Nucleophilic trifluoromethylation of carbonyl compounds and disulfides with trifluoromethane and silicon-containing bases

被引:209
作者
Large, S
Roques, N
Langlois, BR
机构
[1] Univ Lyon 1, CNRS, UMR 5622, Lab Synth Electrosynth & React Composes Organ Fl, F-69622 Villeurbanne, France
[2] Rhodia Co, Ctr Rech Lyon, F-69192 St Fons, France
关键词
D O I
10.1021/jo000150s
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Provided that DMF (or another N,N-dialkylformamide) is present in the reaction medium, at least in a catalytic amount, fluoroform trifluoromethylates efficiently carbonyl compounds, even enolizable ones, when opposed to (TMS)(2)N- M+, generated in situ from N(TMS)(3) and M+ F- or RO- Na+ When F- is used ina catalytic amount, silylated alpha-(trifluoromethyl)carbinols are-obtained: in this case, the four-component system HCF3/N(TMS)(3)/catalytic F-/catalytic DMF behaves like the Ruppert's reagent, especially as far as nonenolizable carbonyl compounds are concerned (CF3SiMe3 remains more efficient for enolizable carbonyl compounds). This process involves an adduct between DMF and -CF3 which is the true trifluoromethylating agent. In the same way, fluoroform efficiently trifluoromethylates disulfides and diselenides when deprotonated with a strong base selected from t-BuOK or N(SiMe3)(3)/Me4NF (or TBAT). t-BuOK is more adapted to the trifluoromethylation of aryl disulfides whereas N(SiMe3)(3)/F- is well suited to that of aliphatic disulfides.
引用
收藏
页码:8848 / 8856
页数:9
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