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

Date

2007-10-26

Author

Demir, Ayhan Sıtkı
Eymur, Serkan

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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 HCl/EtOH/reflux or CAN/NaOH/MeOH/0 °C in 82−90% yields.

Subject Keywords

Organic Chemistry

URI

https://hdl.handle.net/11511/52095

Journal

JOURNAL OF ORGANIC CHEMISTRY

DOI

https://doi.org/10.1021/jo070913c

Collections

Department of Chemistry, Article

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Citation Formats

A. S. Demir and S. Eymur, “Addition of trifluoromethyltrimethylsilane to acyl phosphonates: Synthesis of TMS-Protected 1-alkyl-1-trifluoromethyl-1-hydroxyphosphonates and 1-aryldifluoroethenyl phosphates,” JOURNAL OF ORGANIC CHEMISTRY, pp. 8527–8530, 2007, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/52095.