS 400DS 0SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 196.92DW 20.800 usecDE 6.50 usecTE 298.9 KD1 2.00000000 secD11 0.03000000 secTD0 1




S-174

lenovo

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.575

2.513

3.077

3.089

3.285

3.303

3.317

3.399

3.593

3.802

4.043

4.250

4.269

4.997

5.756

7.854

4.16

1.19

1.91

3.12

1.11

1.10

1.04

1.00

4.03


F2 - Acquisition ParametersDate_ 20180920Time 11.53INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 65536SOLVENT DMSONS 4DS 0SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 70.97DW 62.400 usecDE 6.50 usecTE 295.5 KD1 1.00000000 secTD0 1



S-175

lenovo

图章

-100102030405060708090100110120130140150160170180190200210

zrw-1540

24.73

25.70

39.32

39.53

39.74

39.95

40.16

40.36

55.97

59.97

64.57

123.46

132.08

134.82

158.30

168.46

S-176

lenovo

图章

9 8 7 6 5 4 3 2 1 ppm

2.646

2.658

2.685

2.697

2.772

2.787

2.801

2.816

2.826

2.840

3.272

3.297

3.310

3.328

3.341

3.360

3.372

3.711

3.742

3.802

3.832

4.011

4.027

4.046

4.061

4.286

4.307

4.671

4.692

4.852

6.943

6.962

6.981

7.041

7.060

7.079

7.253

7.273

7.356

7.376

0.99

1.02

3.04

0.99

1.03

1.02

0.99

1.00

0.99

1.00

0.99

1.00

Current Data ParametersNAME zrw-1543(MeOH)EXPNO 1PROCNO 1

F2 - Acquisition ParametersDate_ 20180927Time 20.44INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 65536SOLVENT MeODNS 8DS 0SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 70.97DW 62.400 usecDE 6.50 usecTE 295.3 KD1 1.00000000 secTD0 1



S-177

lenovo

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

21.29

38.57

48.51

48.73

48.94

49.15

49.36

49.58

49.79

50.00

63.81

64.60

71.14

109.53

112.41

119.32

120.40

123.29

127.87

132.77

138.26

160.75

Current Data ParametersNAME zrw-1543(MeOH)EXPNO 2PROCNO 1

F2 - Acquisition ParametersDate_ 20180927Time 20.51INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 65536SOLVENT MeODNS 120DS 0SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 196.92DW 20.800 usecDE 6.50 usecTE 296.2 KD1 2.00000000 secD11 0.03000000 secTD0 1




S-178

lenovo

图章

zengwei lai,ab renwei zhang, qiang feng, and jianwei sunover anhydrous na 2 so 4, filtered and...

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