Sodium Bicarbonate → 3-Methoxy-15,15-dimethylestra-1,3,5(10)-trien-17beta-ol
Reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[CH3:7][O:8][C:9]1[CH:26]=[CH:25][C:24]2[C@@H:23]3[C@H:14]([C@H:15]4[C@@:19]([CH2:21][CH2:22]3)([CH3:20])[C:18](=[O:27])[CH2:17][C:16]4([CH3:29])[CH3:28])[CH2:13][CH2:12][C:11]=2[CH:10]=1.C(=O)([O-])O.[Na+]>O1CCCC1>[CH3:7][O:8][C:9]1[CH:26]=[CH:25][C:24]2[C@@H:23]3[C@H:14]([C@H:15]4[C@@:19]([CH2:21][CH2:22]3)([CH3:20])[C@@H:18]([OH:27])[CH2:17][C:16]4([CH3:29])[CH3:28])[CH2:13][CH2:12][C:11]=2[CH:10]=1Participants
Conditions
- Temperature
- 0 °C
Procedure
Lithium aluminum hydride (30 mg; 0.79 mmol) was added to a solution of the dimethyl ketone (4) (50 mg; 0.16 mmol) in dry tetrahydrofuran (2 ml) at 0° C. The mixture was stirred at 0° C. for 5 min. Saturated aqueous sodium hydrogen carbonate was added and the mixture was filtered. Work-up of the filtrate (ethyl acetate) gave 3-methoxy-15,15-dimethylestra-1,3,5(10)-trien-17β-ol (12) (43 mg; 85%), m.p. 87°-91° C. (from chloroform-hexane), [α]D +75° (c 1.1); νmax 3606 cm-1 (OH); δ0.92 (3H, s, 13β-Me), 1.06 (1H, d, J 11.2 Hz, 14α-H), 1.11 and 1.14 (each 3H, s, 15α- and 15β-Me), 1.61 and 1.90 (each 1H, dd, J 13.0 and 10.2, and 13.0 and 7.9 Hz, 16α- and 16β-H), 2.86 (2H, m, 6-H2), 3.71 (1H, dd, J 10.2 and 7.9 Hz, 17α-H), 3.77 (3H, s, 3-OMe), 6.62 (1H, d, J 2.7 Hz, 4-H), 6.71 (1H, dd, J 8.6 and 2.7 Hz, 2-H), and 7.21 (1H, d, J 8.6 Hz, 1-H); δc 13.5 (C-18), 25.6 (15-Me), 26.1 (C-11), 28.5 (C-7), 29.9 (C-6), 35.0 (C-12), 36.2 (C-15), 37.1 (C-8), 38.8 (15-Me), 44.9 (C-9), 45.6 (C-13), 50.1 (C-16), 55.2 (3-OMe), 58.1 (C-14), 79.8 (C-17), 111.4 (C-2), 113.6 (C-4), 126.3 (C-1), 132.9 (C-10), 137.7 (C-5), and 157.5 (C-3) (Found: C, 80.0; H, 9.5%; M+, 314. C21H30O2 requires C, 80.2; H, 9.6%; M, 314).
Workup
- filtrationthe mixture was filtered
Sources & evidence
- ORD record
- ord-00651d660c21456598aa6979ddf50bcf
- Source dataset
- uspto-grants-1996_12
- Patent number
- US05587496
Reaction notes
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