3alpha-Acetylthioandrostane-6alpha,17beta-diol → 3alpha-Acetylthioandrostane-6,17-dione

HRID 42130Notes

Reaction equation

HRID 42130 reaction equation
[C:1]([S:4][C@@H:5]1[CH2:22][CH2:21][C@@:20]2([CH3:23])[CH:7]([C@@H:8]([OH:25])[CH2:9][C@@H:10]3[C@@H:19]2[CH2:18][CH2:17][C@@:15]2([CH3:16])[C@H:11]3[CH2:12][CH2:13][C@@H:14]2[OH:24])[CH2:6]1)(=[O:3])[CH3:2]>C(Cl)Cl.CCC[N+](CCC)(CCC)CCC.[O-][Ru](=O)(=O)=O>[C:1]([S:4][C@@H:5]1[CH2:22][CH2:21][C@@:20]2([CH3:23])[CH:7]([C:8](=[O:25])[CH2:9][C@@H:10]3[C@@H:19]2[CH2:18][CH2:17][C@@:15]2([CH3:16])[C@H:11]3[CH2:12][CH2:13][C:14]2=[O:24])[CH2:6]1)(=[O:3])[CH3:2]

Participants

4

Reactant 1

HCID 866355973alpha-Acetylthioandrostane-6alpha,17beta-diol

Product 1

HCID 866355963alpha-Acetylthioandrostane-6,17-dioneYield 77.3%

Reagents, catalysts & solvents 2

HCID 178419074HCID 178419074, compoundCatalyst2×HCID 6344DichloromethaneSolvent

Procedure

To a stirred suspension of 3α-acetylthioandrostane-6α,17β-diol (1.40 g) in CH2Cl2 (50 mL), NMNO (1.37 g), TPAP (68 mg) and powdered molecular sieves 4 Å (2.1 g) were added at room temperature. After 2 hrs NMNO (0.7 g), TPAP (34 mg) and molecular sieves 4 Å (1 g) were added again and the reaction was stirred for further 1.5 hrs. The crude product was purified by flash chromatography (SiO2, cyclohexane:EtOAc 7:3) to give 3α-acetylthioandrostane-6,17-dione (1.07 g, 76%). 1H-NMR (300 MHz, acetone-d6, ppm from TMS): δ 3.99 (1H, bb), 2.55-1.20 (23H, m), 0.86 (3H, s), 0.79 (3H, s).

Workup

  1. additionwere added at room temperature
  2. customThe crude product was purified by flash chromatography (SiO2, cyclohexane:EtOAc 7:3)

Sources & evidence

ORD record
ord-092a0b67122a454894e199ec5c4a8b7e
Source dataset
uspto-grants-2013_09
Patent number
US08536160B2

Reaction notes

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