Reaction #93692

ord-1338a2a8b7d4465a94c1fc263f3ee3bc

Reaction equation

CC(C)(C)[Si](C)(C)O[C@H]1CC[C@]2(C)[C@H]3CC[C@]4(C)C(=O)[C@H]5C[C@H]5[C@H]4[C@@H]3[C@@H](O)[C@H]3O[C@]32C1
3β-(tert.-butyldimethylsilyloxy)-5,6β-epoxy-7β-hydroxy-15β,16β-methylene-5β-androstan-17-one
ClCCl
methylene chloride
c1ccc(P(c2ccccc2)c2ccccc2)cc1
triphenylphosphine
→
CC(C)(C)[Si](C)(C)O[C@H]1CC[C@]2(C)[C@H]3CC[C@]4(C)C(=O)[C@H]5C[C@H]5[C@H]4[C@@H]3[C@H](Cl)[C@H]3O[C@]32C1
3β-(tert.-butyldimethylsilyloxy)-7α-chloro-5,6β-epoxy-15β,16β-methylene-5β-androstan-17-one

Reactants

CC(C)(C)[Si](C)(C)O[C@H]1CC[C@]2(C)[C@H]3CC[C@]4(C)C(=O)[C@H]5C[C@H]5[C@H]4[C@@H]3[C@@H](O)[C@H]3O[C@]32C1
3β-(tert.-butyldimethylsilyloxy)-5,6β-epoxy-7β-hydroxy-15β,16β-methylene-5β-androstan-17-one
ClCCl
methylene chloride
c1ccc(P(c2ccccc2)c2ccccc2)cc1
triphenylphosphine

Reagents

None

Solvents

ClC(Cl)(Cl)Cl
carbon tetrachloride
c1ccncc1
pyridine

Conditions

Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    WashThe mixture is then washed with water
  2. 2
    Dryingdried over sodium sulfate
  3. 3
    Concentrationconcentrated under vacuum

Procedure

126 g of 3β-(tert.-butyldimethylsilyloxy)-5,6β-epoxy-7β-hydroxy-15β,16β-methylene-5β-androstan-17-one is dissolved in a mixture of 600 ml of methylene chloride, 600 ml of carbon tetrachloride, and 300 ml of pyridine and stirred with 193.8 g of triphenylphosphine for 2.5 hours. The mixture is then washed with water, dried over sodium sulfate, and concentrated under vacuum. Chromatography on silica gel with hexane-acetone yields 117.4 g of 3β-(tert.-butyldimethylsilyloxy)-7α-chloro-5,6β-epoxy-15β,16β-methylene-5β-androstan-17-one, mp 155.5° C. [α]D =-87° (chloroform).

Source

DOI: 10.6084/m9.figshare.5104873.v1Patent: US04614616uspto-grants-1986_09