K. Takasu et al. / Tetrahedron 60 (2004) 2071–2078
2075
J¼9.4, 9.4 Hz), 2.19–2.08 (m, 1H), 2.00–1.85 (m, 2H),
1.71–1.64 (m, 1H), 1.61–0.75 (m, 15H), 1.34 (s, 3H), 1.22
(s, 3H), 0.97 (t, 9H J¼7.8 Hz), 0.64 (q, 6H, J¼7.8 Hz); 13C
NMR (100 MHz, CDCl3) d 170.9, 151.2, 127.8, 125.4,
125.0, 76.3, 74.5, 50.5, 50.4, 42.0, 40.7, 40.1, 34.6, 32.4,
31.4, 28.0, 27.1, 25.7, 23.5, 21.9, 21.5, 20.5, 19.1, 7.1, 6.2;
LRMS m/z 498 (Mþ); HRMS calcd for C34H56O3Si,
498.3529, found 498.3564.
J¼10.0, 10.0 Hz), 2.46–2.36 (m, 1H), 2.11–1.86 (m, 3H),
1.81–1.66 (m, 4H), 1.60–0.75 (m, 12H), 1.32 (s, 3H), 1.22
(s, 3H), 1.06 (s, 21H); 13C NMR (100 MHz, CDCl3) d 171.3,
151.2, 127.8, 125.4, 125.0, 86.7, 74.5, 50.5, 49.6, 44.8, 42.0,
40.1, 37.8, 34.6, 31.6, 31.4, 27.7, 25.9, 24.5, 21.9, 19.8,
18.3, 13.2; LRMS m/z 526 (Mþ). Anal. calcd for
C33H54O3Si: C, 75.23; H, 10.33, found C, 75.42; H, 10.27.
4.2.10. (1S,5R,7R)-1-Triisopropylsiloxy-7-[(1R,2S,5R)-5-
methyl-2-(1-methyl-1-phenylethyl)cyclohexyloxycar-
bonyl]bicyclo[3.2.0]heptane (cis-3e). Colorless oil; [a]D28
(c 1.01, CHCl3) 211.1; IR (neat) 2947, 2866, 1732, 1231,
4.2.6. (1S,6R,8R)-1-Triethylsiloxy-8-[(1R,2S,5R)-5-
methyl-2-(1-methyl-1-phenylethyl)cyclohexyloxycar-
bonyl]bicyclo[4.2.0]octane (cis-3c). Colorless oil; [a]2D7 (c
0.58, CHCl3) 23.1; IR (neat) 2951, 2936, 2874, 1715, 1182,
1161, 1084, 741, 698 cm21; 1H NMR (400 MHz, CDCl3) d
7.30–7.18 (m, 4H), 7.15–7.09 (m, 1H), 4.88 (ddd, 1H,
J¼4.0, 10.6, 10.6 Hz), 2.72 (dd, 1H, J¼7.0, 7.0 Hz), 2.24–
2.20 (m, 1H), 2.03–1.92 (m, 4H), 1.90–1.73 (m, 3H), 1.66–
0.82 (m, 16H), 1.33 (s, 3H), 1.22 (s, 3H), 0.93 (t, 9H
J¼7.6 Hz), 0.65–0.52 (m, 6H); 13C NMR (100 MHz,
CDCl3) d 170.9, 151.5, 127.8, 125.4, 125.0, 78.4, 74.0,
50.5, 48.3, 42.1, 40.7, 40.0, 36.4, 34.7, 31.4, 28.0, 27.0,
26.4, 23.0, 22.7, 22.2, 21.8, 7.2, 6.6; LRMS m/z 498 (Mþ);
HRMS calcd for C34H56O3Si, 498.3529, found 498.3518.
1163, 1103, 883, 700, 681 cm21 1H NMR (400 MHz,
;
CDCl3) d 7.28–7.22 (m, 4H), 7.16–7.08 (m, 1H), 4.84 (ddd,
1H, J¼10.6, 10.6, 4.1 Hz), 2.75 (dd, 1H, J¼8.5, 8.5 Hz),
2.48–2.38 (m, 1H), 2.35–2.20 (m, 1H), 2.11–2.02 (m, 1H),
2.00–1.90 (m, 1H), 1.90–1.67 (m, 4H), 1.67–0.74 (m,
12H), 1.34 (s, 3H), 1.22 (s, 3H), 1.05 (s, 21H); 13C NMR
(100 MHz, CDCl3) d 170.3, 151.4, 127.8, 125.4, 125.0,
86.6, 74.5, 50.6, 48.7, 43.8, 42.0, 41.6, 40.2, 34.6, 31.3,
28.2, 27.1, 25.2, 24.3, 22.0, 21.8, 18.4, 18.3, 13.5; LRMS
m/z 526 (Mþ); HRMS calcd for C33H54O3Si, 526.3842,
found 526.3888.
4.2.7. (1R,5S,7R)-1-tert-Butyldimethylsiloxy-7-
[(1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclo-
hexyloxycarbonyl]bicyclo[3.2.0]heptane (trans-3d). Pale
yellow oil; [a]2D9 (c 0.66, CHCl3) 233.5; IR (neat) 2953,
4.2.11. (1R,7S,9R)-1-tert-Butyldimethylsiloxy-9-
[(1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclo-
hexyloxycarbonyl]bicyclo[5.2.0]nonane (trans-3f). Color-
less prisms, mp 86–88 8C (from AcOEt–MeOH); [a]2D8 (c
0.54, CHCl3) 231.4; IR (KBr) 2924, 2855, 1728, 1254,
2928, 2855, 1717, 1258, 1225, 1096, 837, 775, 700 cm21
;
1H NMR (400 MHz, CDCl3) d 7.27–7.20 (m, 4H), 7.18–
7.10 (m, 1H), 4.83 (ddd, 1H, J¼4.4, 10.7, 10.7 Hz), 2.93
(dd, 1H, J¼10.1, 10.1 Hz), 2.44–2.36 (m, 1H), 2.05–1.88
(m, 4H), 1.82–1.65 (m, 5H), 1.60–0.70 (m, 10H), 1.33 (s,
3H), 1.23 (s, 3H), 0.86 (s, 9H), 0.12 (s, 3H), 0.10 (s, 3H); 13C
NMR (100 MHz, CDCl3) d 171.4, 151.1, 127.8, 125.4,
125.1, 86.7, 74.5, 50.5, 49.0, 44.4, 42.0, 40.1, 37.6, 34.6,
31.4, 31.4, 27.9, 27.0, 25.8, 24.8, 21.9, 20.0, 17.9, 22.88,
22.95; LRMS m/z 484 (Mþ). Anal. calcd for C30H48O3Si:
C, 74.33; H, 9.98, found C, 74.32; H, 9.83.
1150, 1126, 1065, 837, 775 cm21; H NMR (400 MHz,
1
CDCl3) d 7.25–7.24 (m, 4H), 7.15–7.13 (m, 1H), 4.83 (ddd,
1H, J¼4.4, 10.7, 10.7 Hz), 2.73 (dd, 1H, J¼9.8, 9.8 Hz),
2.14 (m, 1H), 1.99 (m, 1H), 1.91–1.84 (m, 2H), 1.79–0.81
(m, 20H), 1.30 (s, 3H), 1.20 (s, 3H), 0.90 (s, 9H), 0.20 (s,
3H), 0.16 (s, 3H); 13C NMR (100 MHz, CDCl3) d 170.7,
151.2, 127.8, 125.3, 125.0, 82.3, 74.4, 74.1, 50.3, 48.7, 46.7,
40.0, 34.7, 32.7, 31.4, 26.9, 26.7, 26.5, 26.1, 25.9, 23.7,
22.5, 22.0, 21.8, 18.2, 22.67, 22.84; LRMS m/z 455
(Mþ257). Anal. calcd for C32H52O3Si: C, 74.94; H, 10.22,
found C, 75.00; H, 10.11.
4.2.8. (1S,5R,7R)-1-tert-Butyldimethylsiloxy-7-
[(1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclo-
hexyloxycarbonyl]bicyclo[3.2.0]heptane (cis-3d). Pale
yellow oil; [a]2D9 (c 0.34, CHCl3) 213.7; IR (neat) 2951,
2930, 2856, 1732, 1173, 1161, 1097, 905, 835, 775,
4.2.12. (1R,7S,9R)-1-Triisopropylsiloxy-9-[(1R,2S,5R)-5-
methyl-2-(1-methyl-1-phenylethyl)cyclohexyloxycar-
bonyl]bicyclo[5.2.0]nonane (trans-3g). Colorless needles,
mp 87–88 8C (from AcOEt–MeOH); [a]2D8 (c 0.44, CHCl3)
227.9; IR (KBr) 2926, 2866, 1728, 1460, 1252, 1225, 1205,
1
700 cm21; H NMR (400 MHz, CDCl3) d 7.29–7.23 (m,
4H), 7.18–7.10 (m, 1H), 4.78 (ddd, 1H, J¼4.1, 10.5,
10.5 Hz), 2.77 (dd, 1H, J¼8.3, 8.3 Hz), 2.54–2.46 (m, 1H),
2.45–2.34 (m, 1H), 2.18–2.08 (m, 1H), 1.87–1.75 (m, 5H),
1.60–0.70 (m, 12H), 1.38 (s, 3H), 1.25 (s, 3H), 0.90 (s, 9H),
0.11 (s, 3H), 0.03 (s, 3H); 13C NMR (100 MHz, CDCl3) d
171.0, 151.5, 127.8, 125.5, 125.0, 86.2, 74.9, 50.6, 48.3,
43.1, 42.0, 41.6, 40.4, 34.7, 31.5, 31.3, 29.5, 27.2, 25.9,
24.0, 21.8, 21.8, 18.2, 22.47, 22.87; LRMS m/z 484 (Mþ);
HRMS calcd for C30H48O3Si, 484.3373, found 484.3403.
1192, 1130, 772, 700, 683 cm21 1H NMR (400 MHz,
;
CDCl3) d 7.25–7.23 (m, 4H), 7.15–7.10 (m, 1H), 4.84 (ddd,
1H, J¼4.1, 10.5, 10.5 Hz), 2.76 (dd, 1H, J¼10.0, 10.0 Hz),
2.25–2.17 (m, 1H), 2.04–1.97 (m, 1H), 1.90–0.81 (m,
22H), 1.29 (s, 3H), 1.19 (s, 3H), 1.10 (s, 18H), 0.88–0.86
(m, 3H); 13C NMR (100 MHz, CDCl3) d 170.5, 151.3,
127.8, 125.3, 125.0, 82.3, 74.2, 50.3, 49.4, 47.1, 41.9, 40.0,
36.3, 34.6, 34.3, 33.6, 32.2, 31.4, 26.9, 26.7, 26.5, 23.7,
22.1, 21.9, 18.5, 13.4; LRMS m/z 554 (Mþ). Anal. calcd for
C32H52O3Si: C, 74.94; H, 10.22, found C, 75.00; H, 10.11.
4.2.9. (1R,5S,7R)-1-Triisopropylsiloxy-7-[(1R,2S,5R)-5-
methyl-2-(1-methyl-1-phenylethyl)cyclohexyloxycar-
bonyl]bicyclo[3.2.0]heptane (trans-3e). Pale yellow oil;
[a]2D9 (c 1.83, CHCl3) 230.5; IR (neat) 2951, 2889, 2866,
4.2.13. (1S,7R,9R)-1-Triisopropylsiloxy-9-[(1R,2S,5R)-5-
methyl-2-(1-methyl-1-phenylethyl)cyclohexyloxycar-
bonyl]bicyclo[5.2.0]nonane (cis-3g). Colorless oil; [a]2D8 (c
0.87, CHCl3) 29.0; IR (neat) 2924, 2866, 1722, 1454, 1240,
1
1719, 1223, 1194, 1121, 1105, 881, 700 cm21; H NMR
1
(400 MHz, CDCl3) d 7.27–7.22 (m, 4H), 7.18–7.10 (m,
1H), 4.84 (ddd, 1H, J¼4.4, 10.7, 10.7 Hz), 2.98 (dd, 1H,
1092, 762, 700, 677 cm21; H NMR (400 MHz, CDCl3) d
7.27–7.25 (m, 4H), 7.15–7.10 (m, 1H), 4.84 (ddd, 1H,