Defluorinative Alkylboration of Alkenes Enabled by Dual Photoredox and Copper Catalysis.

Abstract

A regioselectivity reversed three-component defluorinative alkylboration of alkenes with trifluoromethyls and bis(pinacolato)diboron via dual photoredox/copper catalysis is reported. The mild conditions are compatible with a wide array of nonactivated trifluoromethyl aromatics bearing electron-donating or electron-neutral substituents, trifluoroacetamides, and various nonactivated terminal and internal alkenes, enabling straightforward access to synthetically valuable γ-gem-difluoroalkyl boronates with high efficiency. Furthermore, this protocol is applicable to alkene-tethered trifluoromethyl aromatics to furnish gem-difluoromethylene-containing cyclic compounds. Synthetic applications and preliminary mechanistic studies are also presented.