Regio- and enantioselective hydrofluorination of internal alkenes via nickel-catalyzed hydrogen atom transfer

Abstract

Here we present a highly efficient protocol utilizing nickel-hydride hydrogen atom transfer catalysis for the regio- and enantioselective hydrofluorination of internal alkenes. This method efficiently assembles a wide array of enantioenriched β-fluoro amides with excellent regio- and enantioselectivity from internal unactivated alkenes. Mechanistic investigations suggest that this transformation proceeds via a NiH-hydrogen atom transfer to alkene, followed by a stereoselective fluorine atom transfer process. The weak coordination effect of the tethered amide group is identified as a crucial factor governing the observed regio- and enantioselectivity.