Supporting Information

© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2007

Supporting Information

Formal Total Synthesis of (–)-Apicularen A by Using a RCM and Transannular Cyclization Strategy

Young-Hee Jung, Young-Ju Kim, Jieun Lee, and Jinsung Tae*

[a] Ms. Y.-H. Jung, Mr. Y.-J. Kim, Ms. J. Lee, Prof. Dr. J. Tae* Department of Chemistry and Center for Bioactive Molecular Hybrids (CBMH) Yonsei University Seoul 120-749, Korea Fax: (+82) 2-364-7050 E-mail: jstae@yonsei.ac.kr

Supporting Information

1. 1H and 13C NMR copies of all new compounds

2. Reference 1H and 13C NMR copies of compound 3

(ref. 5e: B. R. Graetz, S. D. Rychnovsky, Org. Lett.

2003, 5, 3357–3360)

1. 1H and 13C NMR copies of all new compounds

98

76

54

32

10

ppm

1.7691.7901.7971.8081.8191.8291.8461.8523.1523.5513.5733.5883.5993.6103.6343.6553.6703.6793.6923.7164.2914.3114.4865.0555.0965.1995.2055.2105.2685.2735.2795.7805.8025.8215.8455.8715.8905.9137.2287.2397.2607.2777.2957.3117.3237.3307.362

2.04

0.96

2.21

1.062.02

1.031.05

1.00

5.36

−20240

220200

180160

140120

10080

6040

200

ppm

36.32

68.1471.5373.2276.6577.1677.67

114.34

127.69127.72128.43137.95140.60

98

76

54

32

10

ppm 1.6721.6871.7021.9281.9451.9631.9801.9852.0022.0202.0372.3942.4202.4472.4692.5132.5242.5332.5442.7782.7952.8143.0893.1013.1183.1293.1453.7584.3784.3914.4034.4154.4275.0695.1125.1345.7685.7975.8105.8355.8776.8036.8136.8306.8406.8526.8766.8886.8986.9156.925

1.13

1.19

2.091.36

1.09

1.08

3.20

1.05

2.02

1.00

4.05

210200

190180

170160

150140

130120

110100

9080

7060

5040

3020

10ppm

37.5938.72

47.6749.61

55.71

76.6577.1577.66

114.73117.92118.02

133.68

152.19154.29

98

76

54

32

10

ppm

−0.125−0.0030.0230.0920.8550.9110.9411.2881.3061.3231.6641.8001.8231.8291.8351.8511.8581.9081.9161.9311.9392.3302.3482.3662.3842.4172.4262.4302.4342.4432.5142.5283.7604.0924.1004.1074.1144.1224.1944.2124.2304.2484.3434.3514.3604.3675.0695.0745.0815.1105.1135.7625.7795.7865.8065.8306.8127.260

3.1923.348

9.792

3.112

1.0731.063

1.1011.1082.105

3.208

1.1002.0411.067

2.131

1.000

4.265

210200

190180

170160

150140

130120

110100

9080

7060

5040

3020

10ppm −4.73

−4.22

14.16

18.08

25.9228.53

37.96

42.14

55.80

61.92

67.13

73.6875.1276.8577.1677.48

86.06

114.77117.05118.01

133.59

151.83153.81153.94

exam’

98

76

54

32

10

ppm −0.102

0.0160.0430.8490.8741.2741.2781.8491.8561.8711.8781.9141.9231.9381.9451.9601.9742.0022.0212.0362.3622.3802.5262.5393.5263.5413.5573.7583.7694.1184.1324.1404.3694.4995.0875.0945.1235.2055.2325.2935.3365.5195.5355.7775.7935.8035.8205.8375.8466.8287.2607.2827.2877.2977.3037.3387.3467.352

3.0893.068

9.227

1.1603.495

1.2171.1671.992

2.146

3.462

1.1361.0822.145

2.3581.0261.0541.0001.0681.030

4.338

1.1323.938

210200

190180

170160

150140

130120

110100

9080

7060

5040

3020

10ppm −4.72

−4.20

18.07

25.9228.56

34.40

37.92

42.16

55.77

66.0467.1473.2173.6673.9075.0876.8577.1677.4886.36

114.76117.03117.67118.00

127.72127.80128.50133.55135.56138.32

151.78152.94153.93

exam’

98

76

54

32

10

ppm

−0.0440.8681.7391.8141.8392.0452.0592.1002.1182.1342.3362.3542.4172.7342.7522.7682.8322.8483.4903.6413.6573.7624.2144.3534.5074.5374.5704.5995.0735.0955.1345.1905.2165.4015.4445.7405.7555.8135.8305.8715.9136.7796.8016.8176.9006.9207.2607.2807.2917.3007.3407.3597.376

5.980

9.352

1.5601.2191.7121.4111.4451.3221.1501.070

2.0736.028

1.1181.1542.069

2.0490.9521.000

1.0370.8981.025

4.9341.106

2.2643.616

210200

190180

170160

150140

130120

110100

9080

7060

5040

3020

10ppm −4.77

−4.49

17.99

25.97

34.61

38.0041.6642.02

55.6355.70

66.3569.5573.0273.1274.2176.8177.1377.45

108.98114.55117.18117.30117.56123.08124.58127.57127.65128.39129.93133.93136.16137.19138.43

151.93153.71156.42

167.42

exam’

98

76

54

32

10

ppm

1.7821.8821.8922.0392.0582.0752.0922.1812.2002.2152.2232.2502.3822.4112.4162.4452.5893.2783.3093.5823.5943.6093.6153.7473.7824.4664.4954.5234.5525.7495.7875.8065.8115.8266.2886.7916.8046.8106.8206.8276.8316.8556.8636.8696.8806.8867.2297.2437.2497.2697.2817.2867.3097.3147.3287.3397.3457.359

1.1301.0403.0871.1861.030

1.070

2.1623.0322.948

0.987

1.0701.867

2.001

1.000

6.144

5.618

210200

190180

170160

150140

130120

110100

9080

7060

5040

3020

10ppm

33.73

37.5440.8742.68

55.7555.96

66.4568.0072.9873.3476.8477.0477.1677.48

109.83

114.87117.95123.03124.17127.67127.80128.47130.43131.94134.39137.88138.40

151.14154.52156.81

167.63

exam’

98

76

54

32

10

ppm

0.0031.2601.5851.6281.6321.7691.7821.7981.8151.8211.8321.8491.9171.9341.9511.9662.0462.3662.3692.4032.4063.5763.5863.6133.6353.6493.6523.6633.6703.6923.7714.5104.5404.5744.6036.7356.7556.7636.7846.8166.8326.8396.8456.8476.8546.8616.8777.2037.2237.2437.2607.2687.2867.3227.3417.3597.3787.396

1.2992.2611.7372.1181.0471.006

1.0312.0143.0153.0281.023

1.0012.0451.051

1.000

2.0054.041

2.3273.771

210200

190180

170160

150140

130120

110100

9080

7060

5040

3020

10ppm

34.1435.2936.2238.6839.97

55.86

65.8066.5170.8571.4173.4873.9576.8677.1877.49

109.42

114.89117.66122.89125.82127.70127.91128.56130.15

138.63138.90

151.19154.31155.87

169.73

APT−13C spectrum of

98

76

54

32

10

ppm

0.001.591.591.601.621.631.631.691.781.791.801.801.821.831.841.851.871.881.891.891.901.911.931.942.082.082.092.372.382.412.412.782.793.553.583.593.613.773.813.833.843.853.863.863.983.994.004.404.414.514.514.525.295.766.776.796.806.826.826.836.846.846.856.866.876.877.247.267.267.28

1.00

5.49

1.01

0.99

0.97

1.003.033.411.561.05

1.031.00

1.00

1.984.10

1.18

exam’

210200

190180

170160

150140

130120

110100

9080

7060

5040

3020

10ppm

33.8436.3337.2638.5340.39

55.7755.82

60.76

65.6671.2873.9574.0776.8577.1677.48

109.33

114.88117.59

123.04125.17

130.53

139.06

151.12154.32155.53

169.81

exam’

98

76

54

32

10

ppm 0.0001.2561.5711.6071.7681.7811.7971.8151.8321.8431.8692.0452.0582.0722.0832.0922.1022.1172.3112.3302.3492.3622.3992.4132.4322.4503.5343.5623.5713.5983.7713.8013.8534.0054.0174.0314.3904.4144.5064.5175.6176.1916.2276.5806.5986.6166.7326.7516.7926.8146.8226.8386.8506.8666.8737.2157.2367.260

1.49

3.98

1.24

3.44

1.413.263.161.22

1.181.18

1.00

1.03

1.161.224.94

0.80

exam’

210200

190180

170160

150140

130120

110100

9080

7060

5040

3020

10ppm

34.0336.1038.5939.4540.96

55.8156.12

65.4271.2571.6973.9076.8577.1677.4877.90

109.45

114.86117.60

122.78125.45

130.27

138.84141.34

151.10154.29155.98

169.61

exam’

98

76

54

32

10

ppm

1.2541.5501.5951.6021.6361.8171.8321.8541.8651.8721.8821.9741.9862.0072.4322.4362.4573.4923.5193.5273.5553.8653.8784.0564.0714.3024.3145.5165.5245.5305.5365.5445.9046.2336.2696.5486.5656.7416.7606.8166.8367.1797.1997.2197.2597.260

3.4112.3341.091

3.186

1.057

1.0981.072

1.067

1.067

0.948

1.000

1.0481.0181.017

1.057

2030

4050

6070

8090

100110

120130

140150

160170

180190

200210

ppm

37.4938.9039.4339.7641.23

65.1466.4872.5373.3976.8077.1177.4378.47

115.46

122.16122.72

131.35

138.75141.07

153.22

168.58

exam’

2. Reference 1H and 13C NMR copies of compound 3

(ref. 5e: B. R. Graetz, S. D. Rychnovsky, Org. Lett.

2003, 5, 3357–3360)

12

34

56

78

9ppm

Integral

1.0000

0.98240.9938

0.8447

0.9678

1.0011

0.9814

1.1395

1.2284

1.0596

1.0917

0.4594

2.7173

1.1605

2.0405

2.6816

1.9204

1.1449

ppm

7.260137.213777.197947.18211

6.832946.816416.756836.741756.564346.55133

6.265366.23656

5.93750

4.312514.302794.127864.113594.06374

3.86774

3.544613.522823.515943.49411

2.771292.472812.458832.433532.422702.044672.003101.986491.977071.870561.850571.841631.820041.675711.655881.649561.635591.629851.608701.574831.551931.538291.272411.257921.252781.24409

0.20740

BRG5

-122

Fra

ctio

n 1

Current Data Parameters

USER xitian

NAME BRG5-122f1

EXPNO 3

PROCNO 1

F2 - Acquisition Parameters

Date_ 20030521

Time 21.39

INSTRUM omega500

PROBHD 5 mm broadban

PULPROG zg30

TD 65536

SOLVENT CDCl3

NS 8

DS 2

SWH 8012.820 Hz

FIDRES 0.122266 Hz

AQ 4.0894966 sec

RG 456.1

DW 62.400 usec

DE 6.00 usec

TE 300.0 K

D1 0.10000000 sec

============ CHANNEL f1 =============

NUC1 1H

P1 13.00 usec

PL1 -1.00 dB

SFO1 500.2235015 MHz

F2 - Processing parameters

SI 65536

SF 500.2200312 MHz

WDW EM

SSB 0

LB 0.30 Hz

GB 0

PC 4.00

1D NMR plot parameters

CX 22.80 cm

CY 14.04 cm

F1P 10.000 ppm

F1 5002.20 Hz

F2P 0.000 ppm

F2 0.00 Hz

PPMCM 0.43860 ppm/cm

HZCM 219.39476 Hz/cm

OH

OO

I

O

OH

2040

6080

100

120

140

160

180

ppm

ppm

168.48

153.08

140.95138.62

131.20

122.59122.07

115.32

78.35 77.25 77.00 76.74 73.25 72.39

66.39 65.02

41.11 39.61 39.27 38.79 37.39

BRG5

-122

Fra

ctio

n 1

13C

spec

trum

wit

h 1H

dec

oupl

ing

Current Data Parameters

USER xitian

NAME BRG5-122f1

EXPNO 4

PROCNO 1

F2 - Acquisition Parameters

Date_ 20030521

Time 21.43

INSTRUM omega500

PROBHD 5 mm broadban

PULPROG zgdc30

TD 65536

SOLVENT CDCl3

NS 3444

DS 4

SWH 30303.031 Hz

FIDRES 0.462388 Hz

AQ 1.0813940 sec

RG 5160.6

DW 16.500 usec

DE 4.50 usec

TE 300.0 K

D1 0.25000000 sec

D11 0.03000000 sec

============ CHANNEL f1 =============

NUC1 13C

P1 22.50 usec

PL1 -6.00 dB

SFO1 125.7942048 MHz

============ CHANNEL f2 =============

CPDPRG2 waltz16

NUC2 1H

PCPD2 80.00 usec

PL2 -1.00 dB

PL12 14.40 dB

SFO2 500.2230013 MHz

F2 - Processing parameters

SI 65536

SF 125.7804272 MHz

WDW EM

SSB 0

LB 1.00 Hz

GB 0

PC 2.00

1D NMR plot parameters

CX 22.80 cm

CY 152.99 cm

F1P 200.000 ppm

F1 25156.09 Hz

F2P 0.000 ppm

F2 0.00 Hz

PPMCM 8.77193 ppm/cm

HZCM 1103.33716 Hz/cm

OH

OO

I

O

OH