Monofluoroalkenylation of Dimethylamino Compounds through Radical-Radical Cross-Coupling

An unprecedented and challenging radical-radical cross-coupling of alpha-aminoalkyl radicals with monofluoroalkenyl radicals derived from gem-difluoroalkenes was achieved. This first example of tandem C(sp(3))-H and C(sp(2))-F bond functionalization through visible-light photoredox catalysis offers a facile and flexible access to privileged tetrasubstituted monofluoroalkenes under very mild reaction conditions. The striking features of this redox-neutral method in terms of scope, functional-group tolerance, and regioselectivity are illustrated by the late-stage fluoroalkenylation of complex molecular architectures such as bioactive (+)-diltiazem, rosiglitazone, dihydroartemisinin, oleanic acid, and androsterone derivatives, which represent important new alpha-amino C-H monofluoroalkenylations.