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

HRID 42129Notes

Reaction equation

HRID 42129 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O.[C:34]([OH:37])(=[S:36])[CH3:35].[CH3:38][C@:39]12[CH2:56][CH2:55][C@H:54]3[C@@H:44]([CH2:45][C@H:46]([OH:58])[CH:47]4[C@:52]3([CH3:53])[CH2:51][CH2:50][C@H:49](O)[CH2:48]4)[C@@H:43]1[CH2:42][CH2:41][C@@H:40]2[OH:59]>C1COCC1.CCOC(C)=O>[C:34]([S:36][C@@H:49]1[CH2:50][CH2:51][C@@:52]2([CH3:53])[CH:47]([C@@H:46]([OH:58])[CH2:45][C@@H:44]3[C@@H:54]2[CH2:55][CH2:56][C@@:39]2([CH3:38])[C@H:43]3[CH2:42][CH2:41][C@@H:40]2[OH:59])[CH2:48]1)(=[O:37])[CH3:35]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 11266833HCID 11266833, compoundHCID 178418634HCID 178418634, compound

Product 1

HCID 866355973alpha-Acetylthioandrostane-6alpha,17beta-diolYield 66%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of triphenylphosphine (2.38 g) in THF (140 mL) cooled at 0° C., diisopropyl azodicarboxylate (1.79 mL) was added dropwise. After stirring for 30 minutes, thioacetic acid (0.65 mL) and androstane-3β,6α,17β-triol (2.00 g) were added. After 2 hrs at 0° C. and overnight at room temperature EtOAc was added. The mixture was washed with water and the organic layer evaporated to dryness. The crude product was purified by flash chromatography (SiO2, cyclohexane:EtOAc 55:45) to give 3α-acetylthioandrostane-6α,17β-diol (1.60 g, 66%). 1H-NMR (300 MHz, DMSO-d6, ppm from TMS): δ 4.42 (1H, bb), 4.28 (1H, bb), 3.91 (1H, bb), 3.42 (1H, m), 3.11 (1H, m), 2.28 (3H, s), 2.00-0.80 (20H, m), 0.74 (3H, s), 0.60 (3H, s).

Workup

  1. waitAfter 2 hrs at 0° C.
  2. washThe mixture was washed with water
  3. customthe organic layer evaporated to dryness
  4. customThe crude product was purified by flash chromatography (SiO2, cyclohexane:EtOAc 55:45)

Sources & evidence

ORD record
ord-b89e527a7f1b42b1aa87e72b6cd6ab43
Source dataset
uspto-grants-2013_09
Patent number
US08536160B2

Reaction notes

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