K. Nagasawa et al. / Tetrahedron 57 ꢀ2001) 8959±8964
8963
24.55, 24.80, 24.83. HRMS 2FAB, M1H) calcd for
C32H68NO6Si2 618.4585, found 618.4581.
85.84, 75.65, 68.86, 68.58, 68.35, 66.61, 65.74, 58.61,
57.60, 40.94, 39.75, 39.55, 38.49, 37.48, 32.82, 25.91,
25.88, 23.73, 23.69, 22.60, 21.86, 18.14, 18.12, 24.40,
24.44, 24.69, 24.72. HRMS 2FAB, M1H) calcd for
C32H68NO6Si2 618.4585, found 618.4586.
4.1.7. )2S,20R,3S,4S,5S,60S)-2,5-[60-)tert-Butyldimethyl-
silyloxy)-20-hydroxyheptyl]-3-4-dimethoxypyrrolidine
)8b). From 7b 21.89 g, 3.05 mmol) was obtained 8b
2967 mg, 51%) as clear light brown oil after puri®cation
with silica gel chromatography 2hexanes/ethyl acetate, 1:1,
4.1.10. )2S,20S,3R,4R,5S,60R/60S)-2,5-[60-)tert-Butyldi-
methylsilyloxy)-20-hydroxyheptyl]-3,4-dimethoxypyrro-
lidine )8c). From 7c 21.5 g, 2.4 mmol) was obtained 8c
21.0g, 67%) as a clear light brown oil after puri®cation
with silica gel chromatography 2hexanes/ethyl acetate, 1:1,
25
0:1). [a]D 246.4 2c 0.9, CHCl3). IR 2neat) 3375, 2950,
1470, 1260, 1110 cm21. 1H NMR 2CDCl3, 300 MHz) d 5.27
2brs, 1H), 3.86 2m. 2H), 3.75 2m, 2H), 3.62 2m, 2H), 3.54 2m,
2H), 3.69 2s, 6H), 1.88 2m, 4H), 1.66 2m, 2H), 1.53 2m, 2H),
1.39 2m, 10H), 1.09 2d, J7 Hz, 6H), 0.86 2s, 18H), 0.02 2s,
12H). 13C NMR 2CDCl3, 75 MHz) d 88.97, 68.70, 68.55,
58.94, 57.72, 39.69, 37.30, 37.04, 25.90, 23.73, 22.03,
18.12, 24.36, 24.66. HRMS 2FAB, M1H) calcd for
C32H70NO6Si2 620.4742, found 620.4747.
25
0:1). [a]D 211.2 2c 1.0, CHCl3). IR 2neat) 3420, 3375,
1
2850, 1590, 1630, 1465, 1390, 1260, 1220, 1110 cm21. H
NMR 2CDCl3, 300 MHz) d 3.69 2m, 2H), 3.73 2m, 4H), 3.57
2m, 2H), 3.39 2s, 6H), 1.98 2m, 2H), 1.71 2m, 2H), 1.41 2m,
12H), 1.08 2d, J6 Hz, 6H), 0.86 2s, 18H), 0.02 2s, 12H). 13C
NMR 2CDCl3, 75 MHz) d 88.47, 68.55, 68.49, 68.38, 58.89,
58.81, 57.80, 57.78, 39.66, 39.56, 39.56, 36.67, 37.10,
36.97, 25.89, 23.73, 23.66, 21.99, 21.78, 18.11, 24.44,
24.67. HRMS 2FAB, M1H) calcd for C32H70NO6Si2
620.4742, found 620.4733.
4.1.8. )1S,2S,2aS,4R,60S,7R,8aS)-1,2-Dimethoxy-4,7-)60-
methyl-20-tetrahydropyranyl)-2,2a,3,4,5,7,8,8a-octahydro-
1H-5,6,8b-triazaacenaphthylene hydrochloride )1b) and
)1S,2S,2aS,4R,60S,7S,8aS)-1,2-dimethoxy-4,7-)60-methyl-
20-tetrahydropyranyl)-2,2a,3,4,5,7,8,8a-octahydro-1H-
5,6,8b-triazaacenaphthylene hydrochloride )1d). From
8b 2414 mg, 0.67 mmol) in 3 steps after separation and
puri®cation with silica gel chromatography 2CHCl3/
CH3OH, 100:0.5, 100:1) were obtained 1b 298 mg, 34%)
and 1d 290mg, 30%) as white crystals. Data for 1b: mp
4.1.11.
)1S,2S,2aS,4R,60R/60S,7R,8aS)-1,2-Dimethoxy-
4,7-)60-methyl-20-tetrahydropyranyl)-2,2a,3,4,5,7,8,8a-
octahydro-1H-5,6,8b-triaza-acenaphthylene hydrochlo-
ride )1c). From 8c 21.0g, 1.1 mmol) in 3 steps was obtained
1c 2250mg, 50%) after puri®cation with silica gel chroma-
tography 2CHCl3/CH3OH, 100:1) as a white crystal. Mp
24
24
189±1908C 2decomposition). [a]D 192.5 2c 0.6
193±1948C 2decomposition). [a]D 229.5 2c 0.5,
CHCl3). IR 2neat) 3180, 2960, 1650, 1620, 1450, 1180,
CHCl3). IR 2neat) 3180, 2950, 1660, 1630, 1200, 1120,
1
1
1120, 1030 cm21. H NMR 2CDCl3, 500 MHz) d 9.54 2s,
1040 cm21. H NMR 2CDCl3, 500 MHz): d 10.15 2s, 1H),
2H) 3.56 2m, 4H), 3.51 2s, 6H), 2.802d, J12.5 Hz, 2H),
1.82 2m, 6H), 1.12 2d, J6.0Hz, 6H). 13C NMR 2CDCl3,
125 MHz) d 148.7, 86.05, 81.79, 68.55, 59.30, 52.00, 34.77,
31.46, 30.73, 22.07, 20.02. HRMS 2FAB, M1H) calcd for
C21H36N3O4 394.2706, found 394.2714. Data for 1d: mp
9.48 2s, 1H), 3.96 2m, 1H), 3.63 2s, 4H), 3.56 2s, 3H), 3.53 2s,
3H), 2.85 2d, J12 Hz, 1H), 2.27 2s, 2H), 1.75 2m, 12H),
1.35 2m, 1H), 1.17 2d, J6 Hz, 3H), 1.09 2d, J6 Hz, 3H).
13C NMR 2CDCl3, 125 MHz) d 148.80, 86.77, 85.78, 81.81,
80.96, 68.64, 67.18, 59.40, 59.36, 52.24, 52.06, 38.88,
34.87, 34.51, 32.29, 31.60, 30.82, 22.18, 21.85, 20.09,
18.45. HRMS 2FAB, M1H) calcd for C21H36N3O4
394.2706, found 394.2710.
24
161±1628C. [a]D 159.2 2c 0.6, CHCl3). IR 2neat)
3180, 2920, 1660, 1630, 1440, 1110 cm21 1H NMR
.
2CDCl3, 500 MHz) d 10.11 2s, 1H), 9.54 2s, 1H), 4.19 2m,
1H), 3.68 2m, 1H), 3.602m, 3H), 3.54 2s, 3H), 3.53 2s, 3H),
3.39 2m, 1H), 2.87 2d, J13 Hz, 1H), 2.44 2d, J13 Hz,
1H), 2.17 2m, 2H), 2.09 2m, 2H), 1.92 2m, 4H), 1.71 2m,
2H), 1.57 2m, 1H), 1.49 2m, 1H), 1.24 2m, 1H), 1.18 2d,
J6.0Hz, 3H), 1.12 2d, J6 Hz, 3H). 13C NMR 2CDCl3,
125 MHz) d 149.9, 86.93, 86.71, 83.31, 81.76, 68.76,
68.52, 59.53, 59.25, 53.88, 51.96, 42.14, 37.77, 34.62,
32.23, 31.61, 31.24, 22.12, 22.05, 20.06, 18.09. HRMS
2FAB, M1H) calcd for C21H36N3O4 394.2706, found
394.2712.
4.1.12. )1S,2S,2aS,4R,50R,60R,7R,8aS)-1,2-Dimethoxy-
4,7-)60-methyl-50-phenyl-20-tetrahydropyranyl)-2,2a,3,4,
5,7,8,8a-octahydro-1H-5,6,8b-triazaacenaphthylene
hydrochloride )2). Data for 2: mp 256±2598C 2decomposi-
25
tion). [a]D 10.9 2c 0.3, CHCl3). IR 2neat) 2600, 1590,
1620, 1500, 1460, 1300, 1100, 940 cm21. 1H NMR 2CDCl3,
500 MHz) d 10.62 2s, 2H), 7.51 2d, J7 Hz, 4H), 7.32 2m,
2H), 7.202t, J7.0Hz, 4H), 4.102m, 2H), 3.81 2m, 2H),
3.69 2m, 2H), 3.58 2s, 6H), 2.76 2m, 2H), 2.37 2m, 4H), 2.05
2m, 2H), 1.89 2m, 2H), 1.75 2m, 2H), 1.26 2m, 2H), 0.90 2d,
J6.0Hz, 6H). 13C NMR 2CDCl3, 125 MHz) d 149.00,
142.18, 128.59, 128.42, 128.25, 126.65, 86.41, 80.75,
71.57, 59.47, 52.34, 50.03, 38.45, 35.16, 26.08, 19.75.
HRMS 2FAB, M1H) calcd for C33H44N3O4 546.3332,
found 546.3334.
4.1.9. )2R,200R,3aS,4S,40R,5S,6S,600S)-2-[40-)tert-Butyldi-
methylsilyloxy)pentyl]-6-[600-)tert-butyldimethylsilyloxy-
200-hydroxyheptyl)]-4,5-dimethoxyhexahydropyrrolo[1,2-
b]isoxazole )7c). From 6a 22.5 g, 6.7 mmol) and 4b in 2
steps was obtained 7c 25.1 g, 51%) as a clear light brown
oil after puri®cation with silica gel chromatography
25
2hexanes/ether, 7:3). [a]D 217.02 c 2.0, CHCl3). IR
Crystallographic data 2excluding structure factors) for
structures 1a±1c, 2 have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication
numbers CCDC 170374±170377. Copies of the data can be
obtained, free of charge, on application to CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK [fax: 144-20)1223-336033
or e-mail: deposit@ccdc.cam.ac.uk].
1
2neat) 3480, 2950, 1740, 1470, 1380, 1280, 1120 cm21. H
NMR 2CDCl3, 300 MHz) d 4.05 2m, 1H), 3.85 2m, 1H), 3.76
2m, 2H), 3.502m, 3H), 3.43 2s, 3H), 3.35 2s, 3H), 3.18 2m,
1H), 2.14 2m, 2H), 1.76 2t, J5.4 Hz, 2H), 1.402m, 12H),
1.09 2d, J6.0 Hz, 6H), 0.86 2s, 9H), 0.85 2s, 9H), 0.06 2s,
6H), 0.01 2s, 6H). 13C NMR 2CDCl3, 75 MHz) d 89.55,