Addition of trifluoromethyltrimethylsilane to acyl phosphonates: Synthesis of TMS-Protected 1-alkyl-1-trifluoromethyl-1-hydroxyphosphonates and 1-aryldifluoroethenyl phosphates

Demir A. S., Eymur S.

JOURNAL OF ORGANIC CHEMISTRY, vol.72, no.22, pp.8527-8530, 2007 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 72 Issue: 22
  • Publication Date: 2007
  • Doi Number: 10.1021/jo070913c
  • Journal Name: JOURNAL OF ORGANIC CHEMISTRY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.8527-8530
  • Middle East Technical University Affiliated: Yes

Abstract

Addition reactions of nucleophilic CF3TMS to acyl phosphonates were investigated. Various acyl phosphonates reacted readily with CF3TMS in the presence of K2CO3 in DMF at rt to give 1-alkyl-2,2,2-trifluoro-1-trimethylsilyloxyethylphosphonate in 70-90% yields. When benzoyl phosphonates were used as starting material, after addition of CF3, the formed alcoholate undergoes phosphonate-phosphate rearrangement to form the acyl anion, followed by elimination of F- to give 1-aryldifluoroethenyl phosphates in 87-97% yields. As a representative example, vinylphosphate 6a was converted into 2,2-difluoro-1-phenylethanone 7 with 6 N HC1/EtOH/reflux or CAN/NaOH/MeOH/O degrees C in 82-90% yields.