Addition of Trifluoromethyltrimethylsilane to Acyl Phosphonates:  Synthesis of TMS-Protected 1-Alkyl-1-trifluoromethyl-1-hydroxyphosphonates and 1-Aryldifluoroethenyl Phosphates

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 s...

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Bibliographic Details
Published in:Journal of organic chemistry 2007-10, Vol.72 (22), p.8527-8530
Main Authors: Demir, Ayhan S, Eymur, Serkan
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
Hydrocarbons, Fluorinated - chemistry
Molecular Structure
Organic chemistry
Organophosphonates - chemical synthesis
Organophosphonates - chemistry
Silanes - chemistry
Stereoisomerism
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Summary: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo070913c