Hydrogen Peroxide → Estra-16-en-3alpha-ol
Reaction equation
CCC(C)[BH-](C(C)CC)C(C)CC.[Li+].[CH3:15][C@:16]12[CH2:32][CH2:31][C@H:30]3[C@@H:21]([CH2:22][CH2:23][CH:24]4[C@@H:29]3[CH2:28][CH2:27][C:26](=[O:33])[CH2:25]4)[C@@H:20]1[CH2:19][CH:18]=[CH:17]2.[OH-].[Na+].OO>C1COCC1.CCOCC.O>[CH3:15][C@:16]12[CH2:32][CH2:31][C@H:30]3[C@@H:21]([CH2:22][CH2:23][CH:24]4[C@@H:29]3[CH2:28][CH2:27][C@@H:26]([OH:33])[CH2:25]4)[C@@H:20]1[CH2:19][CH:18]=[CH:17]2Participants
Procedure
This synthesis is depicted in FIG. 11. L-Selectride (d, lithium tri(sec-butyl)hydridoborate, 4 ml of a 1M solution in THF, 4 mmol) was added dropwise at 0° to a solution of ketone 10 (800 mg, 3.10 mmol) in dry ether (5 ml). After stirring for 1 h at 0°, water was added (10 ml). The boranes were oxidized by adding 10% aq. NaOH-solution (5 ml), followed by 30% aq. H2O2 -solution (3 ml) and stirring for 3 h at RT. After workup (ether), the crude product (790 mg, Ca. 9:1 mixture of 11 and 12) was chromatographed on silica gel with CH2Cl2 to give 700 mg (87%) of pure alcohol 11. M.p. 119°-120°→123°-124° (from PE), [a]D +40.6° (C=1.0).--IR. (CHCl3): 3640m, 3500 br., 1585w.--1H-NMR. (90 MHz): 0.78 (s, 3H); 4.09 (m, w1/2 ≈8, 1H); 5.71 (m, 1H), 5.87 (m, 1H).
Workup
- stirringstirring for 3 h at RT
- customAfter workup (ether), the crude product (790 mg, Ca. 9:1 mixture of 11 and 12) was chromatographed on silica gel with CH2Cl2
Sources & evidence
- ORD record
- ord-8ea679507e1a43dfb8823c5133c2a071
- Source dataset
- uspto-grants-1997_05
- Patent number
- US05633392
Reaction notes
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