H. Pennemann et al. / Tetrahedron: Asymmetry 11 (2000) 2133±2142
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3.2.5. Major diastereomer: (1R,2R,10R,50R)-8
Yield: 4.27 g (68%) colourless oil, Kugelrohr distillation: oven temperature=140ꢁC (0.008
mbar); Rf-value 0.81 (n-hexane:triethylamine 9:1); [ꢂ]2D0=^95.1 (c=1.00, CH2Cl2); IR (NaCl):
1
1
ꢀmax (cm )=3440 (O±H) and 2960, 2930, 2860 (C±H); H NMR (CDCl3): ꢁ (ppm)=1.12±1.85,
1.90±2.02, 2.05±2.17, 2.25±2.54 (14H+1H+1H+3H, 5m, 2ÂH3, 2ÂH4, 2ÂH5, 2ÂH6, 2ÂH30,
2ÂH40, H50, 2ÂH60, 2ÂH70, 2ÂH80), 2.67±2.77, 3.10±3.20, 3.24±3.33 (1H+1H+1H, 3m, H1, H2,
H10) and 3.92 (1H, s, OH); 13C NMR (DEPT, CDCl3): ꢁ (ppm)=21.6, 23.5, 24.2, 25.5, 32.5, 32.7,
33.1, 33.2 (C3, C4, C5, C6, C40, C60, C70, C80), 41.4 (C50), 45.4 (C30), 63.7, 64.6 (C2, C10) and 70.0
(C1); MS (CI, i-butane): m/z=210 (MH+, 100%). Anal. calcd for C13H23NO (209.3): C, 74.59; H,
11.07; N, 6.69. Found: C, 74.52; H, 11.04; N, 6.63.
3.2.6. Minor diastereomer: (1S,2S,10R,50R)-8
Yield: 1.34 g (21%) colourless oil, Kugelrohr distillation: oven temperature=140ꢁC (0.008
mbar); Rf-value 0.65 (n-hexane:triethylamine 9:1); [ꢂ]2D0=+45.4 (c=1.00, CH2Cl2); IR (NaCl):
1
ꢀmax (cm^1)=3450 (O±H) and 2910, 2840, 2790 (C±H); H NMR (CDCl3): ꢁ (ppm)=1.13±1.94,
2.05±2.16, 2.35±2.60, 2.69±2.84 (15H+1H+2H+2H, 4m, 2ÂH3, 2ÂH4, 2ÂH5, 2ÂH6, 2ÂH30,
2ÂH40, 1ÂH50, 2ÂH60, 2ÂH70, 2ÂH80, H2 or H10), 3.23±3.37 (2H, m, H1, H2 or H10) and 4.03
(1H, br s, OH); 13C NMR (DEPT, CDCl3): ꢁ (ppm)=22.5, 24.3, 25.0, 25.7, 31.9, 32.6, 33.6, 34.4
(C3, C4, C5, C6, C40, C60, C70, C80), 43.5 (C50), 53.7 (C30), 61.1, 66.2 (C2, C10) and 71.2 (C1); MS
(CI, i-butane): m/z=210 (MH+, 100%). Anal. calcd for C13H23NO (209.3): C, 74.59; H, 11.07; N,
6.69. Found: C, 74.68; H, 10.99; N, 6.61.
3.2.7. (1RS,2RS,10R,50R)-2-(20-Aza-bicyclo[3.3.0]oct-20-yl)-cycloheptan-1-ol (1RS,2RS,10R,50R)-9
GP 2: 6.16 g (30 mmol) (all-R)-5; total yield: 5.96 g (89%); dr 81:19 ((1R,2R,10R,50R)-
9:(1S,2S,10R,50R)-9; 13C NMR: C1); column chromatography with (n-hexane:triethylamine, 9:1).
It was not possible to obtain the minor diastereomer in pure form by column chromatography
(minor diastereomer: Rf-value 0.70, n-hexane:triethylamine, 9:1; mixed fraction: 2.37 g, 35%).
3.2.8. Major diastereomer: (1R,2R,10R,50R)-9
Yield: 3.59 g (54%) colourless oil, Kugelrohr distillation: oven temperature=140ꢁC (0.008
mbar); Rf-value 0.79 (n-hexane:triethylamine, 9:1); [ꢂ]2D0=^51.4 (c=0.99, CH2Cl2); IR (NaCl):
1
ꢀmax (cm^1)=3370 (O±H) and 2930, 2860 (C±H); H NMR (CDCl3): ꢁ (ppm)=1.16±1.81, 1.89±
2.11, 2.22±2.52 (16H+2H+3H, 3m, 2ÂH3, 2ÂH4, 2ÂH5, 2ÂH6, 2ÂH7, 2ÂH30, 2ÂH40, H50,
2ÂH60, 2ÂH70, 2ÂH80), 2.66±2.76, 3.08±3.17 (1H+1H, 2m, H2, H10), 3.25±3.37 (1H, m, H1) and
4.40 (1H, br s, OH); 13C NMR (DEPT, CDCl3): ꢁ (ppm)=21.8, 21.9, 23.5, 24.4, 26.9, 32.2, 32.5,
33.2, 33.2 (C3, C4, C5, C6, C7, C40, C60, C70, C80), 41.3 (C50), 45.0 (C30), 64.7, 64.9 (2C, C2, C10)
and 72.2 (C1); MS (CI, i-butane): m/z=224 (MH+, 100%). Anal. calcd for C14H25NO (223.4): C,
75.28; H, 11.28; N, 6.27. Found: C, 75.34; H, 11.37; N, 6.26.
3.2.9. (1R,2R,10R,50R)-2-(20-Aza-bicyclo[3.3.0]oct-20-yl)-cyclooctan-1-ol (1R,2R,10R,50R)-10
GP 2: 6.58 g (30 mmol) (all-R)-6; dr=ꢀ95:5 ((1R,2R,10R,50R)-10:(1S,2S,10R,50R)-10; NMR);
column chromatography with (n-hexane:triethylamine, 9:1, Rf-value 0.80), Kugelrohr distillation:
oven temperature=140ꢁC (0.009 mbar); yield: 6.42 g (90%) colourless oil; [ꢂ]2D0=^41.3 (c=1.00,
CH2Cl2); IR (NaCl): ꢀmax (cm^1)=3370 (O±H) and 2920, 2850 (C±H); ꢁH (300 MHz, CDCl3)
1.18±2.02 (20H, m, 2ÂH3, 2ÂH4, 2ÂH5, 2ÂH6, 2ÂH7, 2ÂH8, 2ÂH40, 2ÂH60, 2ÂH70, 2ÂH80),
2.19±2.80 (4H, m, H10, 2ÂH30, H05), 3.03±3.19 (1H, m, H2), 3.32±3.48 (1H, m, H1) and 4.72 (1H,