Chemodivergent alkylation of trifluoromethyl alkenes via photocatalytic coupling with alkanes

gem-Difluoroalkenes and trifluoromethyl alkanes are prominent structures in biologically active compounds. Radical alkylation of alpha-trifluoromethyl alkenes represents a useful strategy to access these structures. However, reported methods have relied on the use of pre-functionalized radical precursors and examples involving the use of simple hydrocarbons as coupling partners are elusive. Here we report a chemodivergent methodology based on the direct activation of C(sp(3))-H bonds enabled by HAT photoredox catalysis. This protocol provides an efficient platform for preparing both gem-difluoroalkenes and trifluoromethyl alkanes from ubiquitous hydrocarbon feedstocks, including gaseous alkanes. Importantly, chemoselectivity is easily achieved by simple modification of reaction conditions and/or additives.