Photocatalytic gem-Difluoroolefination Reactions by a Formal C-C Coupling/Defluorination Reaction with Diazoacetates

The photolysis of diazoalkanes to conduct singlet carbene transfer reactions of colored diazoalkanes has recently attracted significant interest in organic synthesis. Herein, we describe a photocatalytic approach that allows the access of triplet carbene intermediates via energy transfer to conduct highly efficient gem-difluoroolefination reactions with alpha-trifluoromethyl styrenes. The use of a tertiary amines proved pivotal to unlock this unusual reaction pathway and to prevent undesired cyclopropanation pathways. The amine further facilitates the ultimate abstraction of fluoride to yield gem-difluoroolefins (43 examples, up to 88 % yield), which is supported by experimental and theoretical mechanistic studies. We explored this synthesis method with a broad substrate scope, ranging from simple olefins and heterocyclic olefins towards the decoration of pharmaceutically relevant building blocks.

Automated summary

The study describes a photocatalytic approach for accessing triplet carbene intermediates via energy transfer to conduct efficient gem-difluoroolefination reactions, with the key role played by tertiary amines. The research explores a wide substrate scope, ranging from simple olefins to pharmaceutically relevant building blocks.