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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...

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Detalles Bibliográficos
Autores principales: Li, Fang, Pei, Chao, Koenigs, Rene M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9300101/
https://www.ncbi.nlm.nih.gov/pubmed/34716734
http://dx.doi.org/10.1002/anie.202111892
Descripción
Sumario: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 α‐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.