et3b-mediated two- and three-component coupling reactions ... · supporting information...

Supporting Information

Et3B-Mediated Two- and Three-Component Coupling Reactions via Radical

Decarbonylation of -Alkoxyacyl Tellurides: Single-Step Construction of Densely

Oxygenated Carboskeletons

Masanori Nagatomo, Daigo Kamimura, Yuki Matsui, Keisuke Masuda

and Masayuki Inoue*

Graduate School of Pharmaceutical Sciences, The University of Tokyo,

Hongo, Bunkyo-ku, Tokyo 113-0033, Japan


51 pages

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Electronic Supplementary Material (ESI) for Chemical Science.This journal is © The Royal Society of Chemistry 2015


Contents:

General Information

Experimental

Preparation of Acyl Telluride

Two-Component Radical Reactions Using Glyoxylic Oxime Ether

Two-Component Radical Reactions Using Enones

Three-Component Reactions

References 1H and 13C NMR Spectra of Newly Synthesized Compounds

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S22

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General Information: All Et3B-mediated radical reactions were carried out under air. All

other reactions sensitive to air or moisture were carried out under argon atmosphere in dry

solvents under anhydrous conditions, unless otherwise noted. THF and CH2Cl2 were

purified by Glass Contour solvent dispensing system (Nikko Hansen & Co., Ltd., Osaka,

Japan). All other reagents were used as supplied unless otherwise noted. Analytical

thin-layer chromatography (TLC) was performed using E. Merck Silica gel 60 F254 pre-coated

plates, 0.25 mm. Preparative thin-layer chromatography was performed using Merck silica

gel 60 F254 pre-coated plates, 0.5 mm. Flash chromatography was performed using 40-50

m Silica Gel 60N (Kanto Chemical Co., Inc.), unless otherwise noted. Optical rotations

were measured on JASCO DIP-1000 Digital Polarimeter at room temperature using the

sodium D line. Melting points were measured on Yanaco MP-J3 micro melting point

apparatus, and are uncorrected. Infrared (IR) spectra were recorded on JASCO FT:IR-4100

spectrometer. 1H and 13C NMR spectra were recorded on JEOL JNM-ECX-500,

JNM-ECA-500, or JNM-ECS-400 spectrometer. Chemical shifts were reported in ppm on

the scale relative to CHCl3 ( = 7.26 for 1H NMR), CDCl3 ( = 77.0 for 13C NMR), C6D5H

( = 7.16 for 1H NMR), C6D6 (δ = 128.0 for 13C NMR) and CO(CD3)2 (δ = 206.26 for 13C

NMR) as internal references. Signal patterns are indicated as s, singlet; d, doublet; t, triplet;

q, quartet, m; multiplet, br; broaden peak. High resolution mass spectra was measured on

JEOL JMS-T100LP.

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Experimental

Preparation of Acyl Telluride

General Procedure A: Acyl telluride 1a. N-methylmorpholine (910 L, 8.3 mmol) and

isobutyl chloroformate (950 L, 7.3 mmol) were added to a solution of carboxylic acid 19aS1

(1.5 g, 6.9 mmol) in THF (34 mL) at 0 °C. MeOH (3.4 mL) was added to a suspension of

diphenyl ditelluride (2.8 g, 6.8 mmol) and NaBH4 (780 mg, 20.6 mmol) in THF (34 mL) at

0 °C. After the both reaction mixtures were stirred for 30 min at 0 °C, the former reaction

mixture was added dropwise to the latter one. The resultant reaction mixture was stirred for

another 30 min at room temperature, and then was filtered through a pad of silica gel (30 g,

EtOAc). The filtrate was concentrated, and the residue was purified by flash

chromatography on silica gel (50 g, hexane/EtOAc = 10:1) to afford 1a (2.5 g, 6.2 mmol) in

90% yield: yellow oil; []D27 = -89.5 (c 1.0, CHCl3); m.p. 53-56 °C; IR (film) 1706, 1435,

1374, 1212, 1158, 1091, 1040, 927, 865, 733 cm-1; 1H NMR (400 MHz, CDCl3) 1.32 (3H, s,

CH3 of acetonide), 1.49 (3H, s, CH3 of acetonide), 3.60 (3H, s, -OCH3), 4.38 (1H, d, J = 0.9

Hz, H4), 4.55 (1H, d, J = 6.0 Hz, H2), 5.01 (1H, dd, J = 6.0, 1.4 Hz, H3), 5.15 (1H, s, H1),

7.29-7.41 (3H, m, aromatic), 7.69-7.72 (2H, m, aromatic); 13C NMR (100 MHz, CDCl3)

25.2, 26.6, 57.8, 80.6, 84.5, 97.8, 111.2, 113.0, 113.8, 128.7, 129.4 (2C), 140.0 (2C), 206.5;

HRMS (ESI) calcd for C15H18O5TeNa [M+Na]+ 431.0109, found 431.0101.

Acyl telluride 1b. According to the general procedure A, 1b (1.4 g) was

synthesized in 83% yield from carboxylic acid 19bS2 (1.0 g, 3.6 mmol) by

using N-methylmorpholine (450 L, 4.1 mmol) and isobutyl chloroformate

(530 L, 4.1 mmol) in THF (17 mL), and diphenyl ditelluride (1.5 g, 3.7

mmol), NaBH4 (388 mg, 10.3 mmol) and MeOH (1.7 mL) in THF (17 mL).

The residue was purified by flash chromatography on silica gel (40 g,

hexane/EtOAc 5:1 to 2:1): yellow solid; []D24 = -70.3 (c 1.0, CHCl3); m.p. 144-146 °C; IR

(film) 1711, 1379, 1177, 1121, 1089, 1037, 912, 816, 734 cm-1; 1H NMR (400 MHz, CDCl3)

1.43 (3H, s, CH3 of acetonide), 1.45 (3H, s, CH3 of acetonide), 1.49 (3H, s, CH3 of

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acetonide), 1.53 (3H, s, CH3 of acetonide), 4.17 (1H, dd, J = 13.7, 2.3 Hz, H1A), 4.22 (1H, d,

J = 13.7 Hz, H1B), 4.27 (1H, dd, J = 2.3, 2.3 Hz, H2), 4.33 (1H, d, J = 2.3 Hz, H3), 4.53 (1H,

s, H4), 7.29-7.40 (3H, m, aromatic), 7.72-7.76 (2H, m, aromatic); 13C NMR (100 MHz,

CDCl3) 18.9, 25.8, 27.0, 28.8, 59.9, 72.3, 74.0, 87.2, 98.0, 114.5, 115.0, 116.3, 128.6, 129.4

(2C), 139.9 (2C), 206.4; HRMS (ESI) calcd for C18H22O6TeNa [M+Na]+ 487.0371, found

487.0385.

Acyl telluride 1c. According to the general procedure A, 1c (845 mg)

was synthesized from carboxylic acid 19cS3 (616 mg, 2.25 mmol) in 81%

yield by using N-methylmorpholine (300 L, 2.8 mmol) and isobutyl

chloroformate (350 L, 2.7 mmol) in THF (11 mL), and diphenyl

ditelluride (921 mg, 2.25 mmol), NaBH4 (255 mg, 6.74 mmol) and MeOH

(1.1 mL) in THF (11 mL). The residue was purified by flash

chromatography on silica gel (40 g, hexane/EtOAc 10:1): yellow solid; []D22 = -73.5 (c 1.0,

CHCl3); m.p. 150-153 °C; IR (film) 1717, 1383, 1253, 1212, 1173, 1072, 996, 890, 773,

733 cm-1; 1H NMR (400 MHz, CDCl3) 1.34 (3H, s, CH3 of acetonide), 1.42 (3H, s, CH3 of

acetonide), 1.54 (3H, s, CH3 of acetonide), 1.61 (3H, s, CH3 of acetonide), 3.97 (1H, dd, J =

14.6, 1.4 Hz, H1A), 4.01 (1H, dd, J = 14.6, 1.4 Hz, H1B), 4.27 (1H, ddd, J = 7.8, 1.4, 1.4 Hz,

H2), 4.50 (1H, d, J = 2.8 Hz, H4), 4.58 (1H, dd, J = 7.8, 2.8 Hz, H3), 7.29-7.41 (3H, m,

aromatic), 7.70-7.74 (2H, m, aromatic); 13C NMR (100 MHz, CDCl3) 23.9, 24.7, 26.0, 26.2,

62.0, 69.7, 70.0, 72.0, 104.5, 109.3, 110.3, 114.4, 128.7, 129.3 (2C), 140.0 (2C), 206.4;

HRMS (ESI) calcd for C18H22O6TeNa [M+Na]+ 487.0371, found 487.0371.

Two Component Reactions Using Glyoxylic Oxime Ether

General procedure B: O-Benzyl-hydroxyl amine 7a. Et3B (1.03 M in hexane, 0.36 mL,

0.37 mmol) was added to a solution of acyl telluride 1a (50 mg, 0.12 mmol) and glyoxylic

oxime ether 2S4 (48 mg, 0.25 mmol) in CH2Cl2 (6.2 mL) at room temperature. The reaction

mixture was stirred for 15 min at the same temperature, and was then concentrated. The

residue was purified by flash chromatography on silica gel (5.0 g, hexane/EtOAc 5:1) to

afford 7a (33 mg, 0.090 mmol, dr. 2:1) in 75% yield: colorless oil; IR (film) 3259, 1743,

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1454, 1373, 1239, 1205, 1160, 1093, 1061, 869 cm-1; 1H NMR (400 MHz, CDCl3) 1.27

(1.00H, s, CH3 of acetonide), 1.30 (2.00H, s, CH3 of acetonide), 1.43 (1.00H, s, CH3 of

acetonide), 1.44 (2.00H, s, CH3 of acetonide), 3.31 (3.00H, s, -OCH3), 3.63 (0.67H, d, J =

10.1 Hz, H5), 3.64 (0.33H, d, J = 5.9 Hz, H5), 3.78 (1.00H, s, -CO2CH3), 3.79 (2.00H, s,

-CO2CH3), 4.10 (0.67H, d, J = 10.1 Hz, H4), 4.47 (1.00H, d, J = 6.0 Hz, H2), 4.54 (0.33H, d,

J = 5.9 Hz, H4), 4.56 (0.33H, d, J = 6.0 Hz, H3), 4.64 (0.33H, d, J = 11.9 Hz, -CHAHBPh),

4.68 (0.67H, d, J = 11.9 Hz, -CHAHBPh), 4.71 (0.33H, d, J = 11.9 Hz, -CHAHBPh), 4.72

(0.67H, d, J = 11.9 Hz, -CHAHBPh), 4.75 (0.67H, d, J = 6.0 Hz, H3), 4.86 (0.33H, s, H1), 4.92

(0.67H, s, H1), 7.28-7.38 (5H, m, aromatic); Detectable signals of 13C NMR (100 MHz,

CDCl3) 24.9, 25.1, 26.4, 52.2, 52.3, 55.7, 55.9, 65.9, 66.4, 76.2, 76.4, 82.1, 82.3, 84.8, 84.9,

85.0, 85.6, 110.0, 111.0, 112.3, 112.5, 127.9, 128.26, 128.29, 128.6, 128.8, 137.4, 137.7,

171.1, 172.5; HRMS (ESI) calcd for C18H25NO7Na [M+Na]+ 390.1523, found 390.1513.

O-Benzyl-hydroxyl amine 7b [CAS: 1227367-16-9].S5 According to

the general procedure B, 7b (41 mg, 0.097 mmol, dr. 1:1) was

synthesized in 88% yield from acyl telluride 1b (50 mg, 0.11 mmol) and

glyoxylic oxime ether 2 (42 mg, 0.22 mmol) by using Et3B (1.03 M in

hexane, 0.32 mL, 0.33 mmol) in CH2Cl2 (5.4 mL). The residue was

purified by flash chromatography on silica gel (5.0 g, hexane/EtOAc 2:1):

colorless oil; 1H NMR (400 MHz, CDCl3) 1.24 (1.50H, s, CH3 of

acetonide), 1.29 (1.50H, s, CH3 of acetonide), 1.35 (1.50H, s, CH3 of acetonide), 1.36 (1.50H,

s, CH3 of acetonide), 1.40 (1.50H, s, CH3 of acetonide), 1.41 (1.50H, s, CH3 of acetonide),

1.43 (1.50H, s, CH3 of acetonide), 1.44 (1.50H, s, CH3 of acetonide), 3.80 (1.50H, s,

-CO2CH3), 3.81 (1.50H, s, CH3 of -CO2CH3), 3.97-4.08 (4.00H, m, H1A, 1B, 2, 6), 4.22-4.26

(1.00H, m, H3), 4.53 (0.50H, s, H4), 4.59 (0.50H, s, H4), 4.69 (1.00H, s, -CHAHBPh), 4.74

(0.50H, d, J = 11.9 Hz, -CHAHBPh), 4.78 (0.50H, d, J = 11.9 Hz, -CHAHBPh), 7.26-7.38

(5.00H, m, aromatic); Detectable signals of 13C NMR (100 MHz, CDCl3) 18.7, 18.9, 26.3,

27.3, 27.6, 28.5, 28.7, 52.2, 59.9, 60.1, 66.1, 68.8, 72.77, 72.84, 73.2, 76.1, 76.3, 85.6, 86.6,

97.3, 97.4, 111.9, 112.4, 113.1, 127.7, 128.21, 128.23, 128.6, 128.7, 137.7, 170.3, 171.3.

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O-Benzyl-hydroxyl amine 7c. According to the general procedure B,

7c (16 mg of major diastereomer and 11 mg of minor diastereomer, 0.064

mmol, dr. 1.5:1) was synthesized in 66% yield from acyl telluride 1c (45

mg, 0.097 mmol) and glyoxylic oxime ether 2 (38 mg, 0.20 mmol) by

using Et3B (1.04 M in hexane, 0.28 mL, 0.29 mmol) in CH2Cl2 (0.98 mL).

The residue was purified by flash chromatography on silica gel (5.0 g,

toluene/EtOAc 12:1): major diastereomer: colorless oil; []D28 = -33.6

(c 0.5, CHCl3); IR (film) 3272, 1746, 1454, 1382, 1250, 1217, 1152, 1118 cm-1; 1H NMR

(400 MHz, CDCl3) 1.29 (3H, s, CH3 of acetonide), 1.34 (3H, s, CH3 of acetonide), 1.47 (3H,

s, CH3 of acetonide), 1.52 (3H, s, CH3 of acetonide), 3.68 (1H, d, J = 12.8 Hz, H1A), 3.78 (3H,

s, -CO2CH3), 3.81 (1H, d, J = 12.8 Hz, H1B), 3.96 (1H, br s, H6), 4.19 (1H, d, J = 7.6 Hz, H2),

4.40 (1H, d, J = 2.4 Hz, H4), 4.57 (1H, dd, J = 7.6, 2.4 Hz, H3), 4.65 (1H, d, J = 11.9 Hz,

-CHAHBPh), 4.70 (1H, d, J = 11.9 Hz, -CHAHBPh), 6.13 (1H, br s, NH), 7.26-7.40 (5H, m,

aromatic); 13C NMR (100 MHz, CDCl3) 24.3, 25.2, 25.7, 26.6, 52.2, 61.6, 66.9, 70.2, 70.8,

71.3, 76.0, 101.4, 109.4, 109.6, 127.7, 128.3 (2C), 128.5 (2C), 137.7, 172.0; HRMS (ESI)

calcd for C21H29NO8Na [M+Na]+ 446.1785, found 446.1791.

minor diastereomer: colorless oil; []D28 = -15.6 (c 0.64, CHCl3); IR (film) 3280, 1747,

1454, 1382, 1254, 1210, 1170, 1105 cm-1; 1H NMR (400 MHz, CDCl3) 1.23 (3H, s, CH3 of

acetonide), 1.32 (3H, s, CH3 of acetonide), 1.44 (3H, s, CH3 of acetonide), 1.46 (3H, s, CH3 of

acetonide), 3.74-3.76 (2H, m, H1), 3.80 (3H, s, -CO2CH3), 3.81 (1H, s, H6), 4.15 (1H, d, J =

7.8 Hz, H2), 4.35 (1H, d, J = 2.3 Hz, H4), 4.49 (1H, dd, J = 7.8, 2.3 Hz, H3), 4.69 (1H, d, J =

11.9 Hz, -CHAHBPh), 4.75 (1H, d, J = 11.9 Hz, -CHAHBPh), 7.26-7.37 (5H, m, aromatic); 13C

NMR (100 MHz, CDCl3) 23.9, 24.8, 25.7, 26.2, 52.2, 61.0, 70.0, 70.4, 70.9, 73.0, 76.4,

101.6, 108.5, 109.0, 127.8, 128.2 (2C), 128.7 (2C), 137.7, 170.3; HRMS (ESI) calcd for

C21H29NO8Na [M+Na]+ 446.1785, found 446.1789.

Two-Component Radical Reactions Using Enones

O

1a

3

8a

Et3B, airCH2Cl2, rt

92%

O

MeO

O

O O

O

MeO

O

O

TePh

O

12

34

5

67

8

General procedure C: Ketone 8a [CAS: 81691-16-9].S6 Et3B (1.03 M in hexane, 0.36 mL,

0.37 mmol) was added to a solution of acyl telluride 1a (50 mg, 0.12 mmol) and methyl vinyl

ketone 3 (20 L, 0.24 mmol) in CH2Cl2 (6.2 mL) at room temperature. The reaction mixture

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was stirred for 15 min at the same temperature, and was then concentrated. The residue was

purified by flash chromatography on silica gel (10 g, hexane/EtOAc 3:1) to afford 8a (28 mg,

0.11 mmol) in 92% yield: colorless oil; 1H NMR (400 MHz, CDCl3) 1.29 (3H, s, CH3 of

acetonide), 1.45 (3H, s, CH3 of acetonide), 1.72-1.86 (2H, m, H5A, 5B), 2.14 (3H, s, H8),

2.49-2.64 (2H, m, H6A, 6B), 3.32 (3H, s, -OCH3), 4.10 (1H, dd, J = 9.2, 6.4 Hz, H4), 4.51 (1H,

d, J = 6.0 Hz, H3), 4.58 (1H, d, J = 6.0 Hz, H2), 4.92 (1H, s, H1); 13C NMR (100 MHz,

CDCl3) 25.0, 26.5, 28.8, 30.0, 40.1, 55.1, 84.1, 85.4, 86.3, 109.6, 112.3, 207.7.

Ketone 8b. According to the general procedure C, 8b (27 mg,

0.090 mmol) was synthesized in 82% yield from acyl telluride 1b

(50 mg, 0.11 mmol) and methyl vinyl ketone 3 (18 L, 0.21 mmol)

by using Et3B (1.03 M in hexane, 0.32 mL, 0.33 mmol) in CH2Cl2

(5.4 mL). The residue was purified by flash chromatography on

silica gel (10 g, hexane/EtOAc 2:1): colorless oil; []D19 = 0.36 (c

2.5, CHCl3); IR (film) 1715, 1378, 1239, 1197, 1167, 1120, 1079, 995, 836 cm-1; 1H NMR

(400 MHz, CDCl3) 1.31 (3H, s, CH3 of acetonide), 1.36 (3H, s, CH3 of acetonide), 1.40 (3H,

s, CH3 of acetonide), 1.44 (3H, s, CH3 of acetonide), 2.14 (3H, s, H9), 2.14-2.22 (2H, m, H6A,

6B), 2.70-2.88 (2H, m, H7A, 7B), 3.986 (1H, d J = 13.7 Hz, H1A), 3.989 (1H, dd, J = 2.3, 2.3

Hz, H2), 4.05 (1H, dd, J = 13.7, 2.3 Hz, H1B), 4.207 (1H, d, J = 2.3 Hz, H3), 4.214 (1H, s,

H4); 13C NMR (100 MHz, CDCl3) 18.6, 26.3, 27.2, 28.9, 29.9, 31.7, 38.4, 60.3, 71.8, 73.7,

86.7, 97.3, 110.8, 114.7, 208.4; HRMS (ESI) calcd for C15H24O6Na [M+Na]+ 323.1465, found

323.1459.

Ketone 8c [CAS: 151484-46-7].S 7 According to the general

procedure C, 8c (23 mg, 0.077 mmol) was synthesized in 70% yield

from acyl telluride 1c (50 mg, 0.11 mmol) and methyl vinyl ketone 3

(18 L, 0.21 mmol) by using Et3B (1.03 M in hexane, 0.32 mL, 0.33

mmol) in CH2Cl2 (5.4 mL). The residue was purified by flash

chromatography on silica gel (10 g, hexane/EtOAc 4:1): colorless

oil; 1H NMR (400 MHz, CDCl3) 1.33 (6H, s, CH3x2 of acetonide), 1.48 (3H, s, CH3 of

acetonide), 1.49 (3H, s, CH3 of acetonide), 1.97 (1H, ddd, J = 14.2, 10.1, 5.5 Hz, H6A), 2.13

(1H, m, H6B), 2.14 (3H, s, H9), 2.71 (1H, ddd, J = 18.8, 10.1, 5.5 Hz, H7A), 2.83 (1H, ddd, J

= 18.8, 10.1, 5.5 Hz, H7B), 3.68 (1H, d, J = 13.3 Hz, H1A), 3.81 (1H, dd, J = 13.3, 1.8 Hz,

H1B), 4.10 (1H, d, J = 2.7 Hz, H4), 4.19 (1H, dd, J = 8.2, 1.4 Hz, H2), 4.53 (1H, dd, J = 8.2,

2.3 Hz, H3); 13C NMR (100 MHz, CDCl3) 23.9, 24.9, 25.8, 26.3, 29.9, 34.5, 37.6, 60.8, 70.4,

70.6, 73.8, 103.5, 107.5, 108.8, 208.5.

S8


Ketone 9a. According to the general

procedure C, 9a (25 mg, 0.098 mmol, dr. 3:1)

was synthesized in 82% yield from acyl

telluride 1a (50 mg, 0.12 mmol) and

cyclopentenone 4 (21 L, 0.26 mmol) by

using Et3B (1.03 M in hexane, 0.36 mL, 0.37

mmol) in CH2Cl2 (6.2 mL). The residue was purified by flash chromatography on silica gel

(10 g, hexane/EtOAc 3:1): colorless oil; IR (film) 1743, 1373, 1210, 1160, 1107, 1091, 1061,

1029, 865 cm-1; 1H NMR (400 MHz, CDCl3) 1.31 (0.75H, s, CH3 of acetonide), 1.33 (2.25H,


1.59-1.71 (0.50H, m), 1.76-1.97 (1.50H, m), 2.11-2.47 (5H, m), 3.33 (0.75H, s, -OCH3), 3.39

(2.25H, s, -OCH3), 3.98 (0.75H, dd, J = 10.5, 0.9 Hz, H4), 3.99 (0.25H, d, J = 10.5, 1.4 Hz,

H4), 4.51 (0.75H, dd, J = 5.9, 0.9 Hz, H3), 4.595 (0.75H, d, J = 5.9 Hz, H2), 4.600 (0.25H, d,

J = 6.4 Hz, H2), 4.64 (0.25H, dd, J = 6.4, 1.4 Hz, H3), 4.94 (0.25H, s, H1), 4.97 (0.75H, s,

H1); 13C NMR (100 MHz, CDCl3) 24.95, 24.99, 25.8, 26.47, 26.48, 26.8, 37.8, 37.9, 40.8,

40.9, 41.6, 42.8, 55.37, 55.42, 82.4, 83.0, 85.4, 85.5, 90.7, 90.9, 109.4, 109.6, 112.55, 112.56,

217.7, 218.3; HRMS (ESI) calcd for C13H20O5Na [M+Na]+ 279.1203, found 279.1196.

Ketone 9b. According to the general procedure C, 9c (22 mg, 0.070


mg, 0.11 mmol) and cyclopentenone 5 (18 L, 0.22 mmol) by using Et3B

(1.03 M in hexane, 0.32 mL, 0.33 mmol) in CH2Cl2 (5.4 mL). The

residue was purified by flash chromatography on silica gel (5.0 g,

hexane/EtOAc 2:1): colorless oil; IR (film) 1740, 1375, 1241, 1195,

1121, 1080, 1009, 927, 833 cm-1; 1H NMR (400 MHz, CDCl3) 1.32 (1.70H, s, CH3 of



1.48 (1.30H, s, CH3 of acetonide), 2.06-2.24 (3.00H, m), 2.30-2.59 (3.00H, m), 2.62-2.75

(1.00H, m), 3.96-4.08 (3.00H, m, H1A, 1B, 2), 4.23 (0.43H, d, J = 2.0 Hz, H3), 4.26 (0.57H, d,

J = 2.8 Hz, H3), 4.26 (0.57H, s, H4), 4.30 (0.57H, s, H4); 13C NMR (100 MHz, CDCl3) 18.7,

18.8, 24.2 (2C), 26.78, 26.81, 27.5, 27.6, 28.6, 28.8, 37.8, 38.1, 40.8, 40.9, 43.4, 44.0, 60.27,

60.34, 71.8, 71.9, 73.65, 73.67, 86.2, 86.5, 97.3, 97.5, 111.0, 111.2, 115.9, 116.2, 218.8,

219.1; HRMS (ESI) calcd for C16H24O6Na [M+Na]+ 335.1465, found 335.1453.

S9


Ketone 9c. According to the general procedure C, 9c (18 mg, 0.058


mg, 0.097 mmol) and cyclopentenone 5 (16 L, 0.19 mmol) by using

Et3B (1.04 M in hexane, 0.28 mL, 0.29 mmol) in CH2Cl2 (4.9 mL). The

residue was purified by flash chromatography on silica gel (5.0 g,

hexane/EtOAc 2:1): colorless oil; IR (film) 1742, 1457, 1381, 1254,

1210, 1111 cm-1; 1H NMR (400 MHz, CDCl3) 1.33 (1.25H, s, CH3 of acetonide), 1.35

(3.50H, s, CH3 of acetonide), 1.38 (1.25H, s, CH3 of acetonide), 1.48 (1.75H, s, CH3 of


s, CH3 of acetonide), 2.07-2.19 (3.00H, m), 2.27-2.59 (4.00H, m), 3.74 (0.42H, d, J = 13.2 Hz,

H1A), 3.76 (0.58H, d, J = 13.2 Hz, H1A), 3.87 (0.42H, dd, J = 13.2, 2.0 Hz, H1B), 3.88 (0.58H,

dd, J = 13.2, 1.6 Hz, H1B), 4.15 (0.58H, d, J = 2.4 Hz, H4), 4.16 (0.42H, d, J = 2.8 Hz, H4),

4.20 (0.42H, dd, J = 8.0, 2.0 Hz, H2), 4.22 (0.58H, dd, J = 8.4, 1.6 Hz, H2), 4.53 (0.42H, dd,

J = 8.0, 2.4 Hz, H3), 4.55 (0.58H, dd, J = 8.4, 2.4 Hz, H3); Detectable signals of 13C NMR

(100 MHz, CDCl3) 23.57, 23.60, 23.62, 24.0, 25.47, 25.51, 25.58, 25.61, 26.46, 26.54, 38.1,

40.3, 40.6, 45.7, 45.9, 60.8, 60.9, 70.31, 70.34, 70.4, 73.15, 73.19, 104.7, 104.9, 107.5, 107.6,

108.7, 108.8, 218.9, 219.0; HRMS (ESI) calcd for C16H24O6Na [M+Na]+ 335.1465, found

335.1468.



(50 mg, 0.11 mmol) and (R)-4-TBSoxycyclopentenone 5S8 (46mg,

0.22 mmol) by using Et3B (1.03 M in hexane, 0.32 mL, 0.33 mmol)

in CH2Cl2 (5.4 mL). The residue was purified by flash

chromatography on silica gel (5.0 g, hexane/EtOAc 5:1): colorless

oil; []D25 = 50.1 (c 1.6, CHCl3); IR (film) 1747, 1375, 1255, 1191,

1121, 1080, 1065, 1036, 1007, 835 cm-1; 1H NMR (500 MHz, CDCl3) 0.08 (3H, s, -SiCH3

of TBS), 0.11 (3H, s, -SiCH3 of TBS), 0.87 (9H, s, -C(CH3)3 of TBS), 1.31 (3H, s, CH3 of


acetonide), 2.05 (1H, d, J = 18.3 Hz, H9A), 2.35 (1H, d, J = 18.3 Hz, H7A), 2.64 (1H, ddd, J =

18.3, 9.2, 1.2 Hz, H7B), 2.71 (1H, d, J = 9.2 Hz, H6), 2.86 (1H, ddd, J = 18.3, 5.2, 1.2 Hz,

H9B), 3.96 (1H, d, J = 13.2 Hz, H1A), 4.01-4.06 (2H, m, H1B, 2), 4.27 (1H, d, J = 2.3 Hz, H3),

4.35 (1H, s, H4), 4.86 (1H, d, J = 5.2 Hz, H10); 13C NMR (100 MHz, CDCl3) -4.8, -4.7,

17.9, 18.6, 25.7 (3C), 26.6, 27.5, 28.8, 38.1, 47.4, 52.0, 60.2, 70.8, 72.0, 73.6, 86.3, 97.3,

111.5, 115.3, 218.8; HRMS (ESI) calcd for C22H38O7SiNa [M+Na]+ 465.2279, found

465.2279.

S10


Ketone 10c. According to the general procedure C, 10c (28 mg,

0.063 mmol) was synthesized in 57% yield from acyl telluride 1c

(51 mg, 0.11 mmol) and (R)-4-TBSoxycyclopentenone 5 (47mg,

0.22 mmol) by using Et3B (1.04 M in hexane, 0.32 mL, 0.33 mmol)

in CH2Cl2 (5.6 mL). The residue was purified by flash

chromatography on silica gel (5.0 g, hexane/EtOAc 7:1): colorless

solid; []D28 = 37.5 (c 1.4, CHCl3); m.p. 91-93 °C; IR (film) 1748,

1471, 1461, 1383, 1374, 1254, 1209, 1188, 1171, 1103 cm-1; 1H NMR (400 MHz, CDCl3)

0.06 (3H, s, -SiCH3 of TBS), 0.09 (3H, s, -SiCH3 of TBS), 0.86 (9H, s, -C(CH3)3 of TBS),

1.33 (3H, s, CH3 of acetonide), 1.35 (3H, s, CH3 of acetonide), 1.48 (6H, s, CH3x2 of

acetonide), 2.01 (1H, d, J = 17.8 Hz, H9A), 2.45 (1H, d, J = 16.5 Hz, H7A), 2.52 (1H, d, J =

10.0 Hz, H6), 2.57 (1H, dd, J = 16.5, 10.0 Hz, H7B), 2.70 (1H, ddd, J = 17.8, 5.5, 1.4 Hz,

H9B), 3.69 (1H, d, J = 13.3 Hz, H1A), 3.80 (1H, dd, J = 13.3, 1.8 Hz, H1B), 4.18 (1H, dd, J =

8.2, 1.8 Hz, H2), 4.23 (1H, d, J = 2.3 Hz, H4), 4.53 (1H, dd, J = 8.2, 2.3 Hz, H3), 4.92 (1H, d,

J = 5.5 Hz, H10); 13C NMR (100 MHz, CDCl3) -4.7, -4.6, 17.8, 23.4, 25.3, 25.6, 25.7 (3C),

26.4, 37.3, 47.5, 54.4, 60.7, 70.1, 70.3, 70.4, 73.1, 104.1, 107.5, 108.5, 218.8; HRMS (ESI)

calcd for C22H38O7SiNa [M+Na]+ 465.2279, found 465.2269.



(100 mg, 0.22 mmol) and (R)-cryptone 6S9 (90 mg, 1.1 mmol) by

using Et3B (1.04 M in hexane, 0.63 mL, 0.65 mmol) in CH2Cl2 (2.2

mL). The residue was purified by flash chromatography on silica

gel (10.0 g, hexane/EtOAc 10:1): colorless solid; []D28 = -24.1 (c

1.9, CHCl3); m.p. 93-95 °C; IR (film) 1715, 1382, 1373, 1198,

1121, 1080, 1001 cm-1; 1H NMR (400 MHz, CDCl3) 0.91 (3H, d, J = 6.3 Hz, C12-CH3),

1.00 (3H, d, J = 6.3 Hz, C12-CH3), 1.35 (3H, s, CH3 of acetonide), 1.40 (6H, s, CH3x2 of

acetonide), 1.46 (3H, s, CH3 of acetonide), 1.64 (1H, dddd, J = 17.6, 8.7, 8.7, 6.0 Hz, H10A),

1.91 (1H, dddd, J = 8.7, 8.7, 4.3, 4.3 Hz, H11), 1.96-2.04 (2H, m, H10B, 12), 2.29-2.33 (2H,

m, H9A, 9B), 2.35 (1H, d, J = 14.2 Hz, H7A), 2.40 (1H, dd, J = 8.7, 3.3 Hz, H6), 2.75 (1H, dd,

J = 14.2, 3.3 Hz, H7B), 3.96 (1H, dd, J = 13.1, 1.4 Hz, H1A), 4.05 (1H, dd, J = 13.1, 2.7 Hz,

H1B), 4.06 (1H, ddd, J = 2.7, 2.7, 1.4 Hz, H2), 4.20 (1H, d, J = 2.7 Hz, H3), 4.32 (1H, s, H4); 13C NMR (100 MHz, CDCl3) 17.7, 19.1, 21.3, 21.5, 27.1, 27.6, 28.2, 29.9, 37.8, 39.2, 40.1,

44.0, 60.3, 72.3, 73.7, 86.3, 97.5, 111.0, 117.7, 212.6; HRMS (ESI) calcd for C20H32O6Na

[M+Na]+ 391.2091, found 391.2098.

O

OO

OO

O

TBSO10c

12

3

45

67

8910

H

HNOE

S11


Ketone 11c. According to the general procedure C, 11c (45 mg,

0.12 mmol) was synthesized in 56% yield from acyl telluride 1c

(100 mg, 0.22 mmol) and (R)-cryptone 6 (90 mg, 1.1 mmol) by

using Et3B (1.04 M in hexane, 0.63 mL, 065 mmol) in CH2Cl2 (2.2

mL). The residue was purified by flash chromatography on silica

gel (10.0 g, hexane/EtOAc 10:1): colorless solid; []D28 = -31.9 (c

0.5, CHCl3); m.p. 129-131 °C; IR (film) 1715, 1384, 1373, 1254,

1210, 1178, 1063 cm-1; 1H NMR (400 MHz, CDCl3) 0.90 (3H, d, J = 6.3 Hz, C12-CH3),

0.99 (3H, d, J = 6.3 Hz, C12-CH3), 1.32 (3H, s, CH3 of acetonide), 1.35 (3H, s, CH3 of

acetonide), 1.50 (3H, s, CH3 of acetonide), 1.61 (1H, m, H10A), 1.59 (3H, s, CH3 of

acetonide), 1.96-2.04 (3H, m, H10B, 11, 12), 2.16 (1H, ddd, J = 8.8, 7.2, 4.5 Hz, H6),

2.24-2.30 (3H, m, H7A, 9 A, 9B), 2.75 (1H, dd, J = 16.2, 4.5 Hz, H7B), 3.73 (1H, d, J = 13.3 Hz,

H1A), 3.82 (1H, dd, J = 13.3, 1.8 Hz, H1B), 4.11 (1H, d, J = 1.8 Hz, H4), 4.15 (1H, dd, J = 8.2,

1.8 Hz, H2), 4.47 (1H, dd, J = 8.2, 1.8 Hz, H3); 13C NMR (100 MHz, CDCl3) 17.9, 21.4,

21.6, 23.3, 25.1, 25.6, 26.5, 29.4, 37.8, 38.6, 39.5, 46.7, 60.6, 69.7, 70.5, 74.3, 106.5, 107.0,

108.7, 212.4; HRMS (ESI) calcd for C20H32O6Na [M+Na]+ 391.2091, found 391.2096.

Three-Component Reactions

General procedure D: Alcohol 15b. Et3B (1.03 M in hexane, 0.32 mL, 0.33 mmol) was

added to a solution of acyl telluride 1b (51 mg, 0.11 mmol), (R)-4-TBSoxycyclopentenone 5

(46mg, 0.22 mmol) and benzaldehyde 12 (33 L, 0.33 mmol) in CH2Cl2 (1.1 mL) at room

temperature. The reaction mixture was stirred for 15 min at the same temperature, and was

then concentrated. The residue was purified by flash chromatography on silica gel (5.0 g,

hexane/EtOAc = 4:1) to afford 15b (28 mg, 0.063 mmol) in 88% yield: colorless oil; []D24 =

-17.1 (c 2.7, CHCl3); IR (film) 3484, 1724, 1457, 1377, 1250, 1192, 1119, 1065, 1011, 836

cm-1; 1H NMR (400 MHz, CDCl3) 0.10 (3H, s, -SiCH3 of TBS), 0.12 (3H, s, -SiCH3 of

OO

O

11c

O

OO

12

3

45

67

8

910

11

12

H

HNOE

S12


TBS), 0.52 (3H, s, CH3 of acetonide), 0.94 (9H, s, -C(CH3)3 of TBS), 1.26 (3H, s, CH3 of

acetonide), 1.30 (3H, s, CH3 of acetonide), 1.38 (3H, s, CH3 of acetonide), 2.23-2.28 (2H, m,

H6, 9A), 2.89 (1H, d, J = 9.6 Hz, H7), 3.24 (1H, ddd, J = 18.8, 5.5, 1.4 Hz, H9B), 3.86 (1H, s,

H2), 3.90 (1H, d, J = 13.7 Hz, H1A), 4.00 (1H, dd, J = 13.7, 2.3 Hz, H1B), 4.14 (1H, d, J = 2.3

Hz, H3), 4.18 (1H, s, H4), 4.62 (1H, br s, OH), 4.79 (1H, d, J = 5.0 Hz, H10), 4.92 (1H, d, J =

9.6 Hz, H11), 7.22-7.33 (3H, m, aromatic), 7.40-7.43 (2H, m, aromatic); 13C NMR (100 MHz,

CDCl3) -4.7, -4.5, 17.9, 18.4, 24.7, 25.8 (3C), 26.8, 28.9, 48.9, 54.6, 55.8, 59.8, 70.3, 71.4,

73.8, 75.7, 86.1, 97.3, 110.5, 114.4, 127.9, 128.1 (2C), 128.2 (2C), 141.0, 222.6; HRMS (ESI)

calcd for C29H44O8SiNa [M+Na]+ 571.2698, found 571.2689.

Structural Determination of 15b

OO

O

O

O

OH

TBSO

OHPh

H

H

S1

OO

O

O

O

O

TBSO

OHPh

H

H

15b

S2

OO

O

O

O

O

TBSO

OPh

H

H

HH

H

OO

Ph

OTBS

O

OO

O O

OMeMeO

Zn(BH4)2THF,CH2Cl2

0 °C

53%

H

PPTSacetone, rt

86%

H

NOEsH

J = 9.6 Hz

1

23

45

67

8910

11

1

23

45

67

8910

11

J = 9.2 Hz

HH

General procedure E: Diol S1. A suspension of ZnCl2 (72 mg, 0.53 mmol) and NaBH4 (40

mg, 1.1 mmol) in THF (2.1 mL) was stirred at room temperature for 2 h.S10 A solution of

compound 15b (58 mg, 0.11 mmol) in CH2Cl2 (5.3 mL) was added to the suspension at 0 °C.

The reaction mixture was stirred at the same temperature for 2 h, and was quenched with

saturated aqueous NH4Cl (10 mL). The resultant mixture was extracted with EtOAc (10 mL

x2), and the combined organic layers were washed with brine (10 mL), dried over Na2SO4,

filtered, and concentrated. The residue was purified by flash chromatography on silica gel

(5.0 g, hexane/EtOAc 5:1 to 1:4) to afford diol S1 (22 mg, 0.040 mmol) in 36% yield:

colorless oil; colorless oil; []D23 = 0.50 (c 0.60, CHCl3); IR (film) 3479, 1455, 1377, 1254,

1191, 1120, 1063, 1003, 923, 834 cm-1; 1H NMR (400 MHz, CDCl3) 0.09 (3H, s, -SiCH3 of

S13


TBS), 0.12 (3H, s, -SiCH3 of TBS), 0.91 (9H, s, -C(CH3)3 of TBS), 1.16 (3H, s, CH3 of


acetonide), 1.65 (1H, br s, OH), 2.01 (1H, dd, J = 13.3, 6.9 Hz, H9A), 2.17 (1H, ddd, J = 13.3,

8.2, 5.0 Hz, H9B), 2.35 (1H, d, J = 3.2 Hz, H6), 2.65 (1H, dd, J = 8.7, 4.6 Hz, H7), 3.51 (1H,

br s, OH), 3.97-4.08 (3H, m, H1A, 1B, 2), 4.22 (1H, d, J = 2.3 Hz, H3), 4.30 (1H, s, H4),

4.54-4.64 (2H, m, H8, 10), 4.90 (1H, d, J = 5.0 Hz, H11), 7.24 (1H, m, aromatic), 7.32-7.36

(2H, m, aromatic), 7.48 (2H, d, J = 7.3 Hz, aromatic); 13C NMR (100 MHz, CDCl3) -4.8,

-4.6, 17.8, 18.6, 25.7 (3C), 26.3, 27.3, 28.8, 44.1, 56.8, 58.9, 60.0, 71.7, 73.3, 73.8, 74.0, 75.7,

86.3, 97.3, 110.9, 115.3, 126.5 (2C), 127.2, 128.3 (2C), 143.0; HRMS (ESI) calcd for

C29H46O8SiNa [M+Na]+ 573.2854, found 573.2843.

General procedure F: Acetonide S2. Pyridinium p-toluenesulfonate (PPTS, 2.8 mg, 0.011

mmol) was added to a solution of S1 (12 mg, 0.022 mmol) and 2,2’-dimethoxypropane (0.44

mL, 3.6 mmol) in acetone (0.44 mL) at room temperature. The reaction mixture was stirred

for 24h at the same temperature, and was then concentrated. The residue was purified by

flash chromatography on silica gel [32–53 μm Silica-gel BW-300 (Fuji Silysia Chemical

Ltd.)] (10 g, hexane/EtOAc 10:1) to afford acetonide S2 (11 mg, 0.019 mmol) in 86% yield:

colorless solid; []D25 = -21.1 (c 1.1, CH2Cl2); m.p. 170-175 °C; IR (film) 1461, 1380, 1244,

1186, 1123, 1067, 1010, 834 cm-1; 1H NMR (400 MHz, C6D6, at 70 °C) 0.15 (3H, s, -SiCH3

of TBS), 0.23 (3H, s, -SiCH3 of TBS), 1.01 (3H, s, CH3 of acetonide), 1.03 (9H, s, -C(CH3)3

of TBS), 1.12 (6H, s, CH3x2 of acetonide), 1.36 (3H, s, CH3 of acetonide), 1.56 (3H, s, CH3

of acetonide), 1.64 (3H, s, CH3 of acetonide), 2.12-2.16 (2H, m, H9A, 9B), 2.35 (1H, d, J = 9.2

Hz, H6), 2.45 (1H, br s, H7), 3.49 (1H, dd, J = 13.6, 3.2 Hz, H1A), 3.55 (1H, s, H2), 3.73 (1H,

br s, H4), 3.78 (1H, d, J = 13.2 Hz, H1B), 3.82 (1H, s, H3), 4.58 (1H, ddd, J = 10.0, 8.4, 7.2

Hz, H8), 4.83 (1H, s, H10), 4.94 (1H, d, J = 9.6 Hz, H11), 7.11 (1H, m, aromatic), 7.16-7.20

(2H, m, aromatic), 7.49 (2H, d, J = 7.2 Hz, aromatic); 13C NMR (100 MHz, CO(CD3)2, at

50 °C) -3.6, -3.5, 18.8, 19.7, 21.1, 26.7 (3C), 27.2, 27.8, 29.9, 31.1, 41.3, 49.9, 57.0, 61.2,

72.4, 72.7, 75.6, 75.7, 82.6, 86.4, 98.4, 101.1, 111.2, 116.6, 128.8 (2C), 128.9 (2C), 130.0,

143.0; HRMS (ESI) calcd for C32H50O8SiNa [M+Na]+ 613.3167, found 613.3176.

Alcohol 16b. According to the general procedure D, 16b (49 mg, 0.093

mmol) was synthesized in 85% yield from acyl telluride 1b (50 mg, 0.11

mmol), (R)-4-TBSoxycyclopentenone 5 (46 mg, 0.22 mmol) and

3-methylbutanal 13 (35 L, 0.33 mmol) by using Et3B (1.03 M in hexane,

0.32 mL, 0.33 mmol) in CH2Cl2 (1.1 mL). The residue was purified by

flash chromatography on silica gel (5.0 g, hexane/EtOAc 4:1): colorless

oil; []D24 = 9.7 (c 2.4, CHCl3); IR (film) 3501, 1726, 1469, 1377, 1252,

S14


1192, 1121, 1067, 1010, 836 cm-1; 1H NMR (400 MHz, CDCl3) 0.09 (3H, s, -SiCH3 of TBS),

0.13 (3H, s, -SiCH3 of TBS), 0.87 (9H, s, -C(CH3)3 of TBS), 0.90 (3H, d, J = 6.4 Hz,

C13-CH3), 0.91 (3H, d, J = 6.4 Hz, C13-CH3), 1.26-1.56 (2H, m, H12A, 12B), 1.32 (3H, s,

CH3 of acetonide), 1.35 (3H, s, CH3 of acetonide), 1.42 (3H, s, CH3 of acetonide), 1.44 (3H, s,

CH3 of acetonide), 1.96 (1H, m, H13), 2.16 (1H, d, J = 18.3 Hz, H9A), 2.44 (1H, d, J = 5.5 Hz,

H7), 2.56 (1H, s, H6), 2.97 (1H, dd, J = 18.3, 5.5 Hz, H9B), 3.92-4.07 (5H, m, H1A, 1B, 2, 11,

OH), 4.29 (1H, d, J = 2.3 Hz, H3), 4.39 (1H, s, H4), 4.85 (1H, d, J = 5.5 Hz, H10); 13C NMR

(100 MHz, CDCl3) -4.80, -4.77, 17.8, 18.5, 21.7, 23.6, 24.3, 25.7 (3C), 26.7, 27.5, 28.9,

43.9, 49.0, 53.9, 57.0, 60.1, 70.1, 71.2, 72.0, 73.6, 86.1, 97.3, 111.4, 115.3, 220.5; HRMS

(ESI) calcd for C27H48O8SiNa [M+Na]+ 551.3011, found 551.3020.


OMeMeO

Zn(BH4)2THF,CH2Cl2

0 °C

36%O

O

O

O

O

O

TBSO

OH

H

H

16b S3

OO

O

O

O

OH

TBSO

OH

H

H

S4

HH

H

OO

i-Bu

OTBS

O

OO

O O

OO

O

O

O

O

TBSO

O

H

H

PPTSacetone, rt

86%

H NOEs

H

HJ = 10.1 Hz

1

23

45

67

8910

11

12

13

1

23

45

67

8910

11

12

13

H

J = 10.4 Hz

Diol S3. According to the general procedure E, S3 (25 mg, 0.047 mmol) was synthesized in

59% yield from 16b (42 mg, 0.079 mmol) by using ZnCl2 (54 mg, 0.39 mmol) and NaBH4

(30 mg, 0.79 mmol) in THF (0.79 mL) and CH2Cl2 (1.6 mL). The residue was purified by

flash chromatography on silica gel (5.0 g, hexane/EtOAc 1:1): colorless oil; []D22 = -13.5 (c

1.3, CHCl3); IR (film) 3442, 1466, 1378, 1251, 1192, 1122, 1064, 1003, 835 cm-1; 1H NMR

(400 MHz, CDCl3) 0.08 (3H, s, -SiCH3 of TBS), 0.10 (3H, s, -SiCH3 of TBS), 0.88 (9H, s,

-C(CH3)3 of TBS), 0.93 (3H, d, J = 6.8 Hz, C13-CH3), 0.94 (3H, d, J = 6.9 Hz, C13-CH3),

1.36 (6H, s, CH3x2 of acetonide), 1.40-1.57 (2H, m, H12A, 12B), 1.43 (3H, s, CH3 of

acetonide), 1.47 (3H, s, CH3 of acetonide), 1.85 (1H, m, H13), 2.04-2.17 (2H, m, H9A, 9B),

2.25 (1H, d, J = 2.8 Hz, H6), 2.30 (1H, dd, J = 7.3, 3.2 Hz, H7), 3.81 (1H, ddd, J = 8.2, 5.0,

3.2 Hz, H11), 3.97-4.10 (3H, m, H1A, 1B, 2), 4.25 (1H, d, J = 1.8 Hz, H3), 4.38 (1H, s, H4),

S15


4.52 (1H, ddd, J = 7.8, 7.8, 4.6 Hz, H8), 4.60 (1H, d, J = 4.1 Hz, H10); 13C NMR (100 MHz,

CDCl3) -4.8, -4.6, 17.8, 18.6, 22.4, 23.2, 24.8, 25.7 (3C), 26.7, 27.4, 28.9, 44.0, 45.6, 54.9,

60.0, 60.1, 71.7, 72.0, 73.4, 73.9, 74.0, 86.4, 97.4, 110.9, 115.5; HRMS (ESI) calcd for


Acetonide S4. According to the general procedure F, S4 (21 mg, 0.037 mmol) was

synthesized in 77% yield from S3 (25 mg, 0.048 mmol) by using pyridinium

p-toluenesulfonate (PPTS, 2.4 mg, 9.5 mol) and 2,2’-dimethoxypropane (0.95 mL, 7.8

mmol) in acetone (0.95 mL). The residue was purified by flash chromatography on silica

gel [32–53 μm Silica-gel BW-300 (Fuji Silysia Chemical Ltd.)] (10 g, hexane/EtOAc 10:1):

colorless oil; []D19 = -38.9 (c 1.1, MeOH); IR (film) 1466, 1378, 1255, 1190, 1123, 1065,

1005, 905, 834 cm-1; 1H NMR (400 MHz, C6D6) 0.11 (3H, s, -SiCH3 of TBS), 0.21 (3H, s,

-SiCH3 of TBS), 0.97 (3H, s, CH3 of acetonide), 1.00 (9H, s, -C(CH3)3 of TBS), 1.05 (3H, d, J

= 4.0 Hz, C13-CH3), 1.07 (3H, d, J = 3.6 Hz, C13-CH3), 1.33 (3H, s, CH3 of acetonide), 1.39

(3H, s, CH3 of acetonide), 1.44 (3H, s, CH3 of acetonide), 1.46 (3H, s, CH3 of acetonide), 1.63

(3H, s, CH3 of acetonide), 1.87 (1H, ddd, J = 13.7, 10.0, 3.6 Hz, H12A), 2.07-2.12 (2H, m, H7,

9A), 2.17 (1H, m, H13), 2.20-2.36 (2H, m, H9B, 12B), 2.34 (1H, dd, J = 10.4, 3.2 Hz, H6),

3.42 (1H, dd, J = 13.7, 2.8 Hz, H1A), 3.60 (1H, s, H2), 3.79 (1H, d, J = 13.7 Hz, H1B), 4.00

(1H, d, J = 2.3 Hz, H3), 4.11 (1H, ddd, J = 10.1, 10.1, 1.8 Hz, H11), 4.34 (1H, ddd, J = 10.4,

10.4, 8.0 Hz, H8), 4.83 (1H, ddd, J = 5.6, 3.2, 2.4 Hz, H10), 4.86 (1H, s, H4); 13C NMR (100

MHz, C6D6) -4.2, -3.6, 18.0, 18.6, 20.2, 22.0, 24.5, 24.7, 26.0 (3C), 26.6, 27.5, 29.3, 30.5,

40.5, 44.0, 47.8, 57.7, 59.7, 71.0, 71.8, 74.1, 74.9, 75.8, 86.3, 97.2, 99.3, 110.0, 115.6; HRMS

(ESI) calcd for C30H54O8SiNa [M+Na]+ 593.3480, found 593.3468.

Alcohol 17b. According to the general procedure D, 17b (46 mg, 0.087

mmol) was synthesized in 79% yield from acyl telluride 1b (50 mg, 0.11

mmol), (R)-4-TBSoxycyclopentenone 5 (18 L, 0.22 mmol) and

3-methyl-2-butenal 14 (31 L, 0.33 mmol) by using Et3B (1.03 M in

hexane, 0.32 mL, 0.33 mmol) in CH2Cl2 (1.1 mL). The residue was

purified by flash chromatography on silica gel (5.0 g, hexane/EtOAc 4:1):

colorless oil; []D24 = 0.73 (c 2.3, CHCl3); IR (film) 3487, 1725, 1453,

1377, 1249, 1193, 1120, 1065, 1007, 835 cm-1; 1H NMR (400 MHz, CDCl3) 0.07 (3H, s,

-SiCH3 of TBS), 0.08 (3H, s, -SiCH3 of TBS), 0.87 (9H, s, -C(CH3)3 of TBS), 1.29 (3H, s,

CH3 of acetonide), 1.33 (3H, s, CH3 of acetonide), 1.42 (3H, s, CH3 of acetonide), 1.45 (3H, s,

CH3 of acetonide), 1.71 (3H, s, C13-CH3), 1.72 (3H, s, C13-CH3), 2.19 (1H, d, J = 18.3 Hz,

H9A), 2.43 (1H, s, H6), 2.57 (1H, d, J = 8.2 Hz, H7), 3.09 (1H, dd, J = 17.8, 5.5 Hz, H9B),

3.93 (1H, d, J = 13.7 Hz, H1A), 3.96 (1H, s, H2), 4.04 (1H, dd, J = 13.8, 2.3 Hz, H1B), 4.14

S16


(1H, br s, OH), 4.25 (1H, d, J = 2.3 Hz, H3), 4.40 (1H, s, H4), 4.63 (1H, dd, J = 8.7, 8.7 Hz,

H11), 4.81 (1H, d, J = 5.5 Hz, H10), 5.25 (1H, d, J = 8.7 Hz, H12); 13C NMR (100 MHz,

CDCl3) -4.7, -4.6, 17.9, 18.5, 18.6, 25.8 (3C), 25.9, 26.5, 27.4, 28.9, 49.1, 53.5, 56.4, 60.0,

69.6, 70.3, 71.6, 73.9, 86.4, 97.3, 111.1, 115.0, 125.5, 136.6, 222.2; HRMS (ESI) calcd for



H210% Pd/CNaHCO3EtOAc, rt

36%(brsm 54%)

S5

OO

O

O

O

OH

TBSO

OH

H

H

OO

O

O

O

OH

TBSO

OH

H

H

S3

OO

O

O

O

O

TBSO

OH

H

H

17b

Zn(BH4)2THF,CH2Cl2

0 °C

48%

23

45

67

8910

1112

131


48% yield from 17b (94 mg, 0.18 mmol) by using ZnCl2 (0.12 g, 0.90 mmol) and NaBH4 (68

mg, 1.8 mmol) in THF (3.6 mL) and CH2Cl2 (9.0 mL). The residue was purified by flash

chromatography on silica gel (5.0 g, hexane/EtOAc 1:2): colorless solid; []D24 = -13.7 (c

0.74, CHCl3); m.p. 98-103 °C; IR (film) 3473, 1455, 1378, 1252, 1193, 1121, 1066, 1023,

1001, 836 cm-1; 1H NMR (400 MHz, CDCl3) 0.06 (3H, s, -SiCH3 of TBS), 0.08 (3H, s,

-SiCH3 of TBS), 0.87 (9H, s, -C(CH3)3 of TBS), 1.35 (3H, s, CH3 of acetonide), 1.36 (3H, s,

CH3 of acetonide), 1.42 (3H, s, CH3 of acetonide), 1.47 (3H, s, CH3 of acetonide), 1.71 (3H, d,

J = 1.4 Hz, C13-CH3), 1.73 (3H, d, J = 0.9 Hz, C13-CH3), 2.00 (1H, dd, J = 13.3, 6.9 Hz,

H9A), 2.10 (1H, ddd, J = 12.8, 7.8, 5.0 Hz, H9B), 2.23 (1H, d, J = 3.7 Hz, H6), 2.33 (1H, dd, J

= 9.6, 5.0 Hz, H7), 2.87 (1H, br s, OH), 3.97-4.09 (3H, m, H1A, 1B, 2), 4.24 (1H, d, J = 2.3 Hz,

H3), 4.43 (1H, s, H4), 4.43-4.51 (2H, m, H8, 11), 4.61 (1H, d, J = 4.1 Hz, H10), 5.38 (1H,

ddd, J = 8.7, 1.4, 1.4 Hz, H12); 13C NMR (100 MHz, CDCl3) -4.7, -4.5, 17.7, 18.3, 18.7,

25.7 (3C), 26.0, 26.6, 27.4, 28.8, 44.6, 55.4, 58.5, 59.9, 70.5, 71.6, 73.6, 74.1, 74.7, 86.2, 97.4,

110.8, 115.5, 126.3, 135.4; HRMS (ESI) calcd for C27H48O8SiNa [M+Na]+ 551.3011, found

551.3008.

A suspension of S5 (13 mg, 0.025 mmol), NaHCO3 (11 mg, 0.13 mmol) and 10% Pd/C (2.7

mg) in EtOAc (1.3 mL) was exposed to H2 atmosphere. The reaction mixture was stirred at

room temperature for 40 h, and was then filtered through a pad of Celite. The filtrate was

concentrated and the residue was purified by flash chromatography on silica gel (5.0 g,

hexane/EtOAc 1:1 to 1:2) to afford alcohol S3 (4.7 mg, 8.9 mol) in 36% yield (33% of S5

was recovered). The physical data of S3 were matched with S3, which was derived from

16b.

S17


Alcohol 15c. According to the general procedure D, 15c (38 mg, 0.069

mmol) was synthesized in 73% yield from acyl telluride 1c (44 mg,

0.095 mmol), (R)-4-TBSoxycyclopentenone 5 (40 mg, 0.19 mmol) and

benzaldehyde 12 (29 L, 0.29 mmol) by using Et3B (1.04 M in hexane,

0.27 mL, 0.28 mmol) in CH2Cl2 (0.95 mL). The residue was purified

by flash chromatography on silica gel (5.0 g, hexane/EtOAc 4:1):

colorless oil; []D24 = -25.0 (c 1.1, CHCl3); IR (film) 3484, 1724, 1458,

1381, 1254, 1210, 1187, 1062, 898, 838 cm-1; 1H NMR (400 MHz, CDCl3) 0.10 (3H, s,

-SiCH3 of TBS), 0.13 (3H, s, -SiCH3 of TBS), 0.41 (3H, s, CH3 of acetonide), 0.94 (9H, s,

-C(CH3)3 of TBS), 1.27 (3H, s, CH3 of acetonide), 1.32 (3H, s, CH3 of acetonide), 1.44 (3H, s,

CH3 of acetonide), 2.09 (1H, d, J = 1.8 Hz, H6), 2.23 (1H, d, J = 17.9 Hz, H9A), 2.96 (1H, d, J

= 10.1 Hz, H7), 2.98 (1H, dd, J = 17.9, 5.5 Hz, H9B), 3.62 (1H, d, J = 13.3 Hz, H1A), 3.68

(1H, dd, J = 13.3, 1.8 Hz, H1B), 4.07 (1H, d, J = 2.3 Hz, H4), 4.11 (1H, dd, J = 8.2, 2.3 Hz,

H2), 4.43 (1H, dd, J =8.2, 1.8 Hz, H3), 4.58 (1H, s, OH), 4.91 (1H, d, J = 5.5 Hz, H10), 4.92

(1H, d, J = 10.1 Hz, H11), 7.25 (1H, m, aromatic), 7.30-7.34 (2H, m, aromatic), 7.42-7.44

(2H, m, aromatic); 13C NMR (100 MHz, CDCl3) -4.6, -4.4, 17.9, 23.0, 23.1, 25.6, 25.8, 25.9

(3C), 29.7, 49.1, 53.9, 58.2, 60.1, 69.8, 70.3, 73.2, 75.7, 104.1, 107.0, 108.2, 127.9, 128.1

(2C), 128.3 (2C), 141.2, 222.5; HRMS (ESI) calcd for C29H44O8SiNa [M+Na]+ 571.2698,

found 571.2695.

Structural Determination of 15c

Zn(BH4)2THF,CH2Cl2

0 °C

34%

OMe

O

OO

OO

O

TBSO

PhOH

H

H

15c

O

OO

OO

OH

TBSO

PhOH

H

H

S6

O

OO

OO

O

TBSO

PhO

H

H

S7

HH

H

OO

Ph

OTBS

O

O O

O

O

H

H

NOEsH

(+)-CSA (cat.)CH2Cl2, rt

32%

J = 10.4 Hz

23

45

67

8910

111

23

45

67

8910

111

H

J = 9.2 Hz


S18


34% yield from 15c (32 mg, 0.058 mmol) by using ZnCl2 (40 mg, 0.29 mmol) and NaBH4 (22

mg, 0.58 mmol) in THF (0.59 mL) and CH2Cl2 (1.2 mL). The residue was purified by flash

chromatography on silica gel (1.0 g, hexane/EtOAc 2:1): colorless oil; []D20 = -5.9 (c 0.53,

CHCl3); IR (film) 3474, 1730, 1460, 1378, 1254, 1208, 1060, 1008, 897, 837 cm-1; 1H NMR

(400 MHz, CDCl3) 0.10 (3H, s, -SiCH3 of TBS), 0.12 (3H, s, -SiCH3 of TBS), 0.91 (9H, s,

-C(CH3)3 of TBS), 1.19 (3H, s, CH3 of acetonide), 1.34 (3H, s, CH3 of acetonide), 1.47 (6H, s,

CH3x2 of acetonide), 1.93-2.05 (2H, m, H9A, 9B), 2.18 (1H, d, J = 3.2 Hz, H6), 2.75 (1H, dd,

J = 8.0, 4.4 Hz, H7), 3.74 (1H, d, J = 13.2 Hz, H1A), 3.83 (1H, dd, J = 13.2, 2.4 Hz, H1B),

4.18 (1H, dd, J = 8.0, 1.6 Hz, H2), 4.24 (1H, d, J = 1.6 Hz, H4), 4.52 (1H, dd, J = 8.4, 2.4 Hz,

H3), 4.56 (1H, ddd, J = 7.6, 7.6, 5.2 Hz, H8), 4.71 (1H, d, J = 2.8 Hz, H10), 4.92 (1H, d, J =

4.4 Hz, H11), 7.24 (1H, m, aromatic), 7.31-7.37 (2H, m, aromatic), 7.48-7.51 (2H, m,

aromatic); 13C NMR (100 MHz, CDCl3) -4.7, -4.5, 17.8, 23.5, 24.9, 25.7, 25.8 (3C), 26.2,

44.3, 56.1, 60.8, 61.7, 70.0, 70.6, 72.8, 73.4, 73.5, 75.5, 104.7, 107.3, 108.6, 126.3 (2C),

127.2, 128.3 (2C), 143.1; HRMS (ESI) calcd for C29H46O8SiNa [M+Na]+ 573.2854, found

573.2833.

Acetonide S7. According to the general procedure F, S7 (3.7 mg, 6.3 mol) was

synthesized in 32% yield from S6 (11 mg, 0.020 mmol) by using (+)-10-camphorsulfonic acid

((+)-CSA, 0.5 mg, 0.002 mmol) and 2-methoxypropene (19 L, 0.20 mmol) in CH2Cl2 (2.0

mL) at room temperature. The residue was purified by flash chromatography on silica gel

(1.0 g, hexane/EtOAc 20:1): colorless oil; []D23 = -37.3 (c 0.2, MeOH); IR (film) 1733,

1459, 1380, 1254, 1210, 1105, 1065, 1020, 1002, 832 cm-1; 1H NMR (400 MHz, C6D6, at

70 °C) 0.15 (3H, s, -SiCH3 of TBS), 0.21 (3H, s, -SiCH3 of TBS), 0.99 (3H, s, CH3 of

acetonide), 1.02 (9H, s, -C(CH3)3 of TBS), 1.04 (3H, s, CH3 of acetonide), 1.13 (3H, s, CH3 of


acetonide), 2.00 (1H, ddd, J = 12.0, 12.0, 6.0 Hz, H9A), 2.09 (1H, dd, J = 12.0, 6.0 Hz, H9B),

2.18 (1H, d, J = 9.2 Hz, H6), 2.61 (1H, br d, J = 9.6 Hz, H7), 3.46 (1H, d, J = 13.2 Hz, H1A),

3.52 (1H, d, J = 13.2 Hz, H1B), 3.65 (1H, dd, J = 8.4, 2.4 Hz, H2), 4.18 (1H, br s, H4), 4.27

(1H, d, J = 6.8 Hz, H3), 4.50 (1H, ddd, J = 12.0, 12.0, 6.0 Hz, H8), 4.89 (1H, d, J = 10.4 Hz,

H11), 4.92 (1H, dd, J = 5.6, 2.0 Hz, H10), 7.07-7.16 (3H, m, aromatic), 7.42 (2H, d, J = 6.8

Hz, aromatic); 13C NMR (100 MHz, CO(CD3)2, at 50 °C) -3.5, -3.4, 18.7, 21.0, 24.7, 25.4,

26.4, 26.7 (3C), 27.0, 31.1, 41.3, 48.0, 59.8, 62.0, 71.7, 71.8, 72.4, 73.9, 75.0, 82.7, 100.9,

105.4, 107.9, 109.6, 128.5 (2C), 128.6 (2C), 130.4, 143.0; HRMS (ESI) calcd for


S19


Ketone 18b. According to the general

procedure D, 18b (67 mg, 0.14 mmol)


telluride 1b (100 mg, 0.22 mmol),

(R)-cryptone 6 (90 mg, 0.65 mmol) and

benzaldehyde 12 (110 L, 1.1 mmol) by

using Et3B (1.03 M in hexane, 0.63 mL,

0.65 mmol) in CH2Cl2 (2.2 mL). The residue was purified by flash chromatography on silica

gel (10.0 g, hexane/EtOAc 10:1): colorless oil; []D28 = -7.6 (c 1.4, CHCl3); IR (film) 3460,

1714, 1384, 1374, 1198, 1121, 1079, 756 cm-1; 1H NMR (400 MHz, CDCl3) 0.93 (3H, d, J =

6.8 Hz, C12-CH3), 0.97 (3H, d, J = 6.8 Hz, C12-CH3), 0.98 (3H, s, CH3 of acetonide), 1.38

(3H, s, CH3 of acetonide), 1.40 (3H, s, CH3 of acetonide), 1.48 (3H, s, CH3 of acetonide), 1.70

(1H, m, H10A), 1.77 (1H, qq, J = 6.8, 6.8 Hz, H12), 1.91 (1H, m, H11), 2.13 (1H, m, H10B),

2.15 (1H, dd, J = 3.7, 1.4 Hz, H6), 2.44-2.48 (2H, m, H9A, 9B), 3.29 (1H, dd, J = 9.1, 1.4 Hz,

H7), 3.87 (1H, d, J = 13.2 Hz, H1A), 3.91 (1H, s, H4), 3.95 (1H, dd, J = 2.7, 2.1 Hz, H2), 3.98

(1H, dd, J = 13.2, 2.7 Hz, H1B), 3.99 (1H, d, J = 4.1 Hz, OH), 4.13 (1H, d, J = 2.1 Hz, H3),

4.86 (1H, dd, J = 9.1, 4.1 Hz, H13), 7.28 (1H, tt, J = 7.3, 1.7 Hz, aromatic), 7.36 (2H, t, J =

7.3 Hz, aromatic), 7.44 (2H, dd, J = 7.3, 1.7 Hz, aromatic); 13C NMR (100 MHz, CDCl3)

18.6, 19.0, 20.2, 22.0, 26.3, 27.3, 28.1, 30.8, 37.8, 40.5, 44.1, 53.4, 60.0, 71.9, 73.8, 75.2, 85.5,

97.7, 110.4, 118.2, 127.9 (2C), 128.0, 128.4 (2C), 141.8, 215.8; HRMS (ESI) calcd for

C27H38NaO7 [M+Na]+ 497.2510, found 497.2518.

Ketone 18c. According to the general

procedure D, 18c (47 mg, 0.099 mmol)


telluride 1c (100 mg, 0.22 mmol),

(R)-cryptone 6 (90 mg, 0.65 mmol) and

benzaldehyde 12 (110 L, 1.1 mmol) by

using Et3B (1.03 M in hexane, 0.63 mL,

0.65 mmol) in CH2Cl2 (2.2 mL). The residue was purified by flash chromatography on silica

gel (10.0 g, hexane/EtOAc 10:1): colorless oil; []D26 = -25.6 (c 0.7, CHCl3); IR (film) 3471,

1716, 1385, 1255, 1210, 1062, 757 cm-1; 1H NMR (400 MHz, CDCl3) 0.91 (3H, d, J = 6.8

Hz, C12-CH3), 0.95 (3H, s, CH3 of acetonide), 0.95 (3H, d, J = 6.8 Hz, C12-CH3), 1.35 (3H, s,

CH3 of acetonide), 1.39 (3H, s, CH3 of acetonide), 1.64 (1H, m, H10A), 1.66 (3H, s, CH3 of

acetonide), 1.81 (1H, qq, J = 6.8, 6.8 Hz, H12), 1.86 (1H, dd, J = 3.8, 1.1 Hz, H6), 1.99-2.08

(2H, m, H10B, 11), 2.40 (1H, d, J = 8.7 Hz, H9A), 2.41 (1H, dd, J = 8.7, 3.8 Hz, H9B), 3.33

OO

O

18c

OHPh

HO

OO

H

12

3

45

6 78

910

11

12

13

J = 1.1 Hz

NOEsJ = 3.8 HzO

HH

HO

HHH

H

OO

O

H

O

OH

S20


(1H, dd, J = 9.3, 1.1 Hz, H7), 3.62 (1H, d, J = 2.0 Hz, H4), 3.67 (1H, d, J = 13.3 Hz, H1A),

3.74 (1H, d, J = 13.3 Hz, 1.8 H1B), 4.09 (1H, dd, J = 8.2, 1.8 Hz, H2), 4.36 (1H, dd, J = 8.2,

2.0 Hz, H3), 4.78 (1H, d, J = 9.3 Hz, H13), 7.30 (1H, tt, J = 7.2, 1.7 Hz, aromatic), 7.37 (2H, t,

J = 7.2 Hz, aromatic), 7.47 (2H, dd, J = 7.2, 1.7 Hz, aromatic); 13C NMR (100 MHz, CDCl3)

18.4, 20.0, 22.2, 23.2, 25.0, 25.1, 26.3, 30.8, 37.9, 39.4, 46.2, 53.1, 60.5, 69.6, 70.5, 72.7,

75.5, 106.5, 107.3, 108.9, 128.2, 128.29 (2C), 128.34 (2C), 141.4, 215.9; HRMS (ESI) calcd

for C27H38NaO7 [M+Na]+ 497.2510, found 497.2521.

References

S1) Musich, J. A.; Rapoport, H. J. Am. Chem. Soc. 1978, 100, 4865.

S2) Torii, S.; Inokuchi, T.; Sugiura, T. J. Org. Chem. 1986, 51, 155.

S3) Sabesan, S. U.S. 6664399 B1, Dec 16, 2003.

S4) Miyabe, H.; Shibata, R.; Sangawa, M.; Ushiro, C.; Naito, T. Tetrahedron, 1998, 54,

11431.

S5) Yoshimi, Y.; Kobayashi, K.; Kamakura, H.; Nishikawa, K.; Haga, Y.; Maeda, K.; Morita,

T.; Itou, T.; Okada, Y.; Hatanaka, M. Tetrahedron Lett. 2010, 51, 2332.

S6) a) Kim, K. S.; Szarek, W. A. Carbohydr. Res. 1982, 100, 169. b) Sasmal, P. K.; Maier, M.

E. J. Org. Chem. 2003, 68, 824.

S7) Cubero, I. I.; Lopez-Espinosa, M. T. P.; Richardson, A. C. J. Chem. Ecol. 1993, 19,

1265.

S8) a) Curran, T. T.; Hay, D. A.; Koegel, C. P. Tetrahedron, 1997, 53, 1983. b) Watson, T. J.

N.; Curran, T. T.; Hay, D. A.; Shah, R. S.; Wenstrup, D. L.; Webster, M. E. Org. Process

Res. Dev. 1998, 2, 357. c) Ulbrich, K.; Kreitmeier, K; Reiser, O. Synlett, 2010, 2037. S9) Mori, K. Tetrahedron: Asymmetry, 2006, 17, 2133.

S10) a) Nakata, T.; Oishi, T. Tetrahedron Lett. 1980, 21, 1641. b) Kathawala, F. G.; Prager, B.;

Prasad, K.; Repič, O.; Shapiro, M. J.; Stabler, R. S.; Widler, L. Helv. Chim. Acta, 1986, 69,

803.

S21

PPM

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 0.0 -0.5

DFILE 2b 1H.alsCOMNT single_pulseDATIM 28-10-2013 14:38:45MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.44 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 13107SPO 13107TIMES 8DUMMY 1FREQU 5938.15 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 8ADBIT 16RGAIN 30BF 0.10 HzT1 0.00T2 0.00T3 90.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 147 usecIRATN 79DFILE 2b 1H.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 25.1 cSLVNT CDCL3EXREF 7.26 ppm

single_pulseC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\2b 1H.als

1.9

3 2.9

8

1.0

0

1.0

1

1.03

0.9

2

3.1

8

3.3

7

3.4

2

7.7

155

7.7

120

7.6

949

7.6

914

7.4

053

7.3

939

7.3

870

7.3

813

7.3

687

7.3

653

7.3

355

7.3

172

7.2

989

7.2

600

5.1

474

5.0

147

5.0

112

4.9

998

4.9

964

4.5

535

4.5

386

4.3

795

4.3

772

3.6

036

1.4

899

1.3

240

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0

DFILE 2b-13C.alsCOMNT single pulse decoupled gated NOEDATIM 28-10-2013 14:41:58MENUFOBNUC 13COFR 99.55 MHzOBFRQ 99.55 MHzOBSET 5.13 KHzOBFIN 0.98 HzPW1 3.03 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 26214SPO 26214TIMES 52DUMMY 4FREQU 24999.62 HzFLT 125000 HzDELAY 20.50 usecACQTM 1.0486 secPD 2.0000 secSCANS 52ADBIT 16RGAIN 60BF 1.00 HzT1 0.00T2 0.00T3 90.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 2b-13C.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 25.2 cSLVNT CDCL3EXREF 77.00 ppm

single pulse decoupled gated NOEC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\2b-13C.als

206

.487

5

139

.981

0

129

.442

61

28.6

954

113

.759

71

13.0

411

111

.240

0

97.

818

0

84.

472

6

80.

583

0 7

7.3

162

77.

000

0 7

6.6

743

57.

829

8

26.

578

8 2

5.2

088

TePh

O

OO

O

MeO

1a

TePh

O

OO

O

MeO

1a

S22

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0

DFILE 2c-13C.alsCOMNT single pulse decoupled gated NOEDATIM 07-11-2013 10:42:49MENUFOBNUC 13COFR 99.55 MHzOBFRQ 99.55 MHzOBSET 5.13 KHzOBFIN 0.98 HzPW1 3.03 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 26214SPO 26214TIMES 104DUMMY 4FREQU 24999.62 HzFLT 125000 HzDELAY 20.50 usecACQTM 1.0486 secPD 2.0000 secSCANS 104ADBIT 16RGAIN 60BF 1.00 HzT1 0.00T2 0.00T3 90.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 2c-13C.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 23.2 cSLVNT CDCL3EXREF 77.00 ppm

single pulse decoupled gated NOEC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\2c-13C.als

206

.420

5

139

.856

4

129

.366

01

28.6

187

116

.279

31

15.0

434

114

.526

1

97.

980

9

87.

241

4

77.

316

2 7

7.0

000

76.

674

3 7

4.0

109

72.

315

2

59.

870

4

28.

763

1 2

7.0

003

25.

841

1

18.

857

1

TePh

O

OO

O

O

O

1b

TePh

O

OO

O

O

O

1b

PPM

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 0.0 -0.5

DFILE 2c 1H.alsCOMNT single_pulseDATIM 07-11-2013 09:53:18MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.44 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 13107SPO 13107TIMES 8DUMMY 1FREQU 5938.15 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 8ADBIT 16RGAIN 38BF 0.10 HzT1 0.00T2 0.00T3 90.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 2c 1H.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 23.0 cSLVNT CDCL3EXREF 7.26 ppm

single_pulseC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\2c 1H.als

1.9

5

3.0

0

1.0

0

1.09

1.05 2.1

5

3.26

3.2

4 6.3

9

7.7

532

7.7

498

7.7

326

7.7

292

7.3

996

7.3

962

7.3

928

7.3

847

7.3

779

7.3

710

7.3

630

7.3

596

7.3

561

7.3

378

7.3

229

7.3

195

7.3

023

7.2

978

7.2

600

4.5

260

4.3

360

4.3

303

4.2

754

4.2

697

4.2

662

4.2

605

4.2

376

4.2

022

4.1

850

4.1

804

4.1

507

4.1

449

1.5

254

1.4

888

1.4

510

1.4

338

S23

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0

DFILE 2d-13C.alsCOMNT single pulse decoupled gated NOEDATIM 10-01-2014 17:56:23MENUFOBNUC 13COFR 99.55 MHzOBFRQ 99.55 MHzOBSET 5.13 KHzOBFIN 0.98 HzPW1 3.03 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 26214SPO 26214TIMES 86DUMMY 4FREQU 24999.62 HzFLT 125000 HzDELAY 20.50 usecACQTM 1.0486 secPD 2.0000 secSCANS 86ADBIT 16RGAIN 60BF 1.00 HzT1 0.00T2 0.00T3 90.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 2d-13C.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 21.3 cSLVNT CDCL3EXREF 77.00 ppm

single pulse decoupled gated NOEC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\2d-13C.als

206

.382

2

139

.990

6

129

.346

81

28.6

666

114

.372

8

110

.320

31

09.3

240

104

.476

3

77.

316

2 7

7.0

000

76.

674

3 7

2.0

087

69.

996

8 6

9.7

477

61.

958

9

26.

224

3 2

6.0

327

24.

729

8 2

3.8

772

PPM

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 0.0 -0.5

DFILE 2d-1H.alsCOMNT single_pulseDATIM 27-01-2014 09:33:31MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.44 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 13107SPO 13107TIMES 8DUMMY 1FREQU 5938.15 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 8ADBIT 16RGAIN 38BF 0.10 HzT1 0.00T2 0.00T3 90.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 2d-1H.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 20.9 cSLVNT CDCL3EXREF 7.26 ppm

single_pulseC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\2d-1H.als

1.8

4 2.8

3

1.9

7

1.0

0 2.0

1 3.0

43

.14

3.0

63.

11

7.7

372

7.7

326

7.7

292

7.7

178

7.7

120

7.7

086

7.4

008

7.3

973

7.3

939

7.3

859

7.3

790

7.3

722

7.3

641

7.3

607

7.3

561

7.3

321

7.3

287

7.3

172

7.3

138

7.3

092

7.3

001

7.2

955

7.2

920

7.2

600

4.5

970

4.5

901

4.5

764

4.5

706

4.5

043

4.4

974

4.2

811

4.2

777

4.2

742

4.2

617

4.2

582

4.2

548

4.0

236

4.0

202

3.9

904

3.9

881

3.9

847

3.9

550

3.9

515

1.6

078

1.5

391

1.4

247

1.3

434

OO

O

OO

TePh

O

1c

OO

O

OO

TePh

O

1c

S24

PPM

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 0.0 -0.5

DFILE 10b-1H.alsCOMNT single_pulseDATIM 24-01-2014 15:03:32MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.44 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 13107SPO 13107TIMES 8DUMMY 1FREQU 5938.15 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 8ADBIT 16RGAIN 34BF 0.10 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 10b-1H.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 21.2 cSLVNT CDCL3EXREF 7.26 ppm

single_pulseC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\10b-1H.als

4.5

9

0.67

0.2

9

2.7

20.

59 0.9

7

0.67

2.9

1

1.0

0

2.95

3.0

6

3.1

9

7.3

722

7.3

493

7.3

401

7.3

332

7.3

229

7.3

161

7.3

115

7.3

092

7.3

012

7.2

966

7.2

875

7.2

600

4.9

163

4.8

556

4.7

572

4.7

423

4.7

309

4.7

263

4.7

011

4.6

965

4.6

920

4.6

622

4.6

508

4.6

210

4.5

626

4.5

489

4.5

352

4.4

768

4.4

608

4.1

152

4.0

900

3.7

879

3.7

787

3.6

471

3.6

425

3.6

277

3.6

219

3.3

095

1.4

384

1.4

281

1.2

988

1.2

736

7a

(dr. 2:1)

O

MeO

O

O

O

OMe

HNOBn

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0



172

.467

81

71.0

691

137

.748

81

37.3

943

128

.752

91

28.5

996

128

.293

01

28.2

643

127

.900

2

112

.466

31

12.2

556

110

.991

01

10.0

233

85.

603

1 8

4.9

804

84.

913

3 8

4.7

888

82.

250

0 8

2.0

680

77.

325

7 7

7.0

000

76.

683

8 7

6.3

581

76.

214

4

66.

442

5 6

5.8

773

55.

856

2 5

5.7

030

52.

254

0 5

2.1

870

26.

444

7 2

5.0

939

24.

902

2

79.0 78.0 77.0 76.0 75.0

77.3

257

77.0

000

76.6

838

76.3

581

76.2

144

7a

(dr. 2:1)

O

MeO

O

O

O

OMe

HNOBn

S25

PPM

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 0.0 -0.5

DFILE 10c-1H.alsCOMNT single_pulseDATIM 27-01-2014 18:21:20MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.44 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 13107SPO 13107TIMES 8DUMMY 1FREQU 5938.15 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 8ADBIT 16RGAIN 32BF 0.10 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 10c-1H.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 20.9 cSLVNT CDCL3EXREF 7.26 ppm

single_pulseC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\10c-1H.als

4.7

8

1.03

1.07

0.4

30

.48

1.08 4.0

0

2.79

12.

77

7.3

722

7.3

550

7.3

401

7.3

310

7.3

252

7.3

172

7.3

035

7.2

978

7.2

898

7.2

852

7.2

772

7.2

680

7.2

600

4.7

995

4.7

698

4.7

538

4.7

240

4.6

908

4.5

878

4.5

283

4.2

594

4.2

536

4.2

330

4.2

296

4.0

763

4.0

465

4.0

259

3.9

893

3.9

836

3.9

767

3.8

050

3.7

993

1.4

396

1.4

304

1.4

087

1.3

984

1.3

640

1.3

480

1.2

862

1.2

370

HN

OO

O

O

O

OBn

O

OMe

7b

(dr. 1:1)

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0



171

.32

78

170

.27

39

137

.68

17

128

.72

41

128

.57

08

128

.22

59

128

.20

68

127

.70

86

113

.14

65

112

.37

05

111

.92

02

97.

425

2 9

7.3

390

86.

618

6 8

5.6

319

77.

325

7 7

7.0

000

76.

683

8 7

6.3

390

76.

118

6 7

3.1

583

72.

842

1 7

2.7

655

68.

780

1 6

6.1

455

60.

119

5 5

9.9

470

52.

196

6

28.

657

7 2

8.4

853

27.

584

7 2

7.2

590

26.

281

8

18.

924

1 1

8.7

229

HN

OO

O

O

O

OBn

O

OMe

7b

(dr. 1:1)

S26

PPM

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 0.0 -0.5

DFILE 10d-major-1H.alsCOMNT YUM-2-156-fra20-24-fra13-15DATIM 05-08-2014 18:18:31MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.44 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 16384SPO 16384TIMES 8DUMMY 1FREQU 7422.80 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 8ADBIT 16RGAIN 40BF 0.50 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 147 usecIRATN 79DFILE 10d-major-1H.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 24.8 cSLVNT CDCL3EXREF 7.26 ppm

YUM-2-156-fra20-24-fra13-15C:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\10d-major-1H.als

4.9

0

0.7

3

2.1

71

.04

1.0

6

1.0

3

1.0

1

1.0

9 3.0

01

.12 3.2

83

.17

3.3

53

.36

7.3

985

7.3

893

7.3

767

7.3

653

7.3

481

7.3

264

7.3

161

7.2

920

7.2

817

7.2

703

7.2

600

6.1

293

4.7

126

4.6

828

4.6

691

4.6

393

4.5

878

4.5

809

4.5

672

4.5

615

4.4

047

4.3

990

4.1

976

4.1

770

3.9

641

3.8

245

3.7

925

3.7

776

3.6

975

3.6

643

1.5

208

1.4

705

1.3

434

1.2

908

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0

DFILE 10d-major-13C.alsCOMNT YUM-2-156-fra20-24-fra13-15DATIM 05-08-2014 18:30:03MENUFOBNUC 13COFR 99.55 MHzOBFRQ 99.55 MHzOBSET 5.13 KHzOBFIN 0.98 HzPW1 3.03 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 65536SPO 65536TIMES 221DUMMY 4FREQU 31250.00 HzFLT 125000 HzDELAY 20.50 usecACQTM 1.0486 secPD 2.0000 secSCANS 221ADBIT 16RGAIN 50BF 1.00 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 10d-major-13C.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 25.0 cSLVNT CDCL3EXREF 77.00 ppm

YUM-2-156-fra20-24-fra13-15C:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\10d-major-13C.als

172.

022

4

137.

724

8

128.

489

412

8.26

91

127.

742

1

109.

611

410

9.39

10

101.

444

2

77.

320

9 7

7.0

000

76.

679

1 7

5.9

557

71.

314

1 7

0.7

824

70.

159

7 6

6.8

592

61.

570

9

52.

206

1

26.

593

2 2

5.7

453

25.

180

1 2

4.3

418

OO

O

OO

HN

OMe

O

OBnmajor diastereomer of 7c

OO

O

OO

HN

OMe

O

OBnmajor diastereomer of 7c

S27

PPM

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 0.0 -0.5

DFILE 10d-minor-1H.alsCOMNT YUM-2-156-fra28DATIM 05-08-2014 11:24:46MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.44 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 16384SPO 16384TIMES 8DUMMY 1FREQU 7422.80 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 8ADBIT 16RGAIN 48BF 0.01 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 10d-minor-1H.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 24.4 cSLVNT CDCL3EXREF 7.26 ppm

YUM-2-156-fra28C:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\10d-minor-1H.als

5.1

8

2.0

0

0.9

7

0.9

8

0.9

9 3.8

21

.86

3.3

43

.23

3.11

2.9

9

7.3

653

7.3

607

7.3

447

7.3

390

7.3

218

7.3

023

7.2

909

7.2

863

7.2

806

7.2

772

7.2

680

7.2

600

4.7

618

4.7

320

4.7

091

4.6

794

4.5

066

4.4

997

4.4

860

4.4

802

4.3

486

4.3

429

4.1

644

4.1

426

3.8

108

3.7

982

3.7

547

3.7

501

3.7

478

3.7

455

1.4

647

1.4

350

1.3

228

1.2

313

OO

O

OO

HN

OMe

O

OBnminor diastereomer of 7c

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0

DFILE 10d-minor-13C.alsCOMNT YUM-2-156-fra25-30DATIM 05-08-2014 18:51:17MENUFOBNUC 13COFR 99.55 MHzOBFRQ 99.55 MHzOBSET 5.13 KHzOBFIN 0.98 HzPW1 3.03 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 52428SPO 52428TIMES 309DUMMY 4FREQU 24999.62 HzFLT 125000 HzDELAY 20.50 usecACQTM 1.0486 secPD 2.0000 secSCANS 309ADBIT 16RGAIN 40BF 1.00 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 10d-minor-13C.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 25.0 cSLVNT CDCL3EXREF 77.00 ppm

YUM-2-156-fra25-30C:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\10d-minor-13C.als

170

.29

79

137

.73

44

128

.73

85

128

.24

03

127

.76

61

108

.97

91

108

.45

22

101

.63

10

77.

320

9 7

7.0

000

76.

679

1 7

6.3

629

72.

995

4 7

0.9

165

70.

380

0 6

9.9

680

60.

957

8

52.

201

4

26.

186

0 2

5.6

878

24.

796

9 2

3.8

819

78.0 77.0 76.0

77.3

209

77.0

000

76.6

791

76.3

629

OO

O

OO

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OMe

O

OBnminor diastereomer of 7c

S28

PPM

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 0.0 -0.5



1.00 2

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1.00

3.2

7

2.27 3.1

7

2.4

3 3.4

7

3.6

0

7.2

600

4.9

151

4.5

890

4.5

741

4.5

146

4.4

997

4.1

232

4.1

072

4.1

003

4.0

843

3.3

175

2.6

366

2.6

194

2.5

988

2.5

920

2.5

771

2.5

714

2.5

565

2.5

405

2.5

130

2.4

958

2.1

445

1.8

504

1.8

321

1.8

126

1.8

023

1.7

955

1.7

783

1.7

588

1.7

451

1.7

394

1.7

234

1.4

487

1.2

908

O

MeO

O

OO

8a

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0

DFILE 7b 13C.alsCOMNT single pulse decoupled gated NOEDATIM 29-10-2013 09:12:19MENUFOBNUC 13COFR 99.55 MHzOBFRQ 99.55 MHzOBSET 5.13 KHzOBFIN 0.98 HzPW1 3.03 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 26214SPO 26214TIMES 102DUMMY 4FREQU 24999.62 HzFLT 125000 HzDELAY 20.50 usecACQTM 1.0486 secPD 2.0000 secSCANS 102ADBIT 16RGAIN 60BF 0.10 HzT1 0.00T2 0.00T3 90.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 7b 13C.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 25.4 cSLVNT CDCL3EXREF 77.00 ppm

single pulse decoupled gated NOEC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\7b 13C.als

207

.742

6

112

.293

91

09.6

497

86.

302

5 8

5.4

211

84.

051

1

77.

325

7 7

7.0

000

76.

683

8

55.

080

2

40.

096

6

29.

989

4 2

8.8

302

26.

463

8 2

4.9

501

O

MeO

O

OO

8a

S29

OO

O

O

O

O

8b

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0

DFILE 7c 13C.alsCOMNT single pulse decoupled gated NOEDATIM 11-11-2013 09:14:49MENUFOBNUC 13COFR 124.51 MHzOBFRQ 124.51 MHzOBSET 3.45 KHzOBFIN 6.00 HzPW1 3.70 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 26214SPO 26214TIMES 91DUMMY 4FREQU 31249.52 HzFLT 157000 HzDELAY 20.80 usecACQTM 0.8389 secPD 2.0000 secSCANS 91ADBIT 16RGAIN 48BF 1.00 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 495.13 MHzIRSET 4.38 KHzIRFIN 9.64 HzIRRPW 92 usecIRATN 79DFILE 7c 13C.alsSFLKSET 748.40 KHzLKFIN 98.2 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 22.9 cSLVNT CDCL3EXREF 77.00 ppm

single pulse decoupled gated NOEC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\7c 13C.als

208

.40

68

114

.67

75

110

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05

97.

327

7

86.

651

6

77.

258

5 7

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000

76.

751

1 7

3.6

583

71.

752

9

60.

282

1

38.

393

7

31.

720

0 2

9.8

624

28.

914

5 2

7.2

006

26.

329

3

18.

611

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PPM

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 0.0 -0.5



2.00 3

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2.09

5.2

0

3.0

33

.23

3.1

43

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7.2

600

4.2

136

4.2

044

4.0

705

4.0

648

4.0

362

4.0

305

4.0

030

3.9

939

3.9

904

3.9

881

3.9

847

3.9

698

2.8

712

2.8

506

2.8

312

2.8

243

2.8

071

2.8

025

2.7

865

2.7

694

2.7

488

2.7

407

2.7

213

2.7

030

2.2

178

2.1

994

2.1

949

2.1

800

2.1

685

2.1

571

2.1

434

1.4

396

1.4

018

1.3

583

1.3

148

S30

PPM

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 0.0 -0.5

DFILE 7d-1H.alsCOMNT single_pulseDATIM 17-01-2014 15:45:01MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.44 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 13107SPO 13107TIMES 8DUMMY 1FREQU 5938.15 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 8ADBIT 16RGAIN 30BF 0.10 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 7d-1H.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 20.9 cSLVNT CDCL3EXREF 7.26 ppm

single_pulseC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\7d-1H.als

1.0

0

2.0

1

2.0

3

2.0

0 3.9

1

1.0

7

6.2

2

6.41

7.2

600

4.5

478

4.5

420

4.5

272

4.5

214

4.2

033

4.1

999

4.1

827

4.1

804

4.1

014

4.0

946

3.8

279

3.8

234

3.7

947

3.7

902

3.7

009

3.6

677

2.8

701

2.8

563

2.8

449

2.8

312

2.8

243

2.8

106

2.7

991

2.7

854

2.7

488

2.7

350

2.7

224

2.7

098

2.7

018

2.6

881

2.6

767

2.6

629

2.1

663

2.1

594

2.1

525

2.1

399

2.1

308

2.1

273

2.1

170

2.1

045

2.0

919

2.0

049

1.9

912

1.9

797

1.9

694

1.9

660

1.9

557

1.9

442

1.9

305

1.4

876

1.4

750

1.3

263

O

OO

OO

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8c

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0

DFILE 7d-13C.alsCOMNT single pulse decoupled gated NOEDATIM 17-01-2014 15:49:48MENUFOBNUC 13COFR 99.55 MHzOBFRQ 99.55 MHzOBSET 5.13 KHzOBFIN 0.98 HzPW1 3.03 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 26214SPO 26214TIMES 83DUMMY 4FREQU 24999.62 HzFLT 125000 HzDELAY 20.50 usecACQTM 1.0486 secPD 2.0000 secSCANS 83ADBIT 16RGAIN 60BF 1.00 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 7d-13C.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 21.1 cSLVNT CDCL3EXREF 77.00 ppm

single pulse decoupled gated NOEC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\7d-13C.als

208

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4

108

.806

61

07.4

846

103

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77.

325

7 7

7.0

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76.

683

8 7

3.8

385

70.

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9 7

0.4

471

60.

847

6

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1

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29.

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5 2

6.2

626

25.

783

6 2

4.8

639

23.

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OO

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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 0.0 -0.5



0.63

0.21 1.1

50

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0.9

1

2.0

40

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5.1

5

1.5

0

0.5

6 2.8

3

0.7

7 2.16

7.2

600

4.9

689

4.9

391

4.6

439

4.6

405

4.6

279

4.6

256

4.6

084

4.6

027

4.5

924

4.5

878

4.5

214

4.5

192

4.5

066

4.5

043

3.9

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3.9

893

3.9

870

3.9

756

3.9

630

3.3

873

3.3

290

2.4

649

2.4

466

2.4

226

2.4

157

2.4

020

2.3

974

2.3

814

2.3

768

2.3

688

2.3

665

2.3

551

2.3

448

2.3

345

2.3

310

2.3

150

2.3

104

2.2

990

2.2

807

2.2

761

2.2

670

2.2

612

2.2

509

2.2

464

2.2

395

2.2

212

2.2

166

2.2

143

2.2

097

2.2

006

2.1

983

2.1

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2.1

800

2.1

777

2.1

697

2.1

628

2.1

594

2.1

560

2.1

411

2.1

354

2.1

319

2.1

251

2.1

182

1.9

660

1.9

557

1.9

385

1.9

362

1.9

168

1.9

145

1.9

008

1.8

950

1.8

870

1.8

836

1.8

767

1.8

550

1.8

527

1.8

493

1.8

458

1.8

309

1.8

241

1.8

092

1.8

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1.7

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1.7

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1.7

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1.6

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1.6

810

1.6

707

1.6

639

1.6

490

1.6

410

1.6

341

1.6

261

1.6

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1.5

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1.4

808

1.4

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1.3

251

1.3

091

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(dr. 3:1)

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0



218

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24.

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S32

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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 0.0 -0.5



2.0

0

3.0

5

1.0

1 3.3

3

3.1

2

1.2

91

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1.6

71

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2.59

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7.2

600

4.2

960

4.2

617

4.2

548

4.2

285

4.2

239

4.0

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4.0

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4.0

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4.0

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4.0

374

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3.9

790

3.9

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3.9

653

2.7

407

2.7

213

2.7

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2.6

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2.6

641

2.6

435

2.6

332

2.6

240

2.5

840

2.5

805

2.5

611

2.5

565

2.5

382

2.5

348

2.5

187

2.5

142

2.5

107

2.5

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2.4

947

2.4

752

2.4

638

2.4

546

2.4

455

2.4

306

2.4

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2.3

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2.3

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2.3

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2.3

265

2.3

207

2.3

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2.2

372

2.2

155

2.2

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2.1

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2.1

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2.1

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2.1

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2.1

571

2.1

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2.1

399

2.1

216

2.1

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2.0

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2.0

655

1.4

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1.4

613

1.4

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1.3

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1.3

503

1.3

354

1.3

228

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(dr. 1.3:1)

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220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0



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DFILE 8d-1H.alsCOMNT YUM-2-155-fra7DATIM 05-08-2014 21:53:10MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.44 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 16384SPO 16384TIMES 8DUMMY 1FREQU 7422.80 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 8ADBIT 16RGAIN 42BF 0.01 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 8d-1H.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 25.0 cSLVNT CDCL3EXREF 7.26 ppm

YUM-2-155-fra7C:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\8d-1H.als

1.0

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1.0

31

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1.2

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871

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1.8

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3.6

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7.2

600

4.5

638

4.5

581

4.5

432

4.5

375

4.5

226

4.5

169

4.2

308

4.2

273

4.2

067

4.1

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4.1

816

4.1

598

4.1

529

4.1

472

3.9

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3.8

977

3.8

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3.8

817

3.8

691

3.8

646

3.8

543

3.8

485

3.7

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3.7

581

3.7

501

3.7

478

3.7

249

2.5

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2.5

622

2.5

405

2.5

348

2.5

313

2.5

210

2.5

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2.4

970

2.4

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2.4

741

2.4

604

2.4

512

2.4

478

2.4

283

2.4

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2.4

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2.3

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2.3

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2.3

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2.3

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2.3

322

2.3

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2.2

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2.1

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2.1

674

2.1

502

2.1

434

2.1

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2.1

216

2.1

136

2.1

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2.0

930

2.0

827

2.0

724

1.5

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1.5

174

1.4

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1.4

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1.3

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1.3

457

1.3

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(dr. 1.4:1)

PPM

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4.3

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4.0

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4.0

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4.0

179

4.0

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3.9

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3.9

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3.9

263

2.9

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2.9

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2.9

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2.9

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2.5

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2.4

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2.4

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2.1

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2.1

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1.9

225

1.9

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1.9

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1.8

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1.8

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1.8

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1.5

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1.5

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1.5

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1.5

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1.5

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1.4

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1.4

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1.4

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1.4

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1.4

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1.3

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1.3

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1.3

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1.2

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1.2

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1.2

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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 0.0 -0.5



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5.2

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4.8

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4.6

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4.6

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4.6

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4.4

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4.2

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4.2

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4.1

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4.0

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4.0

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4.0

213

4.0

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3.9

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3.9

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3.9

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3.1

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3.1

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3.0

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3.0

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2.5

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2.5

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2.4

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2.2

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2.1

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1.7

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1.7

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1.4

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1.4

178

1.3

286

1.2

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0.8

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0.0

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0.0

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220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0



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YUM-2-151-fra12C:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\14d-1H.als

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339

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294

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367

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634

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7.2

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383

7.2

302

7.2

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334

4.9

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4.9

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4.9

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4.5

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4.4

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4.4

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4.4

173

4.4

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4.1

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4.1

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4.1

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4.0

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4.0

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4.0

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3.6

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3.6

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3.6

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3.6

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3.6

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3.6

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3.0

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2.9

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2.9

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2.9

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2.9

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2.2

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2.2

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2.0

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884

1.4

418

1.3

171

1.2

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0.9

440

0.4

130

0.1

315

0.1

040

PPM

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YUM-2-151-fra11-13-2C:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\14d-13C.als

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KM-11-135-PTLCC:\Documents and Settings\PC-USER\My Documents\Data\Masuda Keisuke\Te-publiah\5-3H.als

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3.9

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0.9

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0.9

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0.9

349

0.9

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PPM

220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

DFILE 5-3C.alsCOMNT KM-11-131-purify-CDATIM 29-01-2015 08:50:38MENUFOBNUC 13COFR 99.55 MHzOBFRQ 99.55 MHzOBSET 5.13 KHzOBFIN 0.98 HzPW1 3.07 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 26214SPO 26214TIMES 169DUMMY 4FREQU 24999.62 HzFLT 125000 HzDELAY 20.50 usecACQTM 1.0486 secPD 2.0000 secSCANS 169ADBIT 16RGAIN 60BF 1.00 HzT1 0.00T2 0.00T3 90.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 5-3C.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 23.6 cSLVNT CDCL3EXREF 77.00 ppm

KM-11-131-purify-CC:\Documents and Settings\PC-USER\My Documents\Data\Masuda Keisuke\Te-publiah\5-3C.als

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DFILE 6-3C.alsCOMNT KM-9-153-fr14-26-CDATIM 02-09-2014 17:26:26MENUFOBNUC 13COFR 124.51 MHzOBFRQ 124.51 MHzOBSET 3.45 KHzOBFIN 6.00 HzPW1 3.70 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 26214SPO 26214TIMES 135DUMMY 4FREQU 31249.52 HzFLT 157000 HzDELAY 20.80 usecACQTM 0.8389 secPD 2.0000 secSCANS 135ADBIT 16RGAIN 56BF 1.00 HzT1 0.00T2 0.00T3 90.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 495.13 MHzIRSET 4.38 KHzIRFIN 9.64 HzIRRPW 92 usecIRATN 79DFILE 6-3C.alsSFLKSET 748.40 KHzLKFIN 98.2 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 26.5 cSLVNT CDCL3EXREF 77.00 ppm

KM-9-153-fr14-26-CC:\Documents and Settings\PC-USER\My Documents\Data\Masuda Keisuke\Te-publiah\6-3C.als

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DFILE 6-3H.alsCOMNT KM-9-153-fr14-26DATIM 02-09-2014 19:29:29MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.44 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 13107SPO 13107TIMES 8DUMMY 1FREQU 5938.15 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 8ADBIT 16RGAIN 38BF 0.10 HzT1 0.00T2 0.00T3 90.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE 6-3H.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 24.8 cSLVNT CDCL3EXREF 7.26 ppm

KM-9-153-fr14-26C:\Documents and Settings\PC-USER\My Documents\Data\Masuda Keisuke\Te-publiah\6-3H.als

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DFILE S14-13C.alsCOMNT single pulse decoupled gated NOEDATIM 25-11-2013 10:08:07MENUFOBNUC 13COFR 99.55 MHzOBFRQ 99.55 MHzOBSET 5.13 KHzOBFIN 0.98 HzPW1 3.03 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 26214SPO 26214TIMES 112DUMMY 4FREQU 24999.62 HzFLT 125000 HzDELAY 20.50 usecACQTM 1.0486 secPD 2.0000 secSCANS 112ADBIT 16RGAIN 60BF 1.00 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE S14-13C.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 21.5 cSLVNT CDCL3EXREF 77.00 ppm

single pulse decoupled gated NOEC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\S14-13C.als

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DFILE S14-1H.alsCOMNT single_pulseDATIM 25-11-2013 10:01:49MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.44 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 13107SPO 13107TIMES 8DUMMY 1FREQU 5938.15 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 8ADBIT 16RGAIN 34BF 0.10 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE S14-1H.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 21.1 cSLVNT CDCL3EXREF 7.26 ppm

single_pulseC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\S14-1H.als

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9 3.60

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3.2

1

9.8

2

6.4

0

7.4

866

7.4

683

7.3

596

7.3

413

7.3

218

7.2

600

7.2

394

7.2

199

4.9

037

4.8

911

4.6

210

4.6

096

4.5

912

4.5

832

4.5

718

4.2

983

4.2

273

4.2

216

4.0

774

4.0

705

4.0

431

4.0

362

4.0

076

3.9

756

3.5

144

2.6

675

2.6

561

2.6

458

2.6

343

2.3

516

2.3

436

2.1

983

2.1

869

2.1

777

2.1

651

2.1

525

2.1

445

2.1

319

2.1

193

2.1

159

2.0

369

2.0

186

2.0

026

1.9

854

1.6

490

1.4

304

1.4

167

1.3

594

1.1

603

0.9

120

0.1

155

0.0

937

OO

O

O

O

OH

TBSO

OHPh

H

H

S1

OO

O

O

O

OH

TBSO

OHPh

H

H

S1

S45

PPM

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 0.0 -0.5

DFILE S15-1H.alsCOMNT DK-6-004-f4-8DATIM 17-12-2014 11:02:53MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.56 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 13107SPO 13107TIMES 8DUMMY 1FREQU 5938.15 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 8ADBIT 16RGAIN 34BF 0.01 HzT1 0.00T2 0.00T3 90.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 147 usecIRATN 79DFILE S15-1H.alsSFLKSET 13.20 KHzLKFIN 69.6 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 70.0 cSLVNT C6D6EXREF 7.16 ppm

DK-6-004-f4-8C:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\S15-1H.als

1.9

4

1.4

6

0.9

5

1.0

10

.98

1.01 2.5

10

.98

1.09

0.87

1.0

1

2.0

1

3.05

3.07

3.32 5.

869

.00

3.2

2

2.8

92

.88

7.4

999

7.4

816

7.1

943

7.1

749

7.1

600

7.1

280

7.1

245

7.1

211

7.1

119

7.1

051

7.0

879

4.9

502

4.9

261

4.8

346

4.6

148

4.5

965

4.5

908

4.5

702

4.5

450

3.8

275

3.8

229

3.8

000

3.7

668

3.7

268

3.5

528

3.5

071

3.4

990

3.4

727

3.4

659

2.4

542

2.3

649

2.3

421

2.1

567

2.1

452

2.1

406

2.1

269

2.1

212

1.6

428

1.5

639

1.3

602

1.1

244

1.0

329

1.0

088

0.2

306

0.1

482

S2

O

O

O

O

O

O

TBSO

OPh

H

H

S2

OO

O

O

O

O

TBSO

OPh

H

H

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0

DFILE S15-13C.alsCOMNT DK-6-004-f4-8DATIM 18-12-2014 07:45:52MENUFOBNUC 13COFR 99.55 MHzOBFRQ 99.55 MHzOBSET 5.13 KHzOBFIN 0.98 HzPW1 3.07 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 104856SPO 104856TIMES 10000DUMMY 4FREQU 24999.62 HzFLT 125000 HzDELAY 20.50 usecACQTM 1.0486 secPD 2.0000 secSCANS 10000ADBIT 16RGAIN 60BF 1.00 HzT1 0.00T2 0.00T3 90.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE S15-13C.alsSFLKSET 12.90 KHzLKFIN 59.1 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 50.0 cSLVNT ACETNEXREF 206.26 ppm

DK-6-004-f4-8C:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\S15-13C.als

206.

456

420

6.26

00

206.

061

2

142.

984

3

129.

988

612

8.87

97

128.

750

3

116.

602

5

111.

218

3

101.

051

2 9

8.3

591

86.

378

9

82.

647

4

75.

687

3 7

5.5

627

72.

693

4 7

2.3

701

61.

211

4

57.

027

2

49.

901

8

41.

265

2 3

1.1

076

30.

808

2 3

0.6

142

30.

420

2 3

0.2

262

30.

029

8 2

9.9

268

29.

835

8 2

9.6

418

27.

816

8 2

7.2

420

26.

693

5 2

1.0

986

19.

731

0 1

8.7

705

-3.

5109

-3.

5971

32.0 31.0 30.0 29.0

31.1

076

30.8

082

30.6

142

30.4

202

30.2

262

30.0

298

29.9

268

29.8

358

29.6

418

S46

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0



115.

541

6

110.

866

4

97.

396

5

86.

379

1

77.

316

2 7

7.0

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76.

674

3 7

4.0

397

73.

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1 7

3.3

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71.

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1 7

1.7

212

60.

129

1 5

9.9

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54.

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4

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614

9 4

3.9

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28.

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9 2

7.3

548

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1 2

5.7

357

24.

796

9 2

3.2

257

22.

382

6 1

8.5

984

17.

764

9

-4.

6051

-4.

7680

PPM

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 0.0 -0.5



1.9

40

.98

1.05

3.0

4

1.00 2.0

4

2.4

0

1.5

0

8.3

75

.95

6.1

99

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5.96

7.2

600

4.6

061

4.5

958

4.5

398

4.5

283

4.5

214

4.5

100

4.5

020

4.4

905

4.3

818

4.2

525

4.2

479

4.0

866

4.0

591

4.0

534

4.0

122

3.9

790

3.8

314

3.8

234

3.8

176

3.8

108

3.8

028

3.7

982

3.7

902

2.3

173

2.3

093

2.3

001

2.2

910

2.2

521

2.2

452

2.1

651

2.1

525

2.1

445

2.1

308

2.1

228

2.1

182

2.1

102

2.0

987

2.0

816

2.0

655

2.0

472

1.8

985

1.8

824

1.8

653

1.8

458

1.8

298

1.8

126

1.7

966

1.5

689

1.5

529

1.5

483

1.5

334

1.5

185

1.5

139

1.4

979

1.4

842

1.4

716

1.4

464

1.4

430

1.4

281

1.4

064

1.3

629

0.9

452

0.9

360

0.9

280

0.9

189

0.8

754

0.0

995

0.0

777

S3

O

O

O

O

O

OH

TBSO

OH

H

H

S3

O

O

O

O

O

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TBSO

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H

H

S47

S4

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O

O

O

O

TBSO

O

H

H

S4

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O

O

O

O

TBSO

O

H

H

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0 -10.0

DFILE S17-13C2.alsCOMNT single pulse decoupled gated NOEDATIM 18-02-2014 11:20:51MENUFOBNUC 13COFR 99.55 MHzOBFRQ 99.55 MHzOBSET 5.13 KHzOBFIN 0.98 HzPW1 3.03 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 26214SPO 26214TIMES 151DUMMY 4FREQU 24999.62 HzFLT 125000 HzDELAY 20.50 usecACQTM 1.0486 secPD 2.0000 secSCANS 151ADBIT 16RGAIN 58BF 1.00 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE S17-13C2.alsSFLKSET 13.20 KHzLKFIN 69.6 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 21.0 cSLVNT C6D6EXREF 128.00 ppm

single pulse decoupled gated NOEC:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\S17-13C2.als

128.

239

512

8.00

00

127.

750

9

115.

574

3

109.

979

4

99.

345

3 9

7.2

280

86.

277

7

75.

806

4 7

4.8

676

74.

120

3 7

1.8

306

71.

025

8

59.

721

1 5

7.7

188

47.

784

0

44.

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1

40.

464

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30.

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7 2

9.2

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512

0 2

6.6

498

26.

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2 2

4.6

571

24.

494

2 2

1.9

746

20.

202

3 1

8.5

832

17.

960

5

-3.

6144

-4.

1701

PPM

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 0.0 -0.5

DFILE S17-1H.alsCOMNT single_pulseDATIM 18-02-2014 16:21:41MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.44 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 13107SPO 13107TIMES 8DUMMY 1FREQU 5938.15 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 8ADBIT 16RGAIN 30BF 0.10 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE S17-1H.alsSFLKSET 13.20 KHzLKFIN 69.6 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 20.9 cSLVNT C6D6EXREF 7.16 ppm


1.9

6

1.0

0

1.0

20

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1.0

0

0.9

9

1.0

0

2.9

81

.02 1.9

3

1.0

6

3.1

8

6.0

23

.11

3.4

6

6.1

98

.86

3.0

8

2.8

92

.97

7.1

600

4.8

632

4.8

391

4.8

334

4.8

277

4.8

208

4.8

140

4.3

814

4.3

631

4.3

551

4.3

356

4.3

299

4.3

104

4.1

342

4.1

296

4.1

090

4.1

056

4.0

850

4.0

804

4.0

049

3.9

992

3.8

080

3.7

737

3.5

986

3.4

361

3.4

292

3.4

018

3.3

961

2.3

638

2.3

558

2.3

375

2.3

295

2.2

997

2.2

837

2.2

757

2.2

494

2.2

230

2.2

127

2.2

059

2.1

967

2.1

887

2.1

795

2.1

715

2.1

635

2.1

544

2.1

475

2.1

384

2.1

178

2.1

109

2.1

075

2.0

972

2.0

937

2.0

788

1.9

037

1.8

946

1.8

786

1.8

694

1.8

591

1.8

431

1.8

339

1.6

268

1.4

586

1.4

426

1.3

911

1.3

315

1.0

741

1.0

649

1.0

580

1.0

477

1.0

008

0.9

665

0.2

146

0.1

105

S48

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0



135.

401

6

126.

300

3

115.

493

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110.

828

1

97.

415

7

86.

216

3

77.

325

7 7

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76.

683

8 7

4.7

390

74.

097

2 7

3.6

277

71.

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0

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637

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28.

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550

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6.0

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8.6

559

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339

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7.7

170

-4.

4806

-4.

7105

S5

OO

O

O

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TBSO

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PPM

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 0.0 -0.5



1.0

0

1.08 2.0

90

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1.1

4 3.41

0.83

1.2

41

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3.0

4 6.80

14.

24

10.

69

6.6

5

7.2

600

5.3

923

5.3

889

5.3

855

5.3

706

5.3

672

5.3

637

4.6

118

4.6

015

4.5

089

4.4

951

4.4

871

4.4

722

4.4

574

4.4

390

4.4

265

4.2

399

4.2

342

4.0

889

4.0

820

4.0

534

4.0

477

4.0

110

4.0

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3.9

790

2.8

689

2.3

494

2.3

368

2.3

253

2.3

139

2.2

384

2.2

292

2.1

331

2.1

251

2.1

205

2.1

136

2.0

999

2.0

873

2.0

804

2.0

678

2.0

392

2.0

243

2.0

072

1.9

912

1.9

740

1.7

314

1.7

291

1.7

165

1.7

131

1.4

659

1.4

235

1.3

594

1.3

537

0.8

708

0.0

834

0.0

594

S5

OO

O

O

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OH

TBSO

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H

H

S49

PPM

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 0.0 -0.5

DFILE S19-1H.alsCOMNT YUM-2-152-fra15-19DATIM 31-07-2014 16:50:26MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.44 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 16384SPO 16384TIMES 8DUMMY 1FREQU 7422.80 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 8ADBIT 16RGAIN 46BF 0.01 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE S19-1H.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 24.2 cSLVNT CDCL3EXREF 7.26 ppm

YUM-2-152-fra15-19C:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\S19-1H.als

1.9

1

2.10

0.8

7

0.97

0.97 1.9

7

0.95

1.0

1

0.93

1.0

0

0.98

1.0

0

2.1

8

6.27

3.1

5

3.2

9

9.0

0

2.7

93

.00

7.5

015

7.4

820

7.3

664

7.3

619

7.3

481

7.3

275

7.3

184

7.2

600

7.2

383

7.2

199

4.9

220

4.9

105

4.7

160

4.7

091

4.5

809

4.5

684

4.5

615

4.5

500

4.5

420

4.5

363

4.5

317

4.5

169

4.5

111

4.2

411

4.2

365

4.1

964

4.1

919

4.1

758

4.1

713

3.8

531

3.8

474

3.8

199

3.8

142

3.7

570

3.7

238

2.7

613

2.7

499

2.7

407

2.7

293

2.1

880

2.1

800

2.0

472

2.0

369

2.0

266

2.0

140

2.0

037

1.9

934

1.9

831

1.9

728

1.9

397

1.4

727

1.3

400

1.1

912

0.9

143

0.1

178

0.0

972

O

OO

OO

OH

TBSO

Ph

OH

H

H

S6

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0

DFILE S19-13C.alsCOMNT YUM-2-152-fra15-19DATIM 31-07-2014 14:43:54MENUFOBNUC 13COFR 99.55 MHzOBFRQ 99.55 MHzOBSET 5.13 KHzOBFIN 0.98 HzPW1 3.03 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 65536SPO 65536TIMES 312DUMMY 4FREQU 31250.00 HzFLT 125000 HzDELAY 20.50 usecACQTM 1.0486 secPD 2.0000 secSCANS 312ADBIT 16RGAIN 42BF 1.00 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE S19-13C.alsSFLKSET 13.20 KHzLKFIN 75.7 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 24.3 cSLVNT CDCL3EXREF 77.00 ppm

YUM-2-152-fra15-19C:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\S19-13C.als

143.

094

6

128.

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557

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7.30

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104.

672

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77.

320

9 7

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76.

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1 7

5.5

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73.

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72.

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5 7

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25.

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23.

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5189

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S50

PPM

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 0.0 -0.5

DFILE S20-1H.alsCOMNT YUM-3-65-fra8-20DATIM 16-12-2014 15:00:14MENUFOBNUC 1HOFR 395.88 MHzOBFRQ 395.88 MHzOBSET 6.28 KHzOBFIN 0.87 HzPW1 6.56 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 13107SPO 13107TIMES 64DUMMY 1FREQU 5938.15 HzFLT 30000 HzDELAY 16.68 usecACQTM 2.2073 secPD 2.0000 secSCANS 64ADBIT 16RGAIN 44BF 0.01 HzT1 0.00T2 0.00T3 90.00T4 100.00EXMOD single_pulse.ex2EXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE S20-1H.alsSFLKSET 13.20 KHzLKFIN 69.6 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 70.1 cSLVNT C6D6EXREF 7.16 ppm

YUM-3-65-fra8-20C:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\S20-1H.als

1.7

9

2.5

0

1.87

0.98

1.5

5

0.9

2

1.87

0.8

0

0.9

41.

011.

00 2.8

92

.88

2.9

3

3.0

0

14.6

1

2.6

92

.69

7.4

324

7.4

152

7.1

600

7.1

394

7.1

199

7.1

119

7.1

085

7.0

971

7.0

902

7.0

822

7.0

719

4.9

250

4.9

204

4.9

112

4.9

032

4.8

769

4.5

336

4.5

187

4.5

038

4.4

924

4.4

775

4.4

626

4.2

830

4.2

658

4.1

800

3.7

554

3.7

508

3.7

359

3.7

302

3.5

322

3.4

990

3.4

750

3.4

384

2.6

259

2.6

018

2.1

910

2.1

681

2.1

166

2.1

017

2.0

869

2.0

720

2.0

376

2.0

239

2.0

079

1.9

930

1.9

781

1.9

633

1.6

222

1.5

501

1.4

529

1.1

278

1.0

374

1.0

203

0.9

894

0.2

089

0.1

517

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OO

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TBSO

PhO

H

H

S7

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OO

OO

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TBSO

PhO

H

H

S7

PPM

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0

DFILE S20-13C2.alsCOMNT YUM-3-65-fra8-20DATIM 19-12-2014 07:42:07MENUFOBNUC 13COFR 99.55 MHzOBFRQ 99.55 MHzOBSET 5.13 KHzOBFIN 0.98 HzPW1 3.07 usecDEADT 0.00 usecPREDL 0.00000 msecIWT 1.0000 secPOINT 104856SPO 104856TIMES 10000DUMMY 4FREQU 24999.62 HzFLT 125000 HzDELAY 20.50 usecACQTM 1.0486 secPD 2.0000 secSCANS 10000ADBIT 16RGAIN 60BF 1.00 HzT1 0.00T2 0.00T3 100.00T4 100.00EXMOD single_pulse_decEXPCMIRNUC 1HIFR 395.88 MHzIRSET 6.28 KHzIRFIN 0.87 HzIRRPW 115 usecIRATN 79DFILE S20-13C2.alsSFLKSET 12.90 KHzLKFIN 59.1 HzLKLEV 0LGAIN 0LKPHS 0LKSIG 0CSPED 0 HzFILDCFILDFCTEMP 50.0 cSLVNT ACETNEXREF 206.26 ppm

YUM-3-65-fra8-20C:\Documents and Settings\PC-USER\ƒfƒXƒNƒgƒbƒv\matsui\S20-13C2.als

206.

458

820

6.26

00

206.

061

2

143.

046

6

130.

412

512

8.55

87

128.

458

1

109.

640

010

7.85

80

105.

419

8

100.

876

4

82.

733

6

75.

043

0 7

3.8

527

72.

422

8 7

1.8

096

71.

651

6

62.

025

7 5

9.8

318

48.

040

9 4

1.2

939

31.

062

1 3

0.7

747

30.

578

3 3

0.3

843

30.

190

3 2

9.9

963

29.

802

3 2

9.6

059

26.

968

9 2

6.6

695

26.

434

8 2

5.3

953

24.

748

7 2

1.0

435

18.

746

6

-3.

3744

-3.

5133

S51