Organocatalytic Strategies to Stereoselectively Trap Photochemically Generated Hydroxy-o-quinodimethanes

Light excitation of ortho-alkyl aromatic ketones and aldehydes enables access to hydroxy-o-quinodimethanes. These reactive electron-rich intermediates are sufficiently long-lived to productively engage in chemical processes, mainly acting as dienes in [4+2]-cycloadditions with electron-poor alkenes....

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Detalles Bibliográficos
Autores: Cuadros, Sara, Melchiorre, Paolo
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
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:2072/335531
Acceso en línea:http://hdl.handle.net/2072/335531
https://doi.org/10.1002/ejoc.201800081
Access Level:acceso abierto
Palabra clave:54
Descripción
Sumario:Light excitation of ortho-alkyl aromatic ketones and aldehydes enables access to hydroxy-o-quinodimethanes. These reactive electron-rich intermediates are sufficiently long-lived to productively engage in chemical processes, mainly acting as dienes in [4+2]-cycloadditions with electron-poor alkenes. Since the early discovery of this photoenolization mechanism, which dates back to 1961, a variety of transformations has been developed, providing a photochemical alternative to classical Diels-Alder chemistry. However, enantioselective catalytic versions of the photenoliza tion/Diels-Alder sequence have remained elusive until recently. This review describes how the field of enantioselective organocatalysis has provided suitable tools to stereoselectively trap photochemically generated hydroxy-o-quinodimethanes. Recent studies also demonstrated that the chemistry is not limited to cycloaddition-type manifolds, but it can be expanded to develop intermolecular enantioselective addition processes.