Hydrogen Peroxide → Estra-16-en-3alpha-ol

HRID 369701Notes

Reaction equation

HRID 369701 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:21](=[CH:22][CH2:23][C:24]4[CH:25]=[C:26]([OH:33])[CH:27]=[CH:28][C:29]=43)[C@@H:20]1[CH2:19][CH2:18][CH2:17]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]2

Participants

8

Reactant 4

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 3611392Lithium tri-s-butylborohydrideHCID 15870996Estra-1,3,5(10),7-tetraen-3-ol

Product 1

HCID 22849346Estra-16-en-3alpha-olYield 87%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

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, 3 H); 4.09 (m, w1/2 ≈8, 1 H); 5.71 (m, 1 H), 5.87 (m, 1 H).

Workup

  1. stirringstirring for 3 h at RT
  2. 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-46a8b902cc0b4fc69ba46bd7cdd222df
Source dataset
uspto-grants-2000_10
Patent number
US06140316

Reaction notes

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