LAUSR

The gem-difluoroalkene moiety is an ideal carbonyl bioisostere in medicinal chemistry, but efficient synthesis of β-gem-difluoroalkene esters remains challenging so far. Herein, we disclose a photoredox-catalyzed allylic defluorinative alkoxycarbonylation of trifluoromethyl alkenes enabled by intermolecular alkoxycarbonyl radical addition. A wide variety of alcohol oxalate derivatives were amenable, affording various β-gem-difluoroalkene esters with excellent functional group tolerance. Notably, the potential synthetic value of this method is highlighted by successful late-stage modification for bioactive molecules.