Electrolytic Reactions of Fluoroorganic Compounds. 14. Regioselective Anodic Methoxylation of N-(Fluoroethyl)amines. Preparation of Highly Useful Fluoroalkylated Building Blocks

Article abstract of DOI:10.1021/jo00082a018

Anodic methoxylation of various types of N-(fluoroethyl)amines, ArRNCH2R_f (R_f = CF3, CHF2, CH2F, etc.) has been systematically studied and it was found that a methoxy group was exclusively or preferentially introduced into the position α to the fluoromethyl (R_f) group, depending on the R_f and R groups.The effect of the R_f group on the promotion of the anodic α-methoxylation decreased in the order CF3, CHF2, and CH2F.This remarkable promotion effect and unique regioselectivity can be explained mainly in terms of the α-CH kinetic acidities of the cation radicals formed by one-electron oxidation of the amines.The α-methoxylated products are highly useful precursors for the construction of carbon-carbon bonds α to the trifluoromethyl and difluoromethyl groups, which is difficult by other methods.