Photochemical Organocatalytic Regio- and Enantioselective Conjugate Addition of Allyl Groups to Enals

We report the first catalytic enantioselective conjugate addition of allyl groups to a,b-unsaturated aldehydes. The chemistry exploits the visible-light-excitation of chiral iminium ions to activate allyl silanes towards the formation of allylic radicals, which are then intercepted stereoselectively...

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Detalles Bibliográficos
Autores: Berger, Martin, Carboni, Davide, Melchiorre, Paolo
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2021
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/520867
Acceso en línea:http://hdl.handle.net/2072/520867
https://doi.org/10.1002/anie.202111648
Access Level:acceso abierto
Palabra clave:54
Descripción
Sumario:We report the first catalytic enantioselective conjugate addition of allyl groups to a,b-unsaturated aldehydes. The chemistry exploits the visible-light-excitation of chiral iminium ions to activate allyl silanes towards the formation of allylic radicals, which are then intercepted stereoselectively. The underlying radical mechanism of this process overcomes the poor regio- and chemoselectivity that traditionally affects the conjugate allylation of enals proceeding via polar pathways. We also demonstrate how this organocatalytic strategy could selectively install a valuable prenyl fragment at the b-carbon of enals.