Hypervalent iodine-mediated β-difluoroalkylboron synthesis via an unusual 1,2-hydrogen shift enabled by boron substitution

beta-Difluoroalkylborons, featuring functionally important CF2 moiety and synthetically valuable boron group, have great synthetic potential while remaining synthetically challenging. Herein we report a hypervalent iodine-mediated oxidative gem-difluorination strategy to realize the construction of gem-difluorinated alkylborons via an unusual 1,2-hydrogen migration event, in which the (N-methyliminodiacetyl) boronate (BMIDA) motif is responsible for the high regio- and chemoselectivity. The protocol provides facile access to a broad range of beta-difluoroalkylborons under rather mild conditions. The value of these products was demonstrated by further transformations of the boryl group into other valuable functional groups, providing a wide range of difluorine-containing molecules.

Automated summary

In this study, a hypervalent iodine-mediated oxidative gem-difluorination strategy was developed for the construction of gem-difluorinated alkylborons via an unusual 1,2-hydrogen migration event. The protocol showed high regio- and chemoselectivity and provided easy access to a broad range of beta-difluoroalkylborons under mild reaction conditions. The value of these products was demonstrated by transforming the boryl group into other valuable functional groups, offering a wide range of difluorine-containing molecules.