2114
Y. Nakagawa et al. / Tetrahedron 58 *2002) 2101±2115
C-200 using hexane and increasing amounts of EtOAc to
give 44 03.50 g, 9.00 mmol, 95.3%). Compound 44: H
7.18 02H, m), 7.22 02H, m), 7.31 06H, m); HR-EI-MS m/z:
611.4373 0M1, calcd for C37H61NO4Si, 611.4370).
1
NMR d 0CDCl3, 0.081 M, 500 MHz, 300 K) ppm: 0.91
03H, t, J6.9 Hz), 1.28±1.49 06H, m), 1.60 02H, m), 1.96
03H, s), 2.08 03H, s), 2.41 02H, d, J7.0 Hz), 3.14 01H, dd,
J14.0, 8.8 Hz), 3.32 01H, dd, J14.0, 4.3 Hz), 4.09 01H,
dd, J11.9, 5.6 Hz), 4.28 01H, dd, J11.9, 3.9 Hz), 5.34
01H, m), 7.26 01H, d, J8.0 Hz), 7.51 01H, dd, J8.0,
1.7 Hz), 7.93 01H, d, J1.7 Hz); HR-FAB-MS m/z:
390.1934 0MH1, calcd for C21H28NO6, 390.1916).
Compound 48 02.03 g, 3.32 mmol) was treated in a manner
similar to that described for the synthesis of 41 to give 49
0437 mg, 0.869 mmol, 26.2% in two steps), in which two
diastereomers existed in a ratio of 1:0.3. Compound 49: 1H
NMR d 0CDCl3, 0.062 M, 500 MHz, 300 K) ppm for the
major diastereomer: 0.07 03H, s), 0.09 03H, s), 0.88 03H, d,
J7.1 Hz), 0.89 03H, d, J6.7 Hz), 0.90 09H, s), 1.27±1.38
014H, m), 1.58 02H, m), 1.91 02H, m), 2.54 02H, t, J
8.2 Hz), 2.77 03H, s), 2.80 01H, dd, J16.0, 8.3 Hz), 3.20
01H, dd, J16.0, 3.5 Hz), 3.65 01H, dd, J10.6, 5.2 Hz),
3.68 01H, t, J7.8 Hz), 3.75 01H, dd, J10.6, 6.3 Hz), 5.34
01H, m), 6.83 01H, dd, J7.7, 1.4 Hz), 6.91 01H, d, J
1.2 Hz), 6.96 01H, d, J7.7 Hz), for the minor diastereomer:
0.08 03H, s), 0.10 03H, s), 0.87 03H, d, J7.3 Hz), 0.90 03H,
d, J7.6 Hz), 0.92 09H, s), 1.27±1.38 014H, m), 1.58 02H,
m), 1.74 02H, m), 2.56 02H, t, J8.9 Hz), 2.85 01H, dd,
J15.0, 6.1 Hz), 2.85 03H, s), 3.05 01H, dd, J15.0,
2.6 Hz), 3.60 01H, dd, J10.2, 5.9 Hz), 3.61 01H, t, J
7.3 Hz), 3.79 01H, dd, J10.2, 5.8 Hz), 4.64 01H, m), 6.87
01H, dd, J7.7, 1.5 Hz), 6.94 01H, d, J1.4 Hz), 7.01 01H,
d, J7.7 Hz); HR-EI-MS m/z: 503.3797 0M1, calcd for
C30H53NO3Si, 503.3794).
Compound 44 03.50 g, 9.00 mmol) was treated in a manner
similar to that described for the synthesis of 27 to give the
crude aniline. This aniline was treated in a manner similar to
that described for the synthesis of 35 to give 45 02.04 g,
5.22 mmol, 58.0% in two steps), in which two conformers
1
existed in a ratio of 1:0.7. Compound 45: H NMR d
0CDCl3, 0.101 M, 500 MHz, 300 K) ppm for the major
conformer: 0.87 03H, t, J7.0 Hz), 1.26±1.30 010H, m),
1.63 02H, m), 2.07 03H, s), 2.15 03H, s), 2.58 02H, t,
J7.8 Hz), 2.75 01H, dd, J14.3, 10.4 Hz), 2.97 01H, dd,
J14.3, 3.2 Hz), 4.16 01H, dd, J12.3, 6.2 Hz), 4.20 01H,
dd, J12.3, 2.9 Hz), 4.83 01H, m), 6.89 01H, dd, J7.8,
1.4 Hz), 6.98 01H, d, J7.8 Hz), 8.08 01H, d, J1.0 Hz),
8.50 01H, d, J1.6 Hz), 8.67 01H, br.s), for the minor
conformer: 0.87 03H, t, J6.9 Hz), 1.26±1.30 010H, m),
1.63 02H, m), 2.08 03H, s), 2.10 03H, s), 2.58 02H, t, J
7.8 Hz), 2.81 01H, dd, J14.3, 7.5 Hz), 2.95 01H, dd,
J14.3, 6.2 Hz), 4.08 01H, dd, J12.2, 5.7 Hz), 4.27 01H,
dd, J12.2, 3.2 Hz), 4.99 01H, m), 6.98 01H, d, J7.5 Hz),
6.99 01H, s), 7.09 01H, d, J7.5 Hz), 8.38, 01H, br.d,
J10.8 Hz), 8.57 01H, d, J11.0 Hz); HR-EI-MS m/z:
391.2357 0M1, calcd for C22H33NO5, 391.2358).
Compound 49 0420 mg, 0.835 mmol) was treated in a
manner similar to that described for the synthesis of 19 to
give 50 0339 mg, 0.581 mmol, 69.6%), in which two dia-
1
stereomers existed in a ratio of 1:0.3. Compound 50: H
NMR d 0CDCl3, 0.047 M, 500 MHz, 300 K) ppm for the
major diastereomer: 0.07 03H, s), 0.10 03H, s), 0.89 06H, m),
0.90 09H, s), 1.20±1.35 014H, m), 1.57 02H, m), 1.90 02H,
m), 2.65 02H, m), 2.76 03H, s), 2.79 01H, dd, J16.2,
8.3 Hz), 3.14 01H, dd, J16.2, 3.4 Hz), 3.65 01H, dd,
J10.5, 5.4 Hz), 3.66 01H, t, J7.4 Hz), 3.75 01H, dd,
J10.5, 6.1 Hz), 5.23 01H, m), 6.92 01H, s), 7.22 01H, s),
for the minor diastereomer: 0.09 03H, s), 0.11 03H, s), 0.89
06H, m), 0.92 09H, s), 1.20±1.35 014H, m), 1.57 02H, m),
1.68 02H, m), 2.65 02H, m), 2.79 01H, dd, J14.8, 3.3 Hz),
2.84 03H, s), 3.02 01H, dd, J14.8, 3.1 Hz), 3.57 01H, t,
J7.2 Hz), 3.57 01H, dd, J15.3, 6.0 Hz), 3.77 01H, dd,
J15.3, 5.7 Hz), 4.67 01H, m), 6.95 01H, s), 7.26 01H, s);
HR-EI-MS m/z: 581.2882 0M1, calcd for C30H52NO3SiBr,
581.2899).
Compound 45 02.03 g, 5.20 mmol) was treated in a manner
similar to that described for the synthesis of 38 to give 46
01.28 g, 4.37 mmol, 84.0% in two steps). Compound 46: 1H
NMR d 0CDCl3, 0.071 M, 500 MHz, 300 K) ppm: 0.88 03H,
t, J7.0 Hz), 1.27±1.35 010H, m), 1.60 02H, m), 2.55 02H, t,
J7.9 Hz), 2.68 02H, d, J6.4 Hz), 2.83 03H, s), 3.48 01H,
dd, J11.3, 6.2 Hz), 3.65 01H, dd, J11.3, 3.4 Hz), 3.91
01H, m), 6.50 01H, d, J1.4 Hz), 6.56 01H, dd, J7.5,
1.4 Hz), 6.93 01H, d, J7.5 Hz); HR-EI-MS m/z:
293.2343 0M1, calcd for C18H31NO2, 293.2355).
Compound 46 01.26 g, 4.30 mmol) was treated in a manner
similar to that described for the synthesis of 40 to give 48
02.05 g, 3.36 mmol, 78.2% in two steps), in which two
Compound 50: 058.7 mg, 0.101 mmol) was treated in a
manner similar to that described for the synthesis of 4 to
give 8 05.30 mg, 11.3 mmol, 11.3%), 51 01.90 mg, 4.05
mmol, 4.1%), 52 021.6 mg, 46.1 mmol, 46.1%), and 53
06.60 mg, 14.1 mmol, 14.1%). Compound 8: [a]D
2120.08 0c0.62, MeOH, 30.78C); UV lmax 0MeOH) nm
01) 262 03250), 203 021,500); 1H NMR d 0CDCl3, 0.039 M,
500 MHz, 300 K) ppm: 0.88 06H, t, J7.0 Hz), 1.22±1.34
014H, m), 1.57 02H, m), 1.90 02H, m), 2.25 01H, t, J
6.5 Hz), 2.65 02H, t, J7.9 Hz), 2.79 03H, s), 2.99 02H, d,
J5.4 Hz), 3.71 01H, t, J7.4 Hz), 3.72 02H, m), 5.12 01H,
m), 6.90 01H, s), 7.24 01H, s); 13C NMR d 0CDCl3, 0.039 M,
125 MHz, 300 K) ppm: 13.92, 14.12, 22.49, 22.68, 28.28,
28.40, 29.28, 29.36, 29.42, 29.93, 31.90, 35.93, 36.02,
36.60, 65.75, 68.08, 79.62, 118.49, 123.46, 130.81,
135.26, 141.77, 149.70, 172.03; HR-FAB-MS m/z:
467.2019 0M1, calcd for C24H38NO3Br, 467.2034).
1
diastereomers existed in a ratio of 1:1. Compound 48: H
NMR d 0CDCl3, 0.085 M, 500 MHz, 300 K) ppm: 0.04 03H,
s), 0.05 03H, s), 0.06 06H, s), 0.85 03H, t, J7.1 Hz), 0.86
03H, t, J7.1 Hz), 0.87 06H, t, J6.7 Hz), 0.90 09H, s), 0.91
09H, s), 1.25±1.34 028H, m), 1.50 04H, m), 1.74 02H, m),
1.88 02H, m), 2.47 02H, t, J8.1 Hz), 2.48 02H, t, J
7.7 Hz), 2.73 03H, s), 2.77 03H, s), 2.77 01H, dd, J14.1,
7.3 Hz), 2.83 02H, dd, J6.1 Hz), 2.92 01H, dd, J14.1,
4.2 Hz), 3.41 01H, dd, J9.9, 6.0 Hz), 3.47 01H, d, J
10.0, 6.1 Hz), 3.51 01H, dd, J9.9, 6.2 Hz), 3.57 01H, dd,
J10.0, 5.5 Hz), 3.69 02H, dd, J9.1, 5.7 Hz), 3.79 01H,
m), 3.86 01H, m), 3.98 01H, d, J3.4 Hz), 4.37 01H, d,
J3.0 Hz), 5.05 02H, m), 5.08 02H, m), 6.88 01H, dd,
J7.7, 1.5 Hz), 6.89 01H, dd, J7.6, 1.5 Hz), 6.91 02H, d,
J1.7 Hz), 7.10 01H, d, J7.7 Hz), 7.12 01H, d, J7.7 Hz),