Difluoroenol silyl ethers 5 and 6, difluoroketene silyl (O,O-, O,S-, and O,N-) acetals 9 and 21, and 2,2-difluoro-2-trimethylsilylacetates 10 were prepared by electroreductive defluorination of trifluoromethyl ketones and trifluoroacetic acid derivatives in an MeCN-TBAB-chlorotrialkylsilane system using a carbon rod as an anode and a lead plate as a cathode. TBAF- or KF-CuI-promoted alpha-alkylation of 10 with electrophiles such as aldehydes, ketones, imine, acylhalides, and alkylhalides provided alpha-alkylated-alpha,alpha-difluoroacetates in good to excellent yields.
Electroreductive Defluorination of Trifluoromethyl Ketones and Trifluoroacetic Acid Derivatives. -Silyl ethers (III) and (VII), silyl (O,O-, O,S-, and O,N-) acetals, e.g. (V), and silylacetates like (X) are prepared by the title reaction from the corresponding trifluoromethyl precursors employing a carbon rod as anode, a lead plate as cathode, and Bu 4 NBr as supporting electrolyte. The alkylation of silylacetate (X) with electrophiles promoted by Bu 4 NF or KF/CuI provides α-alkylated-α,α-difluoroacetates in good yields.
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