Direct Nucleophilic Difluoromethylation of Carbonyl Compounds.
Phosphonium salt ([Ph3P(+)CF2H] Br(-), DFPB) was found to be an efficient nucleophilic difluoromethylation reagent. Although DFPB is known as a phosphonium ylide precursor, its reaction with carbonyl compounds under traditional "Wittig reaction conditions" did not give the expected Wittig difluoroolefinated products, but afforded the nucleophilic difluoromethylation products, α-CF2H alcohols. Mechanistic investigation reveals that the unexpected transformation proceeded via the direct transfer of the CF2H group, which resulted from the high P-O affinity.
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, China.|University of Chinese Academy of Sciences , Beijing 100049, China.
Zuyong
Z
Deng
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, China.|University of Chinese Academy of Sciences , Beijing 100049, China.
Jin-Hong
JH
Lin
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, China.|University of Chinese Academy of Sciences , Beijing 100049, China.
Ji
J
Cai
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, China.|University of Chinese Academy of Sciences , Beijing 100049, China.
Ji-Chang
JC
Xiao