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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: [email protected]
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