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Supporting Information for
Rh(III)-Catalyzed C−H Activation/[4+3] Cycloaddition of Benzamides and Vinylcarbenoids: Facile Synthesis of Azepinones
Sunliang Cui,* Yan Zhang, Dahai Wang and Qifan Wu Institute of Materia Medica and College of Pharmaceutical Sciences,
Zhejiang University, Hangzhou 310058, P.R.China E-mail: slcui@zju.edu.cn
Contents
General Considerations S2
General Procedure for the Synthesis of 3 - 4 S3
Characterization of 3 - 4 S3-S19
Synthesis of Pyrazole 5 S20
Derivation of Product 3m to 6 and 7 S20-S22
Kinetic Isotope Effect Study S22-S23
References S23
Copies of NMR Spectra S24-S184
S1
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
General Information:
Infrared spectra were obtained on a FTIR spectrometer. 1H NMR and 13C NMR
spectra were recorded on BRUKER AVANCE III 500 or BRUKER AVANCE III 400
spectrometer. CDCl3 was used as solvent and tetramethylsilane (TMS) as internal
standard. Chemical shifts were referenced relative to residual solvent signal (1H NMR:
δ 7.26 ppm, 13C NMR: δ 77.0 ppm). The following abbreviations are used to describe
peak patterns where appropriate: b = broad, s = singlet, d = doublet, t = triplet, q =
quartet, m = multiplet. Coupling constants (J) are reported in Hertz (Hz). HRMS
were performed on Waters GCT Premier Time of Flight Mass Spectrometer (EI) or
Agilent Technologies 6224 TOF LC/MS apparatus (ESI). Melting points were
measured with micro melting point apparatus.
The N-pivaloyloxybenzamides 1, vinyldiazoacetates and ketone 2, were prepared
according to the literature. 1, 2 [Cp*RhCl2]2, CsOAc, anhydrous CH3CN and
d5-benzoic acid were commercial available.
NHOPiv
O
1a
NHOPiv
O
1bMe
NHOPiv
O
1cPh
NHOPiv
O
1dNC
NHOPiv
O
1eF3C
NHOPiv
O
1fMeO
NHOPiv
O
1gCl
NHOPiv
O
1hBr
NHOPiv
O
1iI
NHOPiv
O
1jO2N
NHOPiv
O
1k
MeNHOPiv
O
1l
Me
O2N
NHOPiv
O
1mCl
ClNHOPiv
O
1n
O
O
NHOPiv
O
1o
N2O
O2a
tBu
N2O
O2b
Me
N2O
O2c
BrN2
O
O2d
EtMe
N2O
O2e
EtPh
N2O
O2f
Et
Br
N2O
O2g
Et
O
N2O
O2h
Et
S
N2
O2i
N2O
OH3C
2j
Ph
S2
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
General Procedure:
Typical procedure for synthesis of azepinone: [Cp*RhCl2]2 (2.5 mg, 2 mol%),
benzamide 1a (44.2 mg, 0.2 mmol), CsOAc (38.4 mg, 0.2 mmol) were added to a vial.
CH3CN (1.0 mL) was added, followed by micro-syringe addition of tert-butyl
vinyldiazoacetate 2a (50.4 mg, 0.3 mmol). The micro-syringe was washed with an
additional 0.5 mL CH3CN and added to the reaction solution. The mixture was kept at
room temperature under air. After completion within 6 hours, it was diluted with
CH2Cl2 and transferred to a round bottom flask. Silica was added to the flask and
volatiles were evaporated under vacuum. The purification was performed by flash
column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:1) as
eluent to give product 3a as a white solid (49 mg, 95% yield). White solid; mp.
204-205 oC; 1H NMR (CDCl3, 500 MHz) δ 8.38 (b, 1H), 7.95 (d, J = 7.5 Hz, 1H),
7.50 (m, 2H), 7.45 (m, 1H), 7.28 (m, 1H), 3.51 (t, J = 7.0 Hz, 2H), 1.51 (s, 9H) ppm; 13C NMR (CDCl3, 125 MHz) δ 171.7, 165.2, 138.9, 137.6, 134.7, 132.3, 129.8, 129.6,
129.5, 128.3, 81.7, 37.4, 28.0 ppm; IR (KBr) v 3180, 1703, 1650, 1286, 1177, 1160,
785 cm-1; HRMS (EI) (m/z): calcd for C15H17NO3 [M+] 259.1208; found 259.1208.
Characterization of Products 3-4:
tert-Butyl 1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (3a). White solid;
mp. 204-205 oC; 1H NMR (CDCl3, 500 MHz) δ 8.38 (b, 1H), 7.95 (d, J = 7.5 Hz, 1H),
7.50 (m, 2H), 7.45 (m, 1H), 7.28 (m, 1H), 3.51 (t, J = 7.0 Hz, 2H), 1.51 (s, 9H) ppm; 13C NMR (CDCl3, 125 MHz) δ 171.7, 165.2, 138.9, 137.6, 134.7, 132.3, 129.8, 129.6,
S3
NH
O
OtBuO3a
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
129.5, 128.3, 81.7, 37.4, 28.0 ppm; IR (KBr) v 3180, 1703, 1650, 1286, 1177, 1160,
785 cm-1; HRMS (EI) (m/z): calcd for C15H17NO3 [M+] 259.1208; found 259.1208.
tert-Butyl 7-methyl-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (3b).
Pale yellow solid; mp. 163-165 oC; 1H NMR (CDCl3, 400 MHz) δ 8.33 (b, 1H), 7.85
(d, J = 8.0 Hz, 1H), 7.32 (s, 1H), 7.26 (m, 2H), 3.51 (t, J = 6.4 Hz, 2H), 2.42 (s, 3H),
1.52 (s, 9H) ppm; 13C NMR (CDCl3, 125 MHz) δ 165.3, 140.1, 138.6, 137.6, 132.2,
132.1, 129.9, 129.7, 129.2, 81.6, 37.5, 28.0, 21.4 ppm; IR (KBr) v 3176, 3047, 1710,
1652, 1283, 1158 cm-1; HRMS (EI) (m/z): calcd for C16H19NO3 [M+] 273.1365; found
273.1358. tert-Butyl 1-oxo-7-phenyl-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (3c).
White solid; mp. 222-224 oC; 1H NMR (CDCl3, 400 MHz) δ 8.04 (d, J = 8.0 Hz, 1H),
7.98 (b, 1H), 7.76 (d, J = 1.6 Hz, 1H), 7.68 (dd, J1 = 8.4 Hz, J2 = 2.0 Hz, 1H), 7.63 (m,
2H), 7.47 (m, 2H), 7.36 (m, 2H), 3.58 (t, J = 6.4 Hz, 2H), 1.53 (s, 9H) ppm; 13C NMR
(CDCl3, 100 MHz) δ 171.5, 165.2, 142.7, 139.9, 139.0, 137.8, 133.4, 132.7, 130.3,
128.9, 128.3, 128.0, 127.2, 127.1, 81.8, 37.6, 28.1 ppm; IR (KBr) v 3187, 1702, 1651,
1411, 1280, 1160 cm-1; HRMS (EI) (m/z): calcd for C21H21NO3 [M+] 335.1521; found
335.1523.
S4
NH
O
OtBuO3b
Me
NH
O
OtBuO
3c
Ph
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
tert-Butyl 7-cyano-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (3d).
Yellow solid; mp. 204-205 oC; 1H NMR (CDCl3, 400 MHz) δ 8.04 (d, J = 8.0 Hz, 1H),
7.92 (d, J = 1.6 Hz, 1H), 7.71 (dd, J1 = 8.0 Hz, J2 = 1.2 Hz, 1H), 7.43 (m, 1H), 7.20 (b,
1H), 3.56 (t, J = 7.2 Hz, 2H), 1.54 (s, 9H) ppm; 13C NMR (CDCl3, 100 MHz) δ 169.3,
163.9, 140.6, 138.4, 136.2, 133.8, 133.0, 131.2, 130.8, 117.9, 114.0, 82.8, 37.5, 28.0
ppm; IR (KBr) v 2964, 2227, 1703, 1653, 1474, 1288, 1261, 1092, 801 cm-1; HRMS
(EI) (m/z): calcd for C16H16N2O3 [M+] 284.1161; found 284.1161. tert-Butyl 1-oxo-7-(trifluoromethyl)-2,3-dihydro-1H-benzo[c]azepine-5-carboxy
late (3e). White solid; mp. 210-211 oC; 1H NMR (CDCl3, 400 MHz) δ 8.07 (d, J = 8.0
Hz, 1H), 7.84 (s, 1H), 7.70 (d, J = 8.4 Hz, 1H), 7.48 (b, 1H), 7.42 (m, 1H), 3.56 (t, J =
6.4 Hz, 2H), 1.51 (s, 9H) ppm; 13C NMR (CDCl3, 100 MHz) δ 170.3, 164.3, 140.4,
137.7, 136.9, 132.9, 131.8 (q, J = 32 Hz), 130.5, 127.0 (q, J = 4 Hz), 124.8 (q, J = 3
Hz), 123.6 (d, J = 272 Hz), 82.5, 37.5, 28.0 ppm; IR (KBr) v 3345, 2960, 1690, 1655,
1316, 1158, 1080 cm-1; HRMS (EI) (m/z): calcd for C16H16F3NO3 [M+] 327.1082;
found 327.1092.
S5
NH
O
OtBuO3d
NC
NH
O
OtBuO3e
F3C
NH
O
OtBuO3f
MeO
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
tert-Butyl 7-methoxy-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (3f).
Pale yellow solid; mp. 192-194 oC; 1H NMR (CDCl3, 400 MHz) δ 8.17 (b, 1H), 7.92
(d, J = 8.4 Hz, 1H), 7.27 (m, 1H), 7.01 (m, 2H), 3.86 (s, 3H), 3.52 (t, J = 6.4 Hz, 2H),
1.52 (s, 9H) ppm; 13C NMR (CDCl3, 125 MHz) δ 171.5, 165.2, 160.4, 138.8, 137.5,
134.0, 131.6, 127.4, 114.6, 114.2, 81.7, 55.3, 37.4, 28.0 ppm; IR (KBr) v 3167, 1710,
1649, 1280, 1246, 1170 cm-1; HRMS (EI) (m/z): calcd for C16H19NO4 [M+] 289.1314;
found 289.1317. tert-Butyl 7-chloro-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (3g).
Pale yellow solid; mp. 176-178 oC; 1H NMR (CDCl3, 400 MHz) δ 7.99 (b, 1H), 7.88
(d, J = 8.4 Hz, 1H), 7.56 (d, J = 2.4 Hz, 1H), 7.42 (dd, J1 = 8.8 Hz, J2 = 2.4 Hz, 1H),
7.34 (m, 1H), 3.53 (d, J = 7.0 Hz, 2H), 1.52 (s, 9H) ppm; 13C NMR (CDCl3, 100 MHz)
δ 170.7, 164.5, 139.9, 136.7, 136.2, 133.7, 133.1, 131.2, 129.6, 128.6, 82.2, 37.4, 28.0
ppm; IR (KBr) v 3180, 2986, 1705, 1653, 1292, 1165, 846 cm-1; HRMS (EI) (m/z):
calcd for C15H16ClNO3 [M+] 293.0819; found 293.0808.
tert-Butyl 7-bromo-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (3h).
Pale yellow solid; mp. 183-185 oC; 1H NMR (CDCl3, 400 MHz) δ 7.92 (b, 1H), 7.82
(d, J = 8.4 Hz, 1H), 7.73 (d, J = 2.0 Hz, 1H), 7.58 (dd, J = 8.4 Hz, J = 2.0 Hz, 1H),
7.35 (m, 1H), 3.54 (t, J = 6.8 Hz, 2H), 1.53 (s, 9H) ppm; 13C NMR (CDCl3, 100 MHz)
δ 170.7, 164.4, 140.0, 136.6, 133.9, 133.5, 132.6, 131.5, 131.3, 124.6, 82.2, 37.4, 28.0
S6
NH
O
OtBuO3g
Cl
NH
O
OtBuO
3h
Br
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
ppm; IR (KBr) v 3183, 2983, 1708, 1654, 1290, 1163 cm-1; HRMS (EI) (m/z): calcd
for C15H16BrNO3 [M+] 337.0314; found 337.0314.
tert-Butyl 7-iodo-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (3i). White
solid; mp. 202-204 oC; 1H NMR (CDCl3, 400 MHz) δ 7.93 (m, 2H), 7.79 (dd, J1 = 8.4
Hz, J2 = 1.6 Hz, 1H), 7.65 (d, J = 8.4 Hz, 1H), 7.34 (m, 1H), 3.53 (t, J = 6.4 Hz, 2H),
1.53 (s, 9H) ppm; 13C NMR (CDCl3, 100 MHz) δ 170.9, 164.4, 140.0, 138.6, 137.3,
136.5, 134.1, 133.8, 131.1, 96.7, 82.2, 37.4, 28.0 ppm; IR (KBr) v 3180, 2924, 1699,
1652, 1578, 1280, 1158 cm-1; HRMS (EI) (m/z): calcd for C15H16INO3 [M+] 385.0175;
found 385.0174. tert-Butyl 7-nitro-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (3j).
White solid; mp. 202-203 oC; 1H NMR (CDCl3, 400 MHz) δ 8.49 (d, J = 2.4 Hz, 1H),
8.26 (dd, J1 = 8.8 Hz, J2 = 2.4 Hz, 1H), 8.11 (d, J = 8.4 Hz, 1H), 7.54 (b, 1H), 7.48 (m,
1H), 3.59 (t, J = 6.8 Hz, 2H), 1.54 (s, 9H) ppm; 13C NMR (CDCl3, 100 MHz) δ 169.3,
163.8, 148.3, 140.9, 139.8, 136.4, 133.6, 131.4, 125.1, 122.7, 82.9, 37.5, 28.0 ppm; IR
(KBr) v 3201, 2925, 1710, 1665, 1524, 1346, 1279, 1155 cm-1; HRMS (EI) (m/z):
calcd for C15H16N2O3 [M+] 304.1059; found 304.1056.
S7
NH
O
OtBuO3i
I
NH
O
OtBu3j
O2N
O
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
tert-Butyl 8-methyl-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (3k).
Yellow solid; mp. 198-200 oC; 1H NMR (CDCl3, 400 MHz) δ 7.67 (m, 2H), 7.40 (d, J
= 8.0 Hz, 1H), 7.31 (dd, J1 = 8.4 Hz, J2 = 1.6 Hz, 1H), 7.22 (m, 1H), 3.51 (t, J = 6.4
Hz, 2H), 2.42 (s, 3H), 1.50 (s, 9H) ppm; 13C NMR (CDCl3, 100 MHz) δ 171.4, 165.4,
138.5, 138.0, 137.7, 134.5, 131.0, 130.0, 129.6, 129.5, 81.7, 37.6, 28.0, 21.1 ppm; IR
(KBr) v 2964, 2925, 1706, 1649, 1262, 1095, 802 cm-1; HRMS (EI) (m/z): calcd for
C16H19NO3 [M+] 273.1365; found 273.1366. tert-Butyl 8-methyl-7-nitro-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate
(3l). Pale yellow solid; mp. 214-215 oC; 1H NMR (CDCl3, 400 MHz) δ 8.22 (s, 1H),
7.93 (s, 1H), 7.41 (m, 1H), 7.23 (b, 1H), 3.58 (t, J = 6.4 Hz, 2H), 2.66 (s, 3H), 1.53 (s,
9H) ppm; 13C NMR (CDCl3, 100 MHz) δ 169.5, 164.0, 149.6, 140.2, 138.2, 136.3,
134.2, 133.2, 131.2, 126.2, 82.8, 37.5, 28.0, 20.0 ppm; IR (KBr) v 2960, 1710, 1661,
1520, 1342, 1157 cm-1; HRMS (EI) (m/z): calcd for C16H18N2O5 [M+] 318.1216;
found 318.1211.
tert-Butyl 6,8-dichloro-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (3m).
White solid; mp. 151-153 oC; 1H NMR (CDCl3, 400 MHz) δ 7.86 (d, J = 2.0 Hz
S8
NH
O
OtBuO
Me
3k
NH
O
OtBuO
3l
O2N
Me
NH
O
3m
Cl
ClO OtBu
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
, 1H), 7.57 (d, J = 2.4 Hz, 1H), 7.32 (b, 1H), 7.27 (m, 1H), 3.55 (m, 2H), 1.47 (s, 9H)
ppm; 13C NMR (CDCl3, 100 MHz) δ 168.8, 164.2, 139.5, 137.7, 136.9, 135.1, 134.8,
131.8, 130.3, 128.3, 82.3, 37.6, 27.8 ppm; IR (KBr) v 3425, 2978, 1719, 1656, 1285,
1159 cm-1; HRMS (EI) (m/z): calcd for C15H15Cl2N2O3 [M+] 327.0429; found
327.0429. tert-Butyl 6-oxo-7,8-dihydro-6H-[1,3]dioxolo[4',5':3,4]benzo[1,2-c]azepine-10-
carboxylate (3n). White solid; mp. 203-205 oC; 1H NMR (CDCl3, 400 MHz) δ 7.75
(b, 1H), 7.57 (d, J = 8.0 Hz, 1H), 7.17 (m, 1H), 6.93 (d, J = 8.4 Hz, 1H), 6.05 (s, 2H),
3.56 (t, J = 6.8 Hz, 2H), 1.47 (s, 9H) ppm; 13C NMR (CDCl3, 100 MHz) δ 170.7,
164.7, 149.1, 144.6, 138.9, 134.8, 128.2, 124.9, 115.8, 108.9, 101.6, 81.6, 37.6, 27.9
ppm; IR (KBr) v 2975, 2925, 1715, 1654, 1445, 1282, 1251, 1160 cm-1; HRMS (EI)
(m/z): calcd for C16H17NO5 [M+] 303.1107; found 303.1108. tert-Butyl 1-oxo-2,3-dihydro-1H-naphtho[1,2-c]azepine-5-carboxylate (3o).
Yellow solid; mp. 189-191 oC; 1H NMR (CDCl3, 400 MHz) δ 8.49 (d, J = 8.0 Hz, 1H),
7.88 (m, 2H), 7.57 (m, 3H), 7.42 (m, 1H), 7.34 (b, 1H), 3.54 (m, 2H), 1.53 (s, 9H)
ppm; 13C NMR (CDCl3, 100 MHz) δ 170.2, 165.1, 140.1, 138.5, 133.1, 131.7, 130.8,
130.6, 129.3, 127.9, 127.3, 127.1, 127.0, 125.8, 82.0, 37.9, 28.1 ppm; IR (KBr) v
2974, 2926, 1710, 1654, 1276, 1162, 1086 cm-1; HRMS (EI) (m/z): calcd for
C19H19NO3 [M+] 309.1365; found 309.1366.
S9
NH
O
3nO OtBu
OO
NH
O
OtBuO
3o
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
Methyl 1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (4a). White solid;
mp. 172-174 oC; 1H NMR (CDCl3, 500 MHz) δ 7.96 (m, 1H), 7.75 (b, 1H), 7.49 (m,
3H), 7.39 (m, 1H), 3.82 (s, 3H), 3.54 (m, 2H) ppm; 13C NMR (CDCl3, 125 MHz) δ
171.2, 166.5, 139.9, 136.3, 134.7, 131.8, 130.2, 129.8, 129.4, 128.6, 52.4, 37.5 ppm;
IR (KBr) v 3186, 3071, 1715, 1659, 1264, 1245, 788 cm-1; HRMS (EI) (m/z): calcd
for C12H11NO3 [M+] 217.0739; found 217.0741. 3-Bromopropyl 1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (4b). White
solid; mp. 95-97 oC; 1H NMR (CDCl3, 400 MHz) δ 8.10 (b, 1H), 7.96 (d, J = 7.6 Hz,
1H), 7.50 (m, 3H), 7.38 (m, 1H), 4.37 (t, J = 8.4 Hz, 2H), 3.55 (t, J = 6.4 Hz, 2H),
3.43 (t, J = 6.4 Hz, 2H), 3.21 (m, 2H) ppm; 13C NMR (CDCl3, 100 MHz) δ 171.4,
165.8, 140.2, 136.2, 134.7, 131.7, 130.1, 129.8, 129.3, 128.7, 63.0, 37.5, 31.3, 29.3
ppm; IR (KBr) v 3177, 1716, 1649, 1241, 783 cm-1; HRMS (EI) (m/z): calcd for
C14H14BrNO3 [M+] 323.0157; found 323.0150. 3-Bromopropyl 1-oxo-7-phenyl-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate
S10
NH
O
OMeO4a
NH
O
OOBr
3
4b
NH
O
OOBr
3
Ph
4c
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
(4c). White solid; mp. 173-174 oC; 1H NMR (CDCl3, 400 MHz) δ 8.05 (d, J = 8.0 Hz,
1H), 7.80 (b, 1H), 7.73 (m, 2H), 7.63 (m, 2H), 7.43 (m, 4H), 4.40 (t, J = 6.0 Hz, 2H),
3.62 (t, J = 6.8 Hz, 2H), 3.42 (t, J = 6.4 Hz, 2H), 3.22 (m, 2H) ppm; 13C NMR (CDCl3,
100 MHz) δ 171.2, 165.8, 143.0, 140.3, 139.6, 136.2, 133.4, 132.1, 130.5, 128.9,
128.1, 128.0, 127.3, 63.1, 37.6, 31.5, 29.3 ppm; IR (KBr) v 2962, 1717, 1648, 1418,
1263, 1094, 1025 cm-1; HRMS (EI) (m/z): calcd for C20H18BrNO3 [M+] 399.0470;
found 399.0464. 3-Bromopropyl 1-oxo-2,3-dihydro-1H-naphtho[1,2-c]azepine-5-carboxylate (4d).
Yellow solid; mp. 68-70 oC; 1H NMR (CDCl3, 400 MHz) δ 8.50 (d, J = 8.0 Hz, 1H),
7.89 (m, 3H), 7.59 (m, 2H), 7.51 (m, 2H), 4.40 (m, 2H), 3.63 (m, 1H), 3.47 (m, 3H),
2.22 (m, 2H) ppm; 13C NMR (CDCl3, 100 MHz) δ 170.3, 165.8, 141.7, 136.6, 133.1,
131.8, 130.5, 130.1, 129.5, 128.0, 127.5, 127.11, 127.08, 125.5, 63.0, 37.8, 31.3, 29.4
ppm; IR (KBr) v 2963, 1718, 1652, 1262, 1237, 1088 cm-1; HRMS (EI) (m/z): calcd
for C18H16BrNO3 [M+] 373.0314; found 373.0318.
Ethyl 4-methyl-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (4e).
White solid; mp. 159-161 oC; 1H NMR (CDCl3, 400 MHz) δ 7.97 (m, 2H), 7.44 (m,
2H), 7.28 (m, 1H), 4.26 (q, J = 7.2 Hz, 2H), 3.49 (d, J = 6.0 Hz, 2H), 2.21 (s, 3H),
1.26 (t, J = 7.2 Hz, 3H) ppm; 13C NMR (CDCl3, 100 MHz) δ 171.1, 168.2, 144.7,
134.0, 133.8, 132.0, 130.4, 129.9, 127.9, 127.7, 61.1, 44.8, 21.1, 14.1 ppm; IR (KBr)
S11
NH
O
OO4d
Br3
NH
O
OEt
MeO
4e
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
v 3177, 1713, 1655, 1475, 1097, 817 cm-1; HRMS (EI) (m/z): calcd for C14H15NO3
[M+] 245.1052; found 245.1049.
Ethyl 4-methyl-1-oxo-7-(trifluoromethyl)-2,3-dihydro-1H-benzo[c]azepine-5-
carboxylate (4f). White solid; mp. 126-128 oC; 1H NMR (CDCl3, 400 MHz) δ 8.23
(b, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.65 (d, J = 8.0 Hz, 1H), 7.57 (b, 1H), 4.27 (q, J =
7.2 Hz, 2H), 3.50 (d, J = 6.0 Hz, 2H), 2.27 (s, 3H), 1.26 (t, J = 7.2 Hz, 3H) ppm; 13C
NMR (CDCl3, 100 MHz) δ 169.9, 167.2, 147.7, 136.8, 134.8, 132.2 (q, J = 32 Hz),
130.8, 130.6, 125.2 (q, J = 4 Hz), 124.4 (q, J = 4 Hz), 123.4 (d, J = 271 Hz), 61.4,
45.1, 21.3, 14.0 ppm; IR (KBr) v 3335, 1725, 1625, 1334, 1304, 1220, 1131, 1083
cm-1; HRMS (EI) (m/z): calcd for C15H14F3NO3 [M+] 313.0926; found 313.0930.
Ethyl 7-methoxy-4-methyl-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate
(4g). White solid; mp. 129-131 oC; 1H NMR (CDCl3, 400 MHz) δ 7.92 (d, J = 8.8 Hz,
1H), 7.64 (b, 1H), 6.95 (dd, J1 = 8.8 Hz, J2 = 2.4 Hz, 1H), 6.95 (d, J = 2.4 Hz, 1H),
4.25 (q, J = 7.2 Hz, 2H), 3.82 (s, 3H), 3.48 (d, J = 6.4 Hz, 2H), 2.17 (s, 3H), 1.27 (t, J
= 7.2 Hz, 3H) ppm; 13C NMR (CDCl3, 100 MHz) δ 170.8, 168.2, 160.9, 144.1, 135.7,
132.04, 131.98, 126.5, 114.2, 112.2, 61.1, 55.4, 44.8, 21.1, 14.1 ppm; IR (KBr) v 3171,
2919, 1726, 1650, 1296, 1229 cm-1; HRMS (EI) (m/z): calcd for C15H17NO4 [M+]
275.1158; found 275.1153.
S12
NH
O
OEt
MeO
F3C
4f
NH
O
OEt
MeO
MeO
4g
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
Ethyl 7-iodo-4-methyl-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate
(4h). White solid; mp. 178-180 oC; 1H NMR (CDCl3, 400 MHz) δ 8.15 (b, 1H), 7.73
(dd, J1 = 8.0 Hz, J2= 1.6 Hz, 1H), 7.64 (d, J = 8.4 Hz, 2H), 4.27 (q, J = 7.2 Hz, 2H),
3.46 (d, J = 6.4 Hz, 2H), 2.20 (s, 3H), 1.27 (t, J = 7.2 Hz, 3H) ppm; 13C NMR (CDCl3,
100 MHz) δ 170.5, 167.5, 146.5, 136.9, 136.8, 135.6, 133.2, 131.3, 130.6, 97.2, 61.3,
44.8, 21.2, 14.1 ppm; IR (KBr) v 3283, 1717, 1620, 1222, 1045 cm-1; HRMS (EI)
(m/z): calcd for C14H14INO3 [M+] 371.0018; found 371.0020.
Ethyl 4,8-dimethyl-7-nitro-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate
(4i). Pale yellow solid; mp. 192-194 oC; 1H NMR (CDCl3, 400 MHz) δ 7.94 (s, 1H),
7.93 (s, 1H), 7.77 (b, 1H), 4.29 (q, J = 7.2 Hz, 2H), 3.52 (d, J = 6.4 Hz, 2H), 2.64 (s,
3H), 2.28 (s, 3H), 1.29 (t, J = 6.8 Hz, 3H) ppm; 13C NMR (CDCl3, 100 MHz) δ 169.1,
166.9, 149.8, 147.7, 137.3, 134.4, 133.1, 132.8, 130.3, 124.5, 61.6, 45.2, 21.4, 19.9,
14.1 ppm; IR (KBr) v 2925, 1724, 1667, 1519, 1343, 1215, 1066 cm-1; HRMS (EI)
(m/z): calcd for C15H16N2O3 [M+] 304.1059; found 304.1059.
S13
NH
O
OEt
MeO
I
4h
4i
NH
O
OEt
MeO
O2N
Me
NH
O
Me
4j
Cl
ClOEtO
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Ethyl 6,8-dichloro-4-methyl-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carbo
xylate (4j). Pale yellow solid; mp. 198-200 oC; 1H NMR (CDCl3, 400 MHz) δ 8.51
(b, 1H), 7.80 (d, J = 2.0 Hz, 1H), 7.51 (d, J = 2.0 Hz, 1H), 4.15 (m, 2H), 3.57 (m, 1H),
3.37 (m, 1H), 2.37 (s, 3H), 1.16 (t, J = 7.2 Hz, 3H) ppm; 13C NMR (CDCl3, 100 MHz)
δ 169.1, 165.9, 151.8, 137.3, 134.8, 134.4, 132.4, 131.6, 127.9, 127.8, 61.2, 46.1, 20.5,
13.8 ppm; IR (KBr) v 3334, 1725, 1623, 1228, 1092, 812 cm-1; HRMS (EI) (m/z):
calcd for C14H13Cl2NO3 [M+] 313.0272; found 313.0276.
Ethyl 1-oxo-4-phenyl-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (4k). White
solid; mp. 205-207 oC; 1H NMR (CDCl3, 400 MHz) δ 8.02 (d, J = 7.6 Hz, 1H), 7.64
(b, 1H), 7.49 (m, 3H), 7.35 (m, 5H), 4.02 (q, J = 6.8 Hz, 2H), 3.87 (d, J = 6.4 Hz, 2H),
0.94 (t, J = 7.2 Hz, 3H) ppm; 13C NMR (CDCl3, 100 MHz) δ 170.5, 168.5, 144.8,
139.4, 134.0, 133.9, 133.5, 130.8, 130.4, 128.6, 128.5, 128.4, 127.7, 127.3, 61.2, 45.0,
13.6 ppm; IR (KBr) v 2924, 1717, 1651, 1461, 1260, 1025 cm-1; HRMS (EI) (m/z):
calcd for C19H17NO3 [M+] 307.1208; found 307.1211.
Ethyl 7-methyl-1-oxo-4-phenyl-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate
(4l). White solid; mp. 200-202 oC; 1H NMR (CDCl3, 400 MHz) δ 7.92 (d, J = 8.4 Hz,
1H), 7.33 (m, 8H), 4.02 (q, J = 7.2 Hz, 2H), 3.85 (d, J = 6.4 Hz, 2H), 2.41 (s, 3H),
0.94 (t, J = 6.8 Hz, 3H) ppm; 13C NMR (CDCl3, 100 MHz) δ 170.5, 168.6, 144.4,
141.2, 139.5, 134.0, 133.4, 131.3, 130.5, 129.6, 129.5, 128.3, 128.0, 127.3, 61.2, 45.0,
S14
NH
O
OEt
PhO
4k
NH
O
OEt
PhO
Me
4l
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21.5, 13.6 ppm; IR (KBr) v 3177, 2924, 1719, 1659, 1227, 1084, 1022 cm-1; HRMS
(EI) (m/z): calcd for C20H19NO3 [M+] 321.1365; found 321.1367.
Ethyl 7-cyano-1-oxo-4-phenyl-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate
(4m). White solid; mp. 188-190 oC; 1H NMR (CDCl3, 400 MHz) δ 8.10 (d, J = 9.4 Hz,
1H), 7.90 (d, J = 1.6 Hz, 1H), 7.79 (b, 1H), 7.71 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.40
(m, 3H), 7.33 (m, 2H), 4.03 (q, J = 7.2 Hz, 2H), 3.88 (d, J = 6.4 Hz, 2H), 0.92 (t, J =
6.8 Hz, 3H) ppm; 13C NMR (CDCl3, 100 MHz) δ 168.9, 167.6, 147.4, 138.9, 137.6,
134.4, 131.8, 131.32, 131.25, 128.9, 128.7, 127.2, 117.7, 114.8, 61.7, 44.9, 13.5 ppm;
IR (KBr) v 3315, 2958, 2925, 2230, 1716, 1661, 1623, 1461, 1264, 1088, 1029 cm-1;
HRMS (EI) (m/z): calcd for C20H16N2O3 [M+] 332.1161; found 332.1161.
Ethyl 7-methoxy-1-oxo-4-phenyl-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate
(4n). White solid; mp. 181-183 oC; 1H NMR (CDCl3, 400 MHz) δ 7.99 (d, J = 8.4 Hz,
1H), 7.38 (m, 6H), 7.01 (m, 2H), 4.01 (q, J = 7.2 Hz, 2H), 3.86 (m, 5H), 0.95 (t, J =
7.6 Hz, 3H) ppm; 13C NMR (CDCl3, 100 MHz) δ 170.4, 168.4, 161.1, 144.7, 139.4,
135.1, 133.7, 132.5, 128.5, 128.4, 127.3, 126.7, 114.8, 112.3, 61.2, 55.4, 45.0, 13.6
ppm; IR (KBr) v 3173, 1720, 1656, 1604, 1294, 1239, 1041, 771 cm-1; HRMS (EI)
(m/z): calcd for C20H19NO4 [M+] 337.1314; found 337.1310.
S15
NH
O
OEt
PhO
NC
4m
NH
O
OEt
PhO
MeO
4n
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Ethyl 7-chloro-1-oxo-4-phenyl-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate
(4o). Pale red solid; mp. 168-170 oC; 1H NMR (CDCl3, 400 MHz) δ 7.96 (d, J = 8.4
Hz, 1H), 7.59 (b, 1H), 7.54 (d, J = 1.6 Hz, 1H), 7.43 (dd, J = 8.8 Hz, J = 2.0 Hz, 1H),
7.35 (m, 5H), 4.03 (q, J = 7.2 Hz, 2H), 3.86 (d, J = 6.4 Hz, 2H), 0.94 (t, J = 6.8 Hz,
3H) ppm; 13C NMR (CDCl3, 100 MHz) δ 169.7, 167.9, 146.1, 139.1, 137.1, 135.0,
132.7, 132.4, 132.0, 128.8, 128.6, 127.6, 1273, 61.5, 44.9, 13.5 ppm; IR (KBr) v 3178,
3062, 1722, 1662, 1588, 1452, 1201, 1024 cm-1; HRMS (EI) (m/z): calcd for
C19H16ClNO3 [M+] 341.0819; found 341.0820.
Ethyl 8-methyl-1-oxo-4-phenyl-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate
(4p). Pale yellow solid; mp. 177-179 oC; 1H NMR (CDCl3, 400 MHz) δ 7.84 (s, 1H),
7.34 (m, 7H), 7.11 (b, 1H), 4.02 (q, J = 6.8 Hz, 2H), 3.86 (d, J = 6.4 Hz, 2H), 2.44 (s,
3H), 0.95 (t, J = 7.2 Hz, 3H) ppm; 13C NMR (CDCl3, 100 MHz) δ 170.4, 168.6, 143.8,
139.5, 138.9, 134.0, 133.7, 131.8, 130.8, 128.6, 128.3, 127.8, 127.3, 61.2, 45.0, 21.2,
13.6 ppm; IR (KBr) v 2958, 2924, 1717, 1664, 1088, 1035 cm-1; HRMS (EI) (m/z):
calcd for C20H19NO3 [M+] 321.1365; found 321.1361.
S16
NH
O
OEt
PhO
Cl
4o
4p
NH
O
OEt
PhO
Me
NH
O
OEtO
Br4q
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Ethyl 4-(4-bromophenyl)-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate
(4q). White solid; mp. 177-179 oC; 1H NMR (CDCl3, 400 MHz) δ 8.02 (dd, J1= 7.2
Hz, J2 = 1.2 Hz, 1H), 7.49 (m, 5H), 7.32 (b, 1H), 7.22 (d, J = 8.4 Hz, 2H), 4.05 (q, J =
7.2 Hz, 2H), 4.83 (d, J = 6.4 Hz, 2H), 1.01 (t, J = 7.2 Hz, 3H) ppm; 13C NMR (CDCl3,
100 MHz) δ 170.3, 168.1, 143.4, 138.2, 134.5, 133.9, 133.2, 131.8, 131.0, 130.5,
129.0, 128.9, 127.7, 122.7, 61.5, 44.8, 13.7 ppm; IR (KBr) v 2930, 1721, 1657, 1462,
1261, 1205, 800 cm-1; HRMS (EI) (m/z): calcd for C19H16BrNO3 [M+] 385.0314;
found 385.0318.
Ethyl 4-(4-bromophenyl)-7-chloro-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-
carboxylate (4r). White solid; mp. 228-230 oC; 1H NMR (CDCl3, 400 MHz) δ 7.96
(d, J = 8.4 Hz, 1H), 7.52 (m, 3H), 7.45 (dd, J1= 8.4 Hz, J2= 1.6 Hz, 1H), 7.42 (b, 1H),
7.20 (d, J = 8.4 Hz, 2H), 4.06 (q, J = 7.2 Hz, 2H), 3.83 (d, J = 6.4 Hz, 2H), 1.01 (t, J =
7.2 Hz, 3H) ppm; 13C NMR (CDCl3, 100 MHz) δ 169.5, 167.6, 144.7, 137.9, 137.3,
134.7, 133.3, 132.3, 132.1, 131.9, 129.1, 128.9, 127.7, 122.9, 61.7, 44.8, 13.6 ppm; IR
(KBr) v 2960, 2925, 1720, 1656, 1461, 1261, 1082, 1024 cm-1; HRMS (EI) (m/z):
calcd for C19H15BrClNO3 [M+] 418.9924; found 418.9917.
S17
NH
O
OEtO
O
4s
NH
O
OEtO
Br4r
Cl
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Ethyl 4-(furan-2-yl)-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate (4s).
Red solid; mp. 78-80 oC; 1H NMR (CDCl3, 400 MHz) δ 8.01 (d, J = 7.2 Hz, 1H), 7.78
(b, 1H), 7.47 (m, 4H), 6.65 (d, J = 3.2 Hz, 1H), 6.46 (m, 1H), 4.32 (q, J = 6.8 Hz, 2H),
3.87 (m, 2H), 1.27 (t, J = 7.2 Hz, 3H) ppm; 13C NMR (CDCl3, 100 MHz) δ 170.7,
168.7, 150.2, 144.0, 133.8, 133.3, 131.0, 130.7, 129.9, 129.7, 128.6, 127.1, 112.0,
111.4, 61.7, 40.8, 14.0 ppm; IR (KBr) v 1722, 1655, 1259, 1234, 1203, 1025 cm-1;
HRMS (EI) (m/z): calcd for C17H15NO4 [M+] 297.1001; found 297.1002.
Ethyl 4-(furan-2-yl)-7-methyl-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carbo
xylate (4t). Red solid; mp. 83-85 oC; 1H NMR (CDCl3, 400 MHz) δ 7.91 (d, J = 8.0
Hz, 1H), 7.67 (b, 1H), 7.45 (d, J = 1.2 Hz, 1H), 7.27 (m, 2H), 6.63 (d, J = 3.6 Hz, 1H),
6.45 (m, 1H), 4.32 (q, J = 7.2 Hz, 2H), 3.86 (m, 2H), 2.39 (s, 3H), 1.28 (t, J = 6.8 Hz,
3H) ppm; 13C NMR (CDCl3, 100 MHz) δ 170.7, 168.8, 150.3, 143.9, 141.4, 133.2,
131.1, 130.8, 129.8, 129.63, 129.56, 127.4, 112.0, 111.3, 61.6, 40.9, 21.5, 14.0 ppm;
IR (KBr) v 3396, 1721, 1654, 1235, 1026 cm-1; HRMS (EI) (m/z): calcd for
C18H17NO4 [M+] 311.1158; found 311.1153.
Ethyl 4-(furan-2-yl)-7-iodo-1-oxo-2,3-dihydro-1H-benzo[c]azepine-5-carboxylate
(4u). Red solid; mp. 88-90 oC; 1H NMR (CDCl3, 400 MHz) δ 7.87 (d, J = 1.6 Hz, 1H),
7.78 (dd, J = 8.4 Hz, J = 1.6 Hz, 1H), 7.70 (d, J = 8.4 Hz, 1H), 7.63 (b, 1H), 7.46 (d, J
= 1.6 Hz, 1H), 6.66 (d, J = 3.2 Hz, 1H), 6.48 (m, 1H), 4.34 (q, J = 7.2 Hz, 2H),
S18
NH
O
OEtO
O
Me
4t
NH
O
OEtO
O
I
4u
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3.87 (m, 2H), 1.29 (t, J = 7.2 Hz, 3H) ppm; 13C NMR (CDCl3, 100 MHz) δ 170.0,
168.2, 149.9, 144.3, 137.6, 135.9, 134.9, 133.1, 132.1, 130.9, 128.2, 112.2, 112.0,
98.0, 61.9, 40.8, 14.0 ppm; IR (KBr) v 3404, 1721, 1655, 1578, 1251, 1022, 742 cm-1;
HRMS (EI) (m/z): calcd for C17H14INO4 [M+] 422.9968; found 422.9966.
Ethyl 6-oxo-9-(thiophen-2-yl)-7,8-dihydro-6H-[1,3]dioxolo[4',5':3,4]benzo[1,2-c]
azepine-10-carboxylate (4v). White solid; mp. 220-222 oC; 1H NMR (CDCl3, 400
MHz) δ 7.62 (d, J = 8.4 Hz, 1H), 7.41 (dd, J1 = 4.2 Hz, J2 = 1.2 Hz, 1H), 7.15 (m, 1H),
7.04 (m, 1H), 6.94 (d, J = 8.4 Hz, 1H), 6.81 (b, 1H), 6.04 (s, 2H), 4.14 (q, J = 6.8 Hz,
2H), 3.95 (m, 2H), 1.12 (t, J = 7.2 Hz, 3H) ppm; 13C NMR (CDCl3, 100 MHz) δ
169.4, 167.3, 149.3, 145.0, 139.9, 138.8, 128.5, 128.2, 127.8, 127.6, 127.4, 125.7,
116.9, 109.1, 102.0, 61.4, 46.7, 13.7 ppm; IR (KBr) v 2923, 1720, 1652, 1442, 1247,
1035 cm-1; HRMS (EI) (m/z): calcd for C18H15NO5S [M+] 357.0671; found 357.0668.
7-Iodo-5-pentanoyl-2,3-dihydro-1H-benzo[c]azepin-1-one (4w). White solid; mp.
167-169 oC; 1H NMR (CDCl3, 400 MHz) δ 7.81 (dd, J1= 8.4 Hz, J2 = 1.6 Hz, 1H),
7.68 (m, 2H), 7.26 (b, 1H), 7.13 (m, 1H), 3.57 (t, J = 6.8 Hz, 2H), 2.71 (t, J = 7.2 Hz,
2H), 1.63 (m, 2H), 1.36 (m, 2H), 0.92 (t, J = 7.2 Hz, 3H) ppm; 13C NMR (CDCl3, 100
MHz) δ 200.7, 170.3, 143.7, 138.1, 137.8, 134.1, 133.5, 131.5, 97.1, 39.4, 37.6, 26.4,
22.3, 13.9 ppm; IR (KBr) v 2956, 2926, 1654, 1578, 1147, 1079 cm-1; HRMS (EI)
(m/z): calcd for C15H16INO2 [M+] 369.0226; found 369.0222.
S19
4v
NH
O
OO
O OEt S
NH
O
BuO
I
4w
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Synthesis of Pyrazole 5:
When styryldiazoacetate 2j was subject to the standard reaction condition, pyrazole 5
was obtained exclusively in 83% yield.
methyl 5-phenyl-1H-pyrazole-3-carboxylate (5). Yellow solid; mp. 183-185 oC; 1H
NMR (CDCl3, 500 MHz) δ 12.0 (b, 1H), 7.73 (t, J = 7.5 Hz, 2H), 7.42 (t, J = 7.0 Hz,
2H), 7.35 (t, J = 7.0 Hz, 1H), 7.08 (s, 1H), 3.87 (s, 3H) ppm; 13C NMR (CDCl3, 100
MHz) δ 161.1, 149.4, 130.6, 128.9, 128.4, 125.7, 105.6, 52.2 ppm; HRMS (ESI) (m/z):
calcd for C11H10N2O2 [M+H] + 203.0821; found 203.0813.
Derivation of Product 3m to 6 and 7:
Azepinone 3m (0.12 mmol, 40 mg) was added to Schlenk tube, vacuumed and refilled
with argon for three times. Anhydrous DCM (2 mL) was added and the solution was
stirred for 10 mins at RT. Then the reaction solution was cooled -78 oC, and DIBAL-H
(0.24 mL, 1.5 M in toluene) was added. The reaction solution was stirred for 20 mins
and poured into aqueous solution of Rochelle’s salt (2 mL). The organic layer was
separated and the aqueous layer was extracted with DCM. The combined organic
S20
NH
O
3m
Cl
ClO OtBu
DIBAL-H
DCM-78 oC
NH
OCl
ClO OtBu
6
82%
CsOAc ( 1 equiv)
CH3CN, RT2j 5, 83%
CO2CH3
N2
PhHN N
PhCO2CH3
[Cp*RhCl2]2 (2 mol%)
5
HN N
PhCO2CH3
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layer was washed with brine, dried over MgSO4. The solvent was removed by rotary
evaporation. The residue was subject to flash chromatography on silica gel using ethyl
acetate/petroleum ether (v/v, 1:2) as eluent to give product 6 (33 mg, 82%) as a white
solid.
tert-Butyl 6,8-dichloro-1-oxo-2,3,4,5-tetrahydro-1H-benzo[c]azepine-5-carbo
xylate (6). White solid; mp. 150-151 oC; 1H NMR (CDCl3, 400 MHz) δ 7.65 (d, J =
2.0 Hz, 1H), 7.54 (d, J = 2.4 Hz, 1H), 6.54 (b, 1H), 4.52 (d, J = 7.6 Hz, 1H), 3.24 (m,
1H), 2.97 (m, 2H), 1.97 (m, 1H), 1.33 (s, 9H) ppm; 13C NMR (CDCl3, 100 MHz) δ
171.0, 170.4, 138.0, 134.6, 133.9, 132.5, 131.4, 128.2, 82.4, 43.8, 38.9, 31.8, 27.9
ppm; IR (KBr) v 2925, 1730, 1672, 1251, 1153 cm-1; HRMS (EI) (m/z): calcd for
C15H17Cl2NO3 [M+] 329.0585; found 329.0577.
Azepinone 3m (0.2 mmol, 65.6 mg) was added to flask, DCM (10 mL) was added and
the solution was stirred for 5 min, aqueous NaHCO3 solution (0.5 M, 10 mL) was
added afterward. m-CPBA (69 mg, 0.4 mmol) was added to the biphasic solution and
the solution was kept at RT for 24 h. Then the mixture was poured into separatory
funnel, the organic layer was separated and the aqueous layer was extracted with
DCM. The combined organic layer was washed with NaHCO3 solution, brine, dried
over MgSO4. The solvent was removed by rotary evaporation. The residue was
subject to flash chromatography on silica gel using ethyl acetate/petroleum ether (v/v,
1:1) as eluent to give product 7 (65 mg, 95%) as white solid.
S21
NH
OCl
ClO OtBu
6
NH
O
3m
Cl
ClO OtBu
m-CPBANaHCO3
DCM
NH
OCl
ClO OtBu
O
795%
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tert-Butyl 6,8-dichloro-4-oxo-2,3,4,8b-tetrahydro-1aH-benzo[c]oxireno[2,3-e]
azepine-8b-carboxylate (7). White solid; mp. 69-71 oC; 1H NMR (CDCl3, 400
MHz) δ 7.73 (d, J = 2.0 Hz, 1H), 7.59 (d, J = 2.0 Hz, 1H), 7.47 (b, 1H), 3.94 (m, 1H),
3.83 (m, 1H), 2.91 (m, 1H), 1.38 (s, 9H) ppm; 13C NMR (CDCl3, 100 MHz) δ 169.0,
166.2, 137.6, 136.3, 135.5, 132.1, 128.9, 128.7, 83.9, 61.4, 57.6, 43.4, 27.6 ppm; IR
(KBr) v 2980, 1735, 1666, 1370, 1163 cm-1; HRMS (EI) (m/z): calcd for
C15H15Cl2NO4 [M+] 343.0378; found 343.0379.
Kinetic Isotope Effect Study
[D4]-3a was prepared according to general procedure in 70% yield.
White solid; mp. 203-205 oC; 1H NMR (CDCl3, 400 MHz) δ 7.28 (m, 1H), 6.96 (b,
1H), 3.53 (m, 2H), 1.51 (s, 9H) ppm; 13C NMR (CDCl3, 125 MHz) δ 171.1, 165.2,
138.4, 138.1, 134.5, 132.1, 81.9, 37.6, 28.0 ppm; IR (KBr) v 2924, 2853, 1713, 1656,
1461, 1274, 1148 cm-1; HRMS (EI) (m/z): calcd for C15H13D4NO3 [M+] 263.1460;
found 263.1460.
S22
NH
O
OtBuO[D4]-3a
D4
NHOPiv
O[Cp*RhCl2]2 (2 mol%)
CsOAc (1 equiv)CH3CN, RT, 20 min[D5]-1a/1a
NH
O
OtBuO
H5/D5H4/D4
2a (1.5 equiv)
KIE = 2.8 [D4]-3a/3aparallel experiments
NH
OCl
ClO OtBu
O
7
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
Following general procedure, [Cp*RhCl2]2 (0.6 mg, 2 mol%), benzamide 1a (22.1 mg,
0.1 mmol), CsOAc (20 mg, 0.1 mmol) were added to a vial. CH3CN (0.6 mL) was
added, followed by micro-syringe addition of vinyldiazoacetate 2a (25.2 mg, 0.15
mmol). The micro-syringe was washed with an additional 0.15 mL CH3CN and added
to the reaction solution. In another reaction vial, [D5]-1a (22.6 mg, 0.1 mmol, 1.0
equiv) was used instead of 1a. The two reactions were allowed to stir at RT for 20 min.
Afterwards, the reactions were quenched with water, combined and extracted with
CH2Cl2. The organic layer was washed with brine, dried over Na2SO4. The product
(15.6 mg, 30% combined yield) was isolated by flash chromatography. The value of
KH/KD was obtained based on 1HNMR.
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
9.00
1.98
0.74
1.01
1.74
1.82
1.50
5
3.50
33.
520
3.53
6
7.26
07.
280
7.29
87.
439
7.44
77.
454
7.45
87.
467
7.49
57.
499
7.50
87.
511
7.92
37.
933
7.95
2
Reference:
1 H. Wang, F. Glorius, Angew. Chem., Int. Ed., 2012, 51, 7318-7322.
2 (a) H. M. L. Davies, B. Hu, E. Saikali, P. R. Bruzinski, J. Org. Chem., 1994, 59,
4535-4541; (b) V. V. Pagar, A. M. Jdhav, R.-S. Liu, J. Am. Chem. Soc., 2011, 133,
20728-20731.
S23
NH
O
OtBuO
[D4]-3a/3a
D4/H4
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
9.00
1.98
1.07
0.98
1.96
0.95
0.95
1.50
7
3.50
23.
514
3.52
8
7.26
77.
270
7.28
17.
296
7.43
17.
435
7.44
67.
459
7.46
37.
482
7.49
87.
511
7.52
37.
940
7.95
5
8.37
5
NH
O
OtBuO3a
S24
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
9.00
1.98
1.07
0.98
1.96
0.95
0.95
1.50
7
3.50
23.
514
3.52
8
7.26
77.
270
7.28
17.
296
7.43
17.
435
7.44
67.
459
7.46
37.
482
7.49
87.
511
7.52
37.
940
7.95
5
8.37
5
NH
O
OtBuO3a
S25
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.23.64.04.44.85.25.66.06.46.87.07.27.47.67.88.28.69.09.4f1 (ppm)
1.98
1.07
0.98
1.96
0.95
0.95
3.50
23.
514
3.52
8
7.26
77.
270
7.28
17.
296
7.43
17.
435
7.44
67.
459
7.46
37.
482
7.49
87.
511
7.52
37.
940
7.95
5
8.37
5
NH
O
OtBuO3a
S26
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180f1 (ppm)
27.9
5
37.4
2
76.7
577
.00
77.2
581
.70
128.
2512
9.45
129.
5612
9.83
132.
2913
4.71
137.
6313
8.87
165.
17
171.
71
NH
O
OtBuO3a
S27
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
9.00
2.96
1.94
2.05
0.96
0.96
0.91
1.52
0
2.42
2
3.49
23.
507
3.52
3
7.24
07.
258
7.27
77.
323
7.84
17.
861
8.33
0
NH
O
OtBuO3b
Me
S28
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
9.00
2.96
1.94
2.05
0.96
0.96
0.91
1.52
0
2.42
2
3.49
23.
507
3.52
3
7.24
07.
258
7.27
77.
323
7.84
17.
861
8.33
0
NH
O
OtBuO3b
Me
S29
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
2.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
2.96
1.94
2.05
0.96
0.96
0.91
2.42
2
3.49
23.
507
3.52
3
7.24
07.
258
7.27
77.
323
7.84
17.
861
8.33
0
NH
O
OtBuO3b
Me
S30
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170f1 (ppm)
21.4
3
27.9
8
37.4
5
76.7
577
.00
77.2
581
.57
129.
2012
9.65
129.
8913
2.07
132.
2213
7.62
138.
6114
0.05
165.
25
NH
O
OtBuO3b
Me
S31
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
9.00
1.96
1.96
2.01
1.98
0.99
0.95
0.90
0.99
1.53
1
3.56
63.
583
3.59
9
7.26
07.
317
7.33
57.
354
7.37
07.
389
7.39
37.
407
7.44
97.
469
7.48
27.
487
7.61
97.
636
7.64
07.
670
7.67
47.
690
7.69
57.
754
7.75
87.
964
7.97
88.
025
8.04
5
NH
O
OtBuO
3c
Ph
S32
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
9.00
1.96
1.96
2.01
1.98
0.99
0.95
0.90
0.99
1.53
1
3.56
63.
583
3.59
9
7.26
07.
317
7.33
57.
354
7.37
07.
389
7.39
37.
407
7.44
97.
469
7.48
27.
487
7.61
97.
636
7.64
07.
670
7.67
47.
690
7.69
57.
754
7.75
87.
964
7.97
88.
025
8.04
5
NH
O
OtBuO
3c
Ph
S33
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.48.6f1 (ppm)
1.96
1.96
2.01
1.98
0.99
0.95
0.90
0.99
3.56
63.
583
3.59
9
7.26
07.
317
7.33
57.
354
7.37
07.
389
7.39
37.
407
7.44
97.
469
7.48
27.
487
7.61
97.
636
7.64
07.
670
7.67
47.
690
7.69
57.
754
7.75
87.
964
7.97
88.
025
8.04
5
NH
O
OtBuO
3c
Ph
S34
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
6.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.3f1 (ppm)
1.96
2.01
1.98
0.99
0.95
0.90
0.99
7.26
0
7.31
77.
335
7.35
47.
370
7.38
97.
393
7.40
77.
449
7.46
97.
482
7.48
7
7.61
97.
636
7.64
07.
670
7.67
47.
690
7.69
5
7.75
47.
758
7.96
47.
978
8.02
58.
045
NH
O
OtBuO
3c
Ph
S35
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180f1 (ppm)
28.0
8
37.5
5
76.6
877
.00
77.3
281
.82
127.
0712
7.21
127.
9612
8.27
128.
8713
0.30
132.
6913
3.43
137.
8013
8.97
139.
9214
2.68
165.
19
171.
49
NH
O
OtBuO
3c
Ph
S36
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
124126128130132134136138140142144146148150152154156158160162164166168170172174176f1 (ppm)
127.
0712
7.21
127.
9612
8.27
128.
87
130.
30
132.
6913
3.43
137.
8013
8.97
139.
92
142.
68
165.
19
171.
49
NH
O
OtBuO
3c
Ph
S37
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
9.00
1.92
0.91
0.97
0.96
0.99
0.93
1.53
5
3.54
53.
561
3.57
9
7.20
37.
260
7.41
17.
429
7.44
87.
699
7.70
37.
720
7.72
37.
913
7.91
78.
031
8.05
1
NH
O
OtBuO3d
NC
S38
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
6.46.56.66.76.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.4f1 (ppm)
0.91
0.97
0.96
0.99
0.93
7.20
3
7.26
0
7.41
17.
429
7.44
8
7.69
97.
703
7.72
07.
723
7.91
37.
917
8.03
18.
051
NH
O
OtBuO3d
NC
S39
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180f1 (ppm)
28.0
3
37.4
7
76.6
877
.00
77.3
2
82.7
8
114.
02
117.
87
130.
7613
1.17
133.
0213
3.80
136.
2313
8.36
140.
57
163.
91
169.
34
NH
O
OtBuO3d
NC
S40
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
100105110115120125130135140145150155160165170175f1 (ppm)
114.
02
117.
87
130.
7613
1.17
133.
0213
3.80
136.
23
138.
36
140.
57
163.
91
169.
34
NH
O
OtBuO3d
NC
S41
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
9.00
2.02
0.99
0.95
0.97
0.95
0.98
1.51
4
3.54
63.
563
3.57
9
7.26
07.
404
7.42
27.
441
7.48
07.
687
7.70
87.
841
8.05
68.
076
NH
O
OtBuO3e
F3C
S42
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.2f1 (ppm)
2.02
0.99
0.95
0.97
0.95
0.98
3.54
63.
563
3.57
9
7.26
0
7.40
47.
422
7.44
17.
480
7.68
77.
708
7.84
1
8.05
68.
076
NH
O
OtBuO3e
F3C
S43
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180f1 (ppm)
27.9
6
37.4
5
76.6
877
.00
77.3
2
82.5
0
122.
2012
4.75
124.
7812
4.82
124.
9212
6.89
126.
9312
6.97
127.
0113
0.45
131.
3113
1.63
131.
9613
2.28
132.
8613
6.86
137.
7014
0.37
164.
26
170.
31
NH
O
OtBuO3e
F3C
S44
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
100105110115120125130135140145150155160165170f1 (ppm)
122.
2012
4.78
124.
8212
4.92
126.
8912
6.93
126.
97
130.
4513
1.31
131.
6313
1.96
132.
2813
2.86
136.
8613
7.70
140.
37
164.
26
170.
31
NH
O
OtBuO3e
F3C
S45
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160f1 (ppm)
27.9
6
37.4
6
124.
7612
4.79
124.
8212
4.85
126.
9112
6.94
126.
9712
7.00
130.
46
140.
33
NH
O
OtBuO3e
F3C
S46
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
9.00
1.93
3.01
1.92
1.08
0.95
0.94
1.51
8
3.50
73.
524
3.54
0
3.86
2
6.98
36.
989
7.00
57.
011
7.02
87.
034
7.25
07.
268
7.28
17.
286
7.90
67.
927
8.15
48.
168
8.18
2
NH
O
OtBuO3f
MeO
S47
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.4f1 (ppm)
1.93
3.01
1.92
1.08
0.95
0.94
3.50
73.
524
3.54
0
3.86
2
6.98
36.
989
7.00
57.
011
7.02
87.
034
7.25
07.
268
7.28
17.
286
7.90
67.
927
8.15
48.
168
8.18
2
NH
O
OtBuO3f
MeO
S48
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180f1 (ppm)
28.0
0
37.4
4
55.2
9
76.7
577
.00
77.2
581
.71
114.
2011
4.57
127.
4413
1.59
133.
9913
7.52
138.
83
160.
39
165.
20
171.
53
NH
O
OtBuO3f
MeO
S49
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
9.00
1.97
0.97
1.00
0.91
0.96
0.93
1.51
6
3.50
93.
527
3.54
2
7.26
07.
322
7.34
07.
359
7.40
57.
410
7.42
67.
432
7.55
37.
559
7.87
17.
892
7.99
0
NH
O
OtBuO3g
Cl
S50
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.54.04.55.05.56.06.57.07.58.0f1 (ppm)
1.97
0.97
1.00
0.91
0.96
0.93
3.50
93.
527
3.54
2
7.26
07.
322
7.34
07.
359
7.40
57.
410
7.42
67.
432
7.55
37.
559
7.87
17.
892
7.99
0
NH
O
OtBuO3g
Cl
S51
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180f1 (ppm)
28.0
0
37.4
4
76.6
877
.00
77.3
2
82.2
1
128.
5912
9.59
131.
2413
3.10
133.
7413
6.21
136.
6713
9.91
164.
45
170.
70
NH
O
OtBuO3g
Cl
S52
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
9.00
1.97
0.97
1.00
0.92
0.99
0.98
1.52
7
3.51
83.
535
3.55
2
7.27
07.
332
7.35
17.
369
7.57
17.
576
7.59
27.
597
7.72
57.
730
7.80
57.
826
7.92
0
NH
O
OtBuO
3h
Br
S53
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.2f1 (ppm)
1.97
0.97
1.00
0.92
0.99
0.98
3.51
83.
535
3.55
2
7.27
07.
332
7.35
17.
369
7.57
67.
592
7.59
7
7.72
57.
730
7.80
57.
826
7.92
0
NH
O
OtBuO
3h
Br
S54
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180f1 (ppm)
28.0
1
37.4
3
76.6
877
.00
77.3
282
.23
124.
56
131.
3113
1.49
132.
5513
3.53
133.
8813
6.61
139.
98
164.
42
170.
73
NH
O
OtBuO
3h
Br
S55
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
9.00
1.95
0.97
0.96
1.00
1.88
1.52
5
3.51
33.
530
3.54
6
7.27
07.
322
7.34
17.
359
7.64
07.
661
7.77
77.
781
7.79
87.
802
7.92
07.
924
7.94
2
NH
O
OtBuO3i
I
S56
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.48.6f1 (ppm)
1.95
0.97
0.96
1.00
1.88
3.51
33.
530
3.54
6
7.27
07.
322
7.34
17.
359
7.64
07.
661
7.77
77.
781
7.79
87.
802
7.92
07.
924
7.94
2
NH
O
OtBuO3i
I
S57
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180f1 (ppm)
28.0
0
37.3
9
76.6
877
.00
77.3
282
.19
96.7
0
131.
1213
3.76
134.
0613
6.50
137.
3013
8.57
139.
98
164.
42
170.
91
NH
O
OtBuO3i
I
S58
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
130135140145150155160165170175f1 (ppm)
131.
12
133.
7613
4.06
136.
50
137.
30
138.
57
139.
98
164.
42
170.
91
NH
O
OtBuO3i
I
S59
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
9.00
1.97
0.97
0.91
0.95
0.96
0.93
1.54
0
3.57
03.
587
3.60
4
7.26
07.
459
7.47
87.
496
7.52
17.
536
7.55
08.
104
8.12
58.
248
8.25
48.
270
8.27
68.
490
8.49
6
NH
O
OtBu3j
O2N
O
S60
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.48.68.8f1 (ppm)
1.97
0.97
0.91
0.95
0.96
0.93
3.57
03.
587
3.60
4
7.26
07.
459
7.47
87.
496
7.52
17.
536
7.55
0
8.10
48.
125
8.24
88.
254
8.27
08.
276
8.49
08.
496
NH
O
OtBu3j
O2N
O
S61
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180f1 (ppm)
28.0
2
37.4
8
76.6
877
.00
77.3
2
82.9
3
122.
6712
5.11
131.
3613
3.58
136.
4013
9.84
140.
85
148.
27
163.
82
169.
33
NH
O
OtBu3j
O2N
O
S62
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
9.00
3.10
2.04
1.05
1.09
1.00
2.06
1.50
3
2.41
8
3.49
33.
510
3.52
6
7.20
27.
220
7.23
87.
260
7.29
77.
300
7.31
77.
321
7.39
17.
411
7.75
5
NH
O
OtBuO
Me
3k
S63
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.03.54.04.55.05.56.06.57.07.5f1 (ppm)
2.04
1.05
1.09
1.00
2.06
3.49
33.
510
3.52
6
7.20
27.
220
7.23
87.
260
7.29
77.
300
7.31
77.
321
7.39
17.
411
7.75
5
NH
O
OtBuO
Me
3k
S64
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180f1 (ppm)
21.1
4
28.0
3
37.6
2
76.6
877
.00
77.3
281
.73
129.
4812
9.59
130.
0113
0.95
134.
4513
7.70
138.
0113
8.53
165.
40
171.
42
NH
O
OtBuO
Me
3k
S65
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
128130132134136138140142144146148150152154156158160162164166168170172f1 (ppm)
129.
4812
9.59
130.
0113
0.95
134.
45
137.
7013
8.01
138.
53
165.
40
171.
42
NH
O
OtBuO
Me
3k
S66
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
9.00
3.03
2.06
1.07
1.16
0.95
0.92
1.53
2
2.65
9
3.55
93.
577
3.59
3
7.21
67.
230
7.24
57.
260
7.39
47.
413
7.43
1
7.92
8
8.21
8
NH
O
OtBuO
3l
O2N
Me
S67
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
2.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.4f1 (ppm)
3.03
2.06
1.07
1.16
0.95
0.92
2.65
9
3.55
93.
577
3.59
3
7.21
67.
230
7.24
57.
260
7.39
47.
413
7.43
1
7.92
8
8.21
8
NH
O
OtBuO
3l
O2N
Me
S68
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180f1 (ppm)
19.9
9
28.0
1
37.5
1
76.6
877
.00
77.3
2
82.7
5
126.
16
131.
1513
3.23
134.
2213
6.28
138.
1514
0.18
149.
58
163.
97
169.
45
NH
O
OtBuO
3l
O2N
Me
S69
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
9.00
2.08
2.47
0.89
0.88
1.46
5
3.47
33.
493
3.51
13.
526
3.56
73.
585
3.60
33.
622
7.24
77.
265
7.28
57.
318
7.56
97.
575
7.86
27.
867
NH
O
3m
Cl
ClO OtBu
S70
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
2.08
2.47
0.89
0.88
3.47
33.
493
3.51
13.
526
3.56
73.
585
3.60
33.
622
7.24
77.
265
7.28
57.
318
7.56
97.
575
7.86
27.
867
NH
O
3m
Cl
ClO OtBu
S71
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180f1 (ppm)
27.7
5
37.6
1
76.6
877
.00
77.3
2
82.2
9
128.
2713
0.26
131.
7513
4.82
135.
1113
6.88
137.
7013
9.50
164.
21
168.
80
NH
O
3m
Cl
ClO OtBu
S72
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
122124126128130132134136138140142144146148150152154156158160162164166168170172174f1 (ppm)
128.
27
130.
26
131.
75
134.
8213
5.11
136.
88
137.
70
139.
50
164.
21
168.
80
NH
O
3m
Cl
ClO OtBu
S73
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
9.00
1.97
2.13
0.95
1.00
0.98
0.92
1.47
2
3.54
63.
562
3.57
9
6.04
7
6.92
06.
941
7.15
17.
169
7.18
77.
275
7.55
67.
576
7.75
0
NH
O
3nO OtBu
OO
S74
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.0f1 (ppm)
1.97
2.13
0.95
1.00
0.98
0.92
3.54
63.
562
3.57
9
6.04
7
6.92
06.
941
7.15
17.
169
7.18
77.
275
7.55
67.
576
7.75
0
NH
O
3nO OtBu
OO
S75
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180f1 (ppm)
27.8
5
37.5
8
76.6
877
.00
77.3
281
.55
101.
62
108.
90
115.
75
124.
88
128.
24
134.
76
138.
88
144.
64
149.
09
164.
65
170.
72
NH
O
3nO OtBu
OO
S76
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
9.00
2.00
0.95
1.01
3.03
2.07
0.93
1.53
4
3.43
63.
454
3.47
33.
491
3.50
93.
569
3.58
73.
604
3.62
43.
641
7.26
07.
324
7.34
07.
356
7.40
57.
423
7.44
07.
517
7.53
97.
554
7.55
77.
574
7.57
77.
579
7.59
67.
599
7.61
37.
616
7.85
37.
857
7.88
17.
903
8.47
68.
496
NH
O
OtBuO
3o
S77
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
2.00
0.95
1.01
3.03
2.07
0.93
3.43
63.
454
3.47
33.
491
3.50
93.
569
3.58
73.
604
3.62
43.
641
7.26
07.
324
7.34
07.
356
7.40
57.
423
7.44
07.
517
7.53
97.
554
7.55
77.
574
7.57
77.
579
7.59
67.
599
7.61
37.
616
7.85
37.
857
7.88
17.
903
8.47
68.
496
NH
O
OtBuO
3o
S78
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180190f1 (ppm)
28.0
6
37.9
2
76.6
877
.00
77.3
282
.01
125.
8012
6.95
127.
0612
7.34
127.
9312
9.29
130.
5613
0.76
131.
6513
3.06
138.
4814
0.07
165.
09
170.
23
NH
O
OtBuO
3o
S79
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
122123124125126127128129130131132133134135136137138139140141142f1 (ppm)
125.
80
126.
9512
7.06
127.
34
127.
93
129.
29
130.
5613
0.76
131.
65
133.
06
138.
48
140.
07
NH
O
OtBuO
3o
S80
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
2.04
3.00
1.00
2.98
0.95
0.96
3.53
73.
549
3.55
13.
564
3.82
1
7.26
07.
375
7.38
97.
404
7.45
87.
467
7.47
57.
481
7.48
37.
491
7.49
97.
508
7.51
57.
516
7.52
47.
527
7.75
47.
948
7.95
07.
963
7.96
5
NH
O
OMeO4a
S81
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
6.76.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.3f1 (ppm)
1.00
2.98
0.95
0.96
7.26
0
7.37
57.
389
7.40
47.
458
7.46
77.
475
7.48
17.
483
7.49
17.
499
7.50
87.
515
7.51
67.
524
7.52
7
7.75
4
7.94
87.
950
7.96
37.
965
NH
O
OMeO4a
S82
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180190f1 (ppm)
37.5
2
52.3
7
76.7
577
.00
77.2
5
128.
6312
9.43
129.
8213
0.17
131.
7913
4.70
136.
2613
9.93
166.
50
171.
21
NH
O
OMeO4a
S83
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
125130135140145150155160165170f1 (ppm)
128.
6312
9.43
129.
8213
0.17
131.
79
134.
70
136.
26
139.
93
166.
50
171.
21
NH
O
OMeO4a
S84
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
2.00
2.04
2.23
2.11
1.08
3.24
2.18
2.17
62.
192
2.20
72.
223
2.23
8
3.41
33.
429
3.44
53.
535
3.55
13.
567
4.35
04.
365
4.37
9
7.26
07.
363
7.38
17.
399
7.47
57.
494
7.50
87.
523
7.94
97.
968
8.09
9
NH
O
OOBr
3
4b
S85
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180190f1 (ppm)
29.3
331
.33
37.4
7
62.9
9
76.6
877
.00
77.3
2
128.
6912
9.33
129.
8013
0.11
131.
7313
4.71
136.
1714
0.15
165.
83
171.
35
NH
O
OOBr
3
4b
S86
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
126128130132134136138140142144146148150152154156158160162164166168170172f1 (ppm)
128.
6912
9.33
129.
8013
0.11
131.
73
134.
71
136.
17
140.
15
165.
83
171.
35
NH
O
OOBr
3
4b
S87
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
1.93
1.94
2.07
2.00
4.12
2.05
2.04
0.99
1.01
2.19
32.
209
2.22
42.
240
2.25
5
3.39
93.
415
3.43
13.
603
3.62
03.
637
4.38
24.
397
4.41
2
7.26
07.
376
7.39
47.
412
7.42
27.
440
7.45
17.
459
7.47
07.
488
7.61
97.
637
7.64
07.
701
7.70
67.
722
7.72
67.
748
7.75
27.
783
7.79
77.
812
8.04
18.
061
NH
O
OOBr
3
Ph
4c
S88
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
6.56.66.76.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.4f1 (ppm)
4.12
2.05
2.04
0.99
1.01
7.26
0
7.37
67.
394
7.41
27.
422
7.44
07.
451
7.45
97.
470
7.48
8
7.61
97.
637
7.64
07.
701
7.70
67.
722
7.72
67.
748
7.75
27.
783
7.79
77.
812
8.04
18.
061
NH
O
OOBr
3
Ph
4c
S89
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180190f1 (ppm)
29.2
531
.45
37.5
7
63.1
1
76.6
877
.00
77.3
2
127.
2812
7.39
128.
1112
8.93
130.
5013
2.11
133.
4013
6.19
139.
6314
0.29
143.
01
165.
81
171.
15
NH
O
OOBr
3
Ph
4c
S90
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
122124126128130132134136138140142144146148150152154156158160162164166168170172174f1 (ppm)
127.
2812
7.39
128.
1112
8.93
130.
50
132.
11
133.
40
136.
19
139.
6314
0.29
143.
01
165.
81
171.
15
NH
O
OOBr
3
Ph
4c
S91
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
1.68
2.78
1.12
2.00
1.93
2.16
3.19
0.98
2.16
22.
183
2.19
92.
215
2.23
02.
245
3.42
23.
427
3.43
93.
442
3.45
53.
472
3.49
13.
508
3.59
23.
609
3.62
6
4.35
04.
364
4.37
84.
392
4.40
14.
407
4.41
74.
432
4.44
5
7.26
07.
489
7.50
57.
514
7.52
67.
550
7.55
37.
567
7.57
07.
586
7.59
07.
608
7.61
27.
625
7.62
97.
863
7.86
67.
885
7.90
37.
924
8.49
38.
513
NH
O
OO4d
Br
3
S92
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
6.66.76.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.68.78.8f1 (ppm)
1.93
2.16
3.19
0.98
7.26
0
7.48
97.
505
7.51
47.
526
7.55
07.
553
7.56
77.
570
7.58
67.
590
7.60
87.
612
7.62
57.
629
7.86
37.
866
7.88
57.
903
7.92
4
8.49
38.
513
NH
O
OO4d
Br
3
S93
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180190f1 (ppm)
29.4
431
.27
37.8
2
63.0
4
76.6
877
.00
77.3
2
125.
4812
7.08
127.
1112
7.46
127.
9712
9.51
130.
1313
0.52
131.
8413
3.14
136.
6214
1.66
165.
77
170.
26
NH
O
OO4d
Br
3
S94
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
122124126128130132134136138140142144146148150152154156158160162164166168170172f1 (ppm)
125.
48
127.
0812
7.11
127.
4612
7.97
129.
5113
0.13
130.
52
131.
84
133.
14
136.
62
141.
66
165.
77
170.
26
NH
O
OO4d
Br
3
S95
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
3.21
3.00
1.95
1.92
1.17
1.98
1.89
1.24
41.
255
1.26
11.
279
2.21
0
3.47
93.
494
4.23
24.
250
4.26
84.
286
7.27
17.
290
7.29
37.
396
7.39
97.
415
7.41
87.
433
7.43
77.
444
7.44
87.
463
7.46
77.
482
7.48
67.
953
7.95
77.
972
7.97
57.
986
NH
O
OEt
MeO
4e
S96
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
6.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.3f1 (ppm)
1.17
1.98
1.89
7.27
17.
290
7.29
3
7.39
67.
399
7.41
57.
418
7.43
37.
437
7.44
47.
448
7.46
37.
467
7.48
27.
486
7.95
37.
957
7.97
27.
975
7.98
6
NH
O
OEt
MeO
4e
S97
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180f1 (ppm)
14.0
6
21.0
8
44.8
4
61.1
1
76.6
877
.00
77.3
2
127.
7212
7.93
129.
9013
0.43
132.
0113
3.79
134.
04
144.
66
168.
1517
1.05
NH
O
OEt
MeO
4e
S98
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
110114118122126130134138142146150154158162166170174f1 (ppm)
127.
7212
7.93
129.
9013
0.43
132.
01
133.
7913
4.04
144.
66
168.
15
171.
05
NH
O
OEt
MeO
4e
S99
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
3.55
3.00
1.96
1.87
0.96
0.98
0.97
0.95
1.23
81.
255
1.27
3
2.26
6
3.49
13.
506
4.24
44.
262
4.28
04.
298
7.26
0
7.57
07.
637
7.65
7
8.05
28.
072
8.21
18.
225
8.23
9
NH
O
OEt
MeO
F3C
4f
S100
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
1.96
1.87
0.96
0.98
0.97
0.95
3.49
13.
506
4.24
44.
262
4.28
04.
298
7.26
0
7.57
07.
637
7.65
7
8.05
28.
072
8.21
18.
225
8.23
9
NH
O
OEt
MeO
F3C
4f
S101
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180190f1 (ppm)
13.9
5
21.3
4
45.0
5
61.3
6
76.6
877
.00
77.3
2
122.
0812
4.32
124.
3612
4.39
124.
4312
4.79
125.
1812
5.22
125.
2612
5.30
130.
5813
0.79
132.
0613
2.39
132.
7113
4.77
136.
82
147.
68
167.
2016
9.94
NH
O
OEt
MeO
F3C
4f
S102
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
110114118122126130134138142146150154158162166170174f1 (ppm)
122.
0812
4.32
124.
3612
4.39
124.
4312
4.79
125.
2212
5.26
130.
5813
0.79
131.
7313
2.06
132.
3913
2.71
134.
77
136.
82
147.
68
167.
20
169.
94
NH
O
OEt
MeO
F3C
4f
S103
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
5101520253035404550556065707580859095100105110115120125130135140145150f1 (ppm)
13.9
5
21.3
3
45.0
6
61.3
6
124.
3612
4.39
125.
2312
5.26
130.
59
NH
O
OEt
MeO
F3C
4f
S104
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
3.01
3.08
1.95
3.00
1.98
0.94
0.98
0.93
0.97
1.24
81.
266
1.28
4
2.17
2
3.46
73.
483
3.81
9
4.22
74.
245
4.26
34.
281
6.77
36.
779
6.93
26.
938
6.95
46.
960
7.26
0
7.62
17.
635
7.65
07.
910
7.93
2
NH
O
OEt
MeO
MeO
4g
S105
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180f1 (ppm)
14.1
1
21.0
7
44.7
9
55.3
5
61.1
3
76.6
877
.00
77.3
2
112.
2411
4.17
126.
53
131.
9813
2.04
135.
65
144.
06
160.
89
168.
2017
0.80
NH
O
OEt
MeO
MeO
4g
S106
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
129.0129.5130.0130.5131.0131.5132.0132.5133.0133.5134.0134.5135.0135.5136.0136.5137.0137.5f1 (ppm)
131.
9813
2.04
135.
65
NH
O
OEt
MeO
MeO
4g
S107
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
3.06
3.00
1.97
1.94
1.93
0.97
0.94
1.25
51.
273
1.29
1
2.20
1
3.45
43.
470
4.23
94.
257
4.27
44.
292
7.26
07.
630
7.65
17.
720
7.72
47.
740
7.74
48.
138
8.15
28.
166
NH
O
OEt
MeO
I
4h
S108
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170f1 (ppm)
14.0
7
21.2
4
44.8
4
61.2
9
76.6
877
.00
77.3
2
97.2
1
130.
6413
1.30
133.
1913
5.64
136.
7513
6.92
146.
49
167.
45
170.
48
NH
O
OEt
MeO
I
4h
S109
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
95100105110115120125130135140145150155160165170f1 (ppm)
97.2
1
130.
6413
1.30
133.
19
135.
6413
6.75
136.
92
146.
49
167.
45
170.
48
NH
O
OEt
MeO
I
4h
S110
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
2.89
2.96
3.00
1.99
1.86
0.99
0.91
0.86
1.27
11.
289
1.30
6
2.27
7
2.63
9
3.50
73.
523
4.26
44.
282
4.29
94.
317
7.26
0
7.77
07.
925
7.93
8
4i
NH
O
OEt
MeO
O2N
Me
S111
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180f1 (ppm)
14.0
7
19.9
221
.44
45.1
9
61.5
6
76.6
877
.00
77.3
2
124.
52
130.
2813
2.76
133.
1113
4.35
137.
26
147.
6814
9.79
166.
8916
9.09
4i
NH
O
OEt
MeO
O2N
Me
S112
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
110114118122126130134138142146150154158162166170f1 (ppm)
124.
52
130.
28
132.
7613
3.11
134.
35
137.
26
147.
68
149.
79
166.
89
169.
09
4i
NH
O
OEt
MeO
O2N
Me
S113
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
3.00
3.00
0.99
0.99
1.96
0.91
0.92
0.94
1.14
61.
164
1.18
2
2.37
3
3.34
63.
362
3.38
13.
398
3.54
73.
562
3.58
33.
598
4.09
84.
107
4.11
54.
125
4.13
14.
143
4.14
94.
160
4.16
74.
176
4.18
54.
194
7.26
0
7.50
97.
514
7.79
67.
801
8.50
8
NH
O
Me
4j
Cl
ClOEtO
S114
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
6.66.76.86.97.07.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.68.7f1 (ppm)
0.91
0.92
0.94
7.26
0
7.50
97.
514
7.79
67.
801
8.50
8
NH
O
Me
4j
Cl
ClOEtO
S115
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180f1 (ppm)
13.8
4
20.5
2
46.0
8
61.1
8
76.6
877
.00
77.3
2
127.
7712
7.87
131.
5513
2.43
134.
3713
4.83
137.
25
151.
80
165.
87
169.
13
NH
O
Me
4j
Cl
ClOEtO
S116
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
124126128130132134136138140142144146148150152154156158160162164166168170f1 (ppm)
127.
7712
7.87
131.
55
132.
43
134.
3713
4.83
137.
25
151.
80
165.
87
169.
13
NH
O
Me
4j
Cl
ClOEtO
S117
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
2.69
2.00
1.78
4.95
3.01
0.96
0.95
0.92
70.
944
0.96
2
3.85
73.
873
3.99
14.
009
4.02
74.
044
7.26
07.
332
7.33
87.
349
7.36
17.
369
7.37
57.
390
7.39
57.
451
7.46
07.
466
7.47
97.
486
7.50
17.
504
7.51
67.
520
7.64
28.
012
8.03
1
NH
O
OEt
PhO
4k
S118
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.48.68.8f1 (ppm)
2.00
1.78
4.95
3.01
0.96
0.95
3.85
73.
873
3.99
14.
009
4.02
74.
044
7.26
07.
332
7.33
87.
349
7.36
17.
369
7.37
57.
390
7.39
57.
451
7.46
07.
466
7.47
97.
486
7.50
17.
504
7.51
67.
520
7.64
28.
012
8.03
1
NH
O
OEt
PhO
4k
S119
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180f1 (ppm)
13.5
6
44.9
5
61.2
4
76.6
877
.00
77.3
2
127.
3312
7.71
128.
3912
8.54
128.
6113
0.44
130.
8213
3.47
133.
9013
3.99
139.
42
144.
79
168.
4517
0.45
NH
O
OEt
PhO
4k
S120
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
126127128129130131132133134135136137138139140141142143144145146147148149f1 (ppm)
127.
33
127.
71
128.
3912
8.54
128.
61
130.
44
130.
82
133.
4713
3.90
133.
99
139.
42
144.
79
NH
O
OEt
PhO
4k
S121
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
2.61
3.00
2.01
1.77
8.20
0.97
0.92
40.
942
0.95
9
2.40
5
3.84
43.
860
3.99
74.
015
4.03
34.
051
7.26
07.
272
7.29
07.
322
7.33
87.
348
7.35
17.
359
7.37
07.
373
7.37
77.
382
7.91
47.
935
NH
O
OEt
PhO
Me
4l
S122
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
4.04.55.05.56.06.57.07.58.0f1 (ppm)
2.01
1.77
8.20
0.97
3.84
43.
860
3.99
74.
015
4.03
34.
051
7.26
07.
272
7.29
07.
322
7.33
87.
348
7.35
17.
359
7.37
07.
373
7.37
77.
382
7.91
47.
935
NH
O
OEt
PhO
Me
4l
S123
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170f1 (ppm)
13.5
5
21.4
6
44.9
7
61.2
0
76.6
877
.00
77.3
2
127.
3212
8.04
128.
3212
8.53
129.
6013
0.53
131.
2813
3.36
134.
0013
9.51
141.
2114
4.40
168.
5717
0.50
NH
O
OEt
PhO
Me
4l
S124
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
116120124128132136140144148152156160164168172f1 (ppm)
127.
3212
8.04
128.
3212
8.53
129.
6013
0.53
131.
28
133.
3613
4.00
139.
51
141.
21
144.
40
168.
57
170.
50
NH
O
OEt
PhO
Me
4l
S125
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
2.56
2.00
1.69
1.87
2.92
0.98
0.91
0.88
0.99
0.90
60.
924
0.94
1
3.87
03.
886
4.00
24.
019
4.03
74.
055
7.26
07.
316
7.32
17.
325
7.32
87.
334
7.34
07.
388
7.40
67.
702
7.70
67.
722
7.72
67.
792
7.89
37.
897
8.09
38.
114
NH
O
OEt
PhO
NC
4m
S126
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.2f1 (ppm)
2.00
1.69
1.87
2.92
0.98
0.91
0.88
0.99
3.87
03.
886
4.00
24.
019
4.03
74.
055
7.26
07.
316
7.32
17.
325
7.32
87.
334
7.34
07.
388
7.40
6
7.70
27.
706
7.72
27.
726
7.79
27.
893
7.89
7
8.09
38.
114
NH
O
OEt
PhO
NC
4m
S127
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180f1 (ppm)
13.4
5
44.8
5
61.7
3
76.6
877
.00
77.3
2
114.
77
117.
66
127.
1912
8.69
128.
8913
1.25
131.
3213
1.83
134.
3913
7.63
138.
85
147.
44
167.
5816
8.93
NH
O
OEt
PhO
NC
4m
S128
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
105110115120125130135140145150155160165170f1 (ppm)
114.
77
117.
66
127.
1912
8.69
128.
89
131.
2513
1.32
131.
83
134.
39
137.
63
138.
85
147.
44
167.
58
168.
93
NH
O
OEt
PhO
NC
4m
S129
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
2.57
5.00
1.71
1.97
5.94
0.97
0.92
80.
946
0.96
4
3.85
03.
869
3.98
44.
002
4.01
94.
037
6.98
96.
995
7.01
77.
022
7.26
07.
329
7.33
67.
347
7.36
07.
373
7.42
7
7.98
28.
003
NH
O
OEt
PhO
MeO
4n
S130
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.2f1 (ppm)
5.00
1.71
1.97
5.94
0.97
3.85
03.
869
3.98
44.
002
4.01
94.
037
6.98
96.
995
7.01
77.
022
7.26
07.
329
7.33
67.
347
7.36
07.
373
7.39
07.
394
7.41
17.
427
7.98
28.
003
NH
O
OEt
PhO
MeO
4n
S131
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180f1 (ppm)
13.5
7
44.9
6
55.4
0
61.2
4
76.6
877
.00
77.3
2
112.
2611
4.78
126.
6512
7.32
128.
3712
8.53
132.
4813
3.67
135.
1113
9.41
144.
66
161.
14
168.
4417
0.37
NH
O
OEt
PhO
MeO
4n
S132
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
105110115120125130135140145150155160165170175f1 (ppm)
112.
26
114.
78
126.
6512
7.32
128.
3712
8.53
132.
4813
3.67
135.
11
139.
41
144.
66
161.
14
168.
44
170.
37
NH
O
OEt
PhO
MeO
4n
S133
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
2.59
2.00
1.73
4.92
1.00
0.90
0.91
0.99
0.92
00.
938
0.95
5
3.85
63.
872
3.99
84.
016
4.03
44.
052
7.26
07.
318
7.33
37.
338
7.35
57.
371
7.38
27.
390
7.42
07.
425
7.44
27.
447
7.53
77.
541
7.59
37.
951
7.97
2
NH
O
OEt
PhO
Cl
4o
S134
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
4.04.55.05.56.06.57.07.58.0f1 (ppm)
2.00
1.73
4.92
1.00
0.90
0.91
0.99
3.85
63.
872
3.99
84.
016
4.03
44.
052
7.26
07.
318
7.33
37.
338
7.35
57.
371
7.38
27.
390
7.42
07.
425
7.44
27.
447
7.53
77.
541
7.59
3
7.95
17.
972
NH
O
OEt
PhO
Cl
4o
S135
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180f1 (ppm)
13.5
1
44.9
3
61.4
8
76.6
877
.00
77.3
2
127.
2712
7.64
128.
6212
8.84
132.
0113
2.38
132.
7313
4.95
137.
1213
9.14
146.
08
167.
9116
9.67
NH
O
OEt
PhO
Cl
4o
S136
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
124126128130132134136138140142144146148150152154156158160162164166168170172f1 (ppm)
127.
2712
7.64
128.
6212
8.84
132.
0113
2.38
132.
73
134.
95
137.
12
139.
14
146.
08
167.
91
169.
67
NH
O
OEt
PhO
Cl
4o
S137
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
2.63
3.00
2.06
1.85
1.13
7.13
1.01
0.93
20.
950
0.96
8
2.43
5
3.85
13.
867
3.99
24.
010
4.02
84.
045
7.10
67.
260
7.31
17.
315
7.33
17.
335
7.34
97.
360
7.37
07.
378
7.84
3
4p
NH
O
OEt
PhO
Me
S138
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.0f1 (ppm)
2.06
1.85
1.13
7.13
1.01
3.85
13.
867
3.99
24.
010
4.02
84.
045
7.10
67.
260
7.31
17.
315
7.33
17.
335
7.34
97.
360
7.37
07.
378
7.84
3
4p
NH
O
OEt
PhO
Me
S139
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180f1 (ppm)
13.5
8
21.1
7
45.0
4
61.2
1
76.6
877
.00
77.3
2
127.
3412
7.77
128.
3212
8.55
130.
7913
1.84
133.
7113
4.04
138.
9113
9.48
143.
75
168.
5917
0.40
4p
NH
O
OEt
PhO
Me
S140
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
122124126128130132134136138140142144146148150152154156158160162164166168170172174176178f1 (ppm)
127.
3412
7.77
128.
3212
8.55
130.
79
131.
84
133.
7113
4.04
138.
9113
9.48
143.
75
168.
59
170.
40
4p
NH
O
OEt
PhO
Me
S141
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
2.80
2.00
1.82
1.97
0.96
4.89
0.96
0.99
61.
013
1.03
1
3.82
13.
837
4.02
54.
042
4.06
04.
078
7.20
67.
227
7.26
07.
317
7.45
57.
458
7.46
07.
468
7.47
37.
477
7.48
67.
491
7.50
67.
513
7.52
37.
527
7.53
28.
010
8.01
58.
030
8.03
3
NH
O
OEtO
Br4q
S142
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
6.856.957.057.157.257.357.457.557.657.757.857.958.058.15f1 (ppm)
1.97
0.96
4.89
0.96
7.20
67.
227
7.26
0
7.31
7
7.45
57.
458
7.46
07.
468
7.47
37.
477
7.48
67.
491
7.50
67.
513
7.52
37.
527
7.53
2
8.01
08.
015
8.03
08.
033
NH
O
OEtO
Br4q
S143
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180f1 (ppm)
13.6
7
44.8
2
61.4
5
76.6
877
.00
77.3
2
122.
6512
7.73
128.
8812
9.02
130.
5313
0.95
131.
7713
3.18
138.
24
143.
40
168.
1317
0.27
NH
O
OEtO
Br4q
S144
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
122124126128130132134136138140142144146148150152154156158160162164166168170172f1 (ppm)
122.
65
127.
7312
8.88
129.
02
130.
5313
0.95
131.
77
133.
1813
3.92
134.
50
138.
24
143.
40
168.
13
170.
27
NH
O
OEtO
Br4q
S145
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
2.80
2.00
1.79
1.92
0.89
1.03
2.81
0.97
0.99
21.
010
1.02
8
3.81
83.
834
4.03
44.
051
4.06
94.
087
7.19
47.
215
7.26
07.
415
7.44
17.
446
7.46
37.
467
7.50
57.
509
7.51
67.
537
7.94
97.
970
NH
O
OEtO
Br4r
Cl
S146
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
4.04.55.05.56.06.57.07.58.0f1 (ppm)
2.00
1.79
1.92
0.89
1.03
2.81
0.97
3.81
83.
834
4.03
44.
051
4.06
94.
087
7.19
47.
215
7.26
07.
415
7.44
17.
446
7.46
37.
467
7.50
57.
509
7.51
67.
537
7.94
97.
970
NH
O
OEtO
Br4r
Cl
S147
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170f1 (ppm)
13.6
3
44.7
8
61.6
9
76.6
877
.00
77.3
2
122.
9212
7.66
128.
9412
9.11
131.
8513
2.08
132.
3013
7.27
137.
94
144.
69
167.
5916
9.51
NH
O
OEtO
Br4r
Cl
S148
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
116118120122124126128130132134136138140142144146148150152154156158160162164166168170172f1 (ppm)
122.
92
127.
6612
8.94
129.
11
131.
8513
2.08
132.
3013
3.30
134.
65
137.
2713
7.94
144.
69
167.
59
169.
51
NH
O
OEtO
Br4r
Cl
S149
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
2.76
2.00
1.64
0.85
0.86
3.56
0.89
0.92
1.25
61.
273
1.29
1
3.83
33.
894
3.90
3
4.29
34.
311
4.32
94.
346
6.45
26.
457
6.46
16.
465
6.64
26.
650
7.44
97.
453
7.46
67.
496
7.49
97.
505
7.51
1
7.77
6
8.00
28.
020
NH
O
OEtO
O
4s
S150
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.2f1 (ppm)
2.00
1.64
0.85
0.86
3.56
0.89
0.92
3.83
33.
894
3.90
3
4.29
34.
311
4.32
94.
346
6.45
26.
457
6.46
16.
465
6.64
26.
650
7.26
07.
449
7.45
37.
466
7.49
67.
499
7.50
57.
511
7.77
6
8.00
28.
020
NH
O
OEtO
O
4s
S151
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180f1 (ppm)
14.0
1
40.8
3
61.6
6
76.6
877
.00
77.3
2
111.
4411
2.02
127.
1012
8.57
129.
6712
9.87
130.
6913
0.99
133.
2813
3.75
143.
96
150.
21
168.
7017
0.65
NH
O
OEtO
O
4s
S152
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
110114118122126130134138142146150154158162166170174f1 (ppm)
111.
4411
2.02
127.
1012
8.57
129.
6712
9.87
130.
6913
0.99
133.
2813
3.75
143.
96
150.
21
168.
70
170.
65
NH
O
OEtO
O
4s
S153
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
3.03
3.00
2.17
1.76
0.95
0.96
2.08
0.92
0.97
0.97
1.25
81.
276
1.29
3
2.39
2
3.83
73.
876
3.88
9
4.29
74.
315
4.33
34.
351
6.44
86.
452
6.45
66.
461
6.62
46.
633
7.24
67.
260
7.26
57.
294
7.44
57.
448
7.66
67.
898
7.91
8
NH
O
OEtO
O
Me
4t
S154
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.0f1 (ppm)
2.17
1.76
0.95
0.96
2.08
0.92
0.97
0.97
3.83
73.
876
3.88
9
4.29
74.
315
4.33
34.
351
6.44
86.
452
6.45
66.
461
6.62
46.
633
7.24
67.
260
7.26
57.
294
7.44
57.
448
7.66
6
7.89
87.
918
NH
O
OEtO
O
Me
4t
S155
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170180f1 (ppm)
14.0
0
21.4
7
40.8
6
61.6
1
76.6
877
.00
77.3
2
111.
2811
1.98
127.
4412
9.56
129.
6312
9.79
130.
7713
1.10
133.
17
141.
3714
3.86
150.
31
168.
8017
0.71
NH
O
OEtO
O
Me
4t
S156
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
126127128129130131132133134135136137138139140141142143144145146147148149150151f1 (ppm)
127.
44
129.
5612
9.63
129.
79
130.
7713
1.10
133.
17
141.
37
143.
86
150.
31
NH
O
OEtO
O
Me
4t
S157
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
2.67
2.00
1.59
0.85
0.86
0.82
0.61
1.08
0.89
0.70
1.27
41.
291
1.30
9
3.85
33.
883
4.31
34.
330
4.34
84.
366
6.46
96.
474
6.47
86.
482
6.65
86.
666
7.26
07.
467
7.47
17.
632
7.68
67.
707
7.76
37.
767
7.78
47.
788
7.86
97.
873
NH
O
OEtO
O
I
4u
S158
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
4.04.55.05.56.06.57.07.58.0f1 (ppm)
2.00
1.59
0.85
0.86
0.82
0.61
1.08
0.89
0.70
3.85
33.
883
4.31
34.
330
4.34
84.
366
6.46
96.
474
6.47
86.
482
6.65
86.
666
7.26
0
7.46
77.
471
7.63
27.
686
7.70
77.
763
7.76
77.
784
7.78
87.
869
7.87
3
NH
O
OEtO
O
I
4u
S159
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170f1 (ppm)
14.0
2
40.7
5
61.8
8
76.6
877
.00
77.3
2
97.9
8
112.
0311
2.16
128.
2113
0.86
132.
0813
3.11
134.
9113
5.85
137.
60
144.
33
149.
89
168.
1617
0.02
NH
O
OEtO
O
I
4u
S160
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
95100105110115120125130135140145150155160165170f1 (ppm)
97.9
8
112.
0311
2.16
128.
21
130.
8613
2.08
133.
1113
4.91
135.
8513
7.60
144.
33
149.
89
168.
16
170.
02
NH
O
OEtO
O
I
4u
S161
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
3.00
2.25
1.99
2.37
1.09
1.16
1.12
1.13
1.06
1.08
1.10
21.
120
1.13
8
3.94
73.
963
4.11
44.
132
4.15
04.
167
6.03
6
6.80
96.
925
6.94
67.
030
7.04
07.
043
7.05
27.
147
7.15
07.
157
7.15
97.
264
7.40
07.
402
7.41
27.
415
7.61
17.
632
4v
NH
O
OO
O OEt S
S162
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
4.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.6f1 (ppm)
2.25
1.99
2.37
1.09
1.16
1.12
1.13
1.06
1.08
3.94
73.
963
4.11
44.
132
4.15
04.
167
6.03
6
6.80
96.
925
6.94
67.
040
7.04
37.
052
7.14
77.
150
7.15
9
7.26
4
7.40
07.
402
7.41
27.
415
7.61
17.
632
4v
NH
O
OO
O OEt S
S163
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170f1 (ppm)
13.6
6
46.6
6
61.3
9
76.6
877
.00
77.3
2
101.
99
109.
14
116.
85
125.
7212
7.43
127.
5912
7.81
128.
1812
8.50
138.
7813
9.89
144.
99
149.
30
167.
3116
9.36
4v
NH
O
OO
O OEt S
S164
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
126128130132134136138140142144146148150152154156158160162164166168170f1 (ppm)
125.
72
127.
4312
7.59
127.
8112
8.18
128.
50
138.
78
139.
89
144.
99
149.
30
167.
31
169.
36
4v
NH
O
OO
O OEt S
S165
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
3.00
2.07
2.29
1.92
1.91
0.95
1.68
1.87
0.97
0.90
00.
918
0.93
61.
300
1.31
81.
337
1.35
61.
375
1.38
71.
393
1.59
21.
611
1.63
01.
643
1.64
71.
667
2.69
02.
709
2.72
7
3.55
83.
574
3.59
1
7.10
87.
126
7.14
47.
260
7.66
27.
683
7.68
97.
693
7.80
17.
805
7.82
27.
826
NH
O
BuO
I
4w
S166
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
6.36.46.56.66.76.86.97.07.17.27.37.47.57.67.77.87.98.08.1f1 (ppm)
0.95
1.68
1.87
0.97
7.10
87.
126
7.14
4
7.26
0
7.66
27.
683
7.68
97.
693
7.80
17.
805
7.82
27.
826
NH
O
BuO
I
4w
S167
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
13.8
5
22.3
0
26.4
4
37.6
039
.40
76.6
877
.00
77.3
2
97.1
4
131.
5313
3.50
134.
1413
7.78
138.
11
143.
69
170.
33
200.
69
NH
O
BuO
I
4w
S168
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
95100105110115120125130135140145150155160165170175180185190195200205f1 (ppm)
97.1
4
131.
5313
3.50
134.
14
137.
7813
8.11
143.
69
170.
33
200.
69
NH
O
BuO
I
4w
S169
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)
3.00
0.92
1.00
1.91
1.90
0.79
3.86
9
7.07
57.
260
7.33
97.
354
7.36
87.
401
7.41
77.
431
7.72
47.
739
12.0
24
5
HN N
PhCO2CH3
S170
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-100102030405060708090100110120130140150160170f1 (ppm)
52.1
5
76.6
877
.00
77.3
2
105.
59
125.
6912
8.64
128.
9313
0.64
149.
39
161.
08
5
HN N
PhCO2CH3
S171
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
9.00
1.04
1.96
0.97
0.96
0.90
0.89
0.88
1.33
1
1.94
51.
955
1.96
51.
977
1.98
51.
997
2.90
72.
919
2.93
82.
950
2.96
42.
970
2.98
12.
994
3.01
23.
026
3.20
13.
218
3.23
23.
239
3.25
13.
269
3.27
8
4.51
34.
532
6.53
7
7.26
0
7.53
77.
543
7.64
87.
653
NH
OCl
ClO OtBu
6
S172
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
2.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.8f1 (ppm)
1.04
1.96
0.97
0.96
0.90
0.89
0.88
1.94
51.
955
1.96
51.
977
1.98
51.
997
2.90
72.
919
2.93
82.
950
2.96
42.
970
2.98
12.
994
3.01
23.
026
3.20
13.
218
3.23
23.
239
3.25
13.
269
3.27
8
4.51
34.
532
6.53
7
7.26
0
7.53
77.
543
7.64
87.
653
NH
OCl
ClO OtBu
6
S173
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170f1 (ppm)
27.5
0
31.7
9
38.9
2
43.7
6
76.6
877
.00
77.3
2
82.4
0
128.
2213
1.40
132.
4813
3.89
134.
5513
7.97
170.
3717
0.97
NH
OCl
ClO OtBu
6
S174
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
124126128130132134136138140142144146148150152154156158160162164166168170172174f1 (ppm)
128.
22
131.
40
132.
48
133.
8913
4.55
137.
97
170.
3717
0.97
NH
OCl
ClO OtBu
6
S175
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
9.00
0.98
0.95
0.94
0.89
0.86
0.88
1.38
3
2.87
52.
889
2.89
72.
912
2.92
62.
934
2.94
83.
801
3.81
43.
817
3.83
13.
837
3.85
13.
854
3.86
83.
924
3.93
73.
945
3.95
8
7.26
07.
454
7.46
97.
485
7.59
17.
596
7.73
17.
736
NH
OCl
ClO OtBu
O
7
S176
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
2.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.8f1 (ppm)
0.98
0.95
0.94
0.89
0.86
0.88
2.87
52.
889
2.89
72.
912
2.92
62.
934
2.94
8
3.80
13.
814
3.81
73.
831
3.83
73.
851
3.85
43.
868
3.92
43.
937
3.94
53.
958
7.26
0
7.45
47.
469
7.48
57.
591
7.59
67.
731
7.73
6
NH
OCl
ClO OtBu
O
7
S177
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170f1 (ppm)
27.6
2
43.4
3
57.6
4
61.4
1
76.6
877
.00
77.3
2
83.9
4
128.
6712
8.89
132.
1313
5.45
136.
2713
7.57
166.
20
169.
04
NH
OCl
ClO OtBu
O
7
S178
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
130135140145150155160165170f1 (ppm)
128.
6712
8.89
132.
13
135.
45
136.
27
137.
57
166.
20
169.
04
NH
OCl
ClO OtBu
O
7
S179
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
9.00
1.99
1.03
1.18
1.51
4
3.51
63.
532
3.53
43.
549
6.96
0
7.26
07.
265
7.28
37.
302
NH
O
OtBuO[D4]-3a
D4
S180
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.6f1 (ppm)
1.99
1.03
1.18
3.51
63.
532
3.53
43.
549
6.96
0
7.26
07.
265
7.28
37.
302
NH
O
OtBuO[D4]-3a
D4
S181
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0102030405060708090100110120130140150160170f1 (ppm)
28.0
4
37.6
1
76.7
577
.00
77.2
581
.88
132.
1413
4.53
138.
0813
8.41
165.
21
171.
08
NH
O
OtBuO[D4]-3a
D4
S182
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0
f1 (ppm)
9.00
1.98
0.74
1.01
1.74
1.82
1.50
5
3.50
33.
520
3.53
6
7.26
07.
280
7.29
87.
439
7.44
77.
454
7.45
87.
467
7.49
57.
499
7.50
87.
511
7.92
37.
933
7.95
2
NH
O
OtBuO
[D4]-3a/3a
D4/H4
S183
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
3.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.4f1 (ppm)
1.98
0.74
1.01
1.74
1.82
3.50
33.
520
3.53
6
7.26
07.
280
7.29
87.
447
7.45
87.
467
7.49
57.
499
7.50
87.
511
7.92
37.
933
7.95
2
NH
O
OtBuO
[D4]-3a/3a
D4/H4
S184
Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013
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