m-Chloroperbenzoic acid → (2alpha-3alpha,5alpha)-2,3-Epoxypregnan-20-ol

HRID 244246Notes

Reaction equation

[CH3:1][CH:2]([OH:22])[C@@H:3]1[C@:20]2([CH3:21])[C@H:6]([C@H:7]3[C@H:17]([CH2:18][CH2:19]2)[C@:15]2([CH3:16])[C@H:10]([CH2:11][CH:12]=[CH:13][CH2:14]2)[CH2:9][CH2:8]3)[CH2:5][CH2:4]1.C1C=C(Cl)C=C(C(OO)=[O:31])C=1>ClCCl>[O:31]1[C@H:12]2[CH2:11][C@H:10]3[C@:15]([CH3:16])([CH2:14][C@@H:13]12)[C@@H:17]1[C@H:7]([C@H:6]2[C@:20]([CH3:21])([CH2:19][CH2:18]1)[C@@H:3]([CH:2]([OH:22])[CH3:1])[CH2:4][CH2:5]2)[CH2:8][CH2:9]3

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of 5-α-pregn-2-en-20-ol (12) (660 mg, 2.18 mmol) in anhydrous dichloromethane (20 mL) at 0° C. under an atmosphere of argon was added in six portions m-CPBA (733 mg, 3.27 mmol). The solution was stirred over a period of 1 h at 0° C. and then allowed to return to room temperature overnight. The resulting solution was diluted with dichloromethane (30 mL) and successively washed with a Na2S2O3 aqueous solution (10%) and a Na2CO3 aqueous solution (10%), dried with MgSO4, filtered and evaporated to dryness. Purification by FCC (EtOAc/hexanes, 5:95) yielded 511 mg (73%) of title compound 13 as a white solid. 1H NMR (acetone-d6) δ: 0.74 (s, 18-CH3), 0.79 (s, 19-CH3), 1.07 (d, J=6.1 Hz, 21-CH3), 0.60-2.30 (residual CH and CH2), 3.06 (m, 2×CH of epoxide), 3.62 (m, 20-CH); 13C NMR (CDCl3) δ: 12.4, 12.9, 20.7, 23.6, 24.4, 25.6, 28.4, 29.0, 31.7, 33.6, 35.4, 36.2, 38.2, 39.9, 42.3, 51.1, 52.4, 53.7, 55.7, 58.5, 70.6, LRMS for C21H34O2 [M+H]+: 319.1 m/z.

Workup

waitto return to room temperature overnight
washsuccessively washed with a Na2S2O3 aqueous solution (10%)
dry with materiala Na2CO3 aqueous solution (10%), dried with MgSO4
filtrationfiltered
customevaporated to dryness
customPurification by FCC (EtOAc/hexanes, 5:95)

Sources & evidence

ORD record: ord-ea08dc18dfec488c89dc86c267ba2dfb
Source dataset: uspto-grants-2014_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08653054B2

Reaction notes

Loading…