A Domino Process towards Functionally Dense Quaternary Carbons through Pd-Catalyzed Decarboxylative Csp3-Csp3 Bond Formation

An efficient protocol was developed to construct functionally dense quaternary carbons with concomitant formation of a new Csp3-Csp3 bond via Pd-catalyzed decarboxylative transformation of vinyl cyclic carbonates. This redox neutral catalytic system features stereocontrolled formation of multi-subst...

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Detalles Bibliográficos
Autores: Guo, Wusheng, Kuniyil, Rositha, Gómez, José Enrique, Maseras, Feliu, Kleij, Arjan W.
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:2072/356262
Acceso en línea:http://hdl.handle.net/2072/356262
https://doi.org/10.1021/jacs.7b12608
Access Level:acceso abierto
Palabra clave:54
Descripción
Sumario:An efficient protocol was developed to construct functionally dense quaternary carbons with concomitant formation of a new Csp3-Csp3 bond via Pd-catalyzed decarboxylative transformation of vinyl cyclic carbonates. This redox neutral catalytic system features stereocontrolled formation of multi-substituted allylic scaffolds with an aldehyde functionality generated in situ, and it typically can be performed at room temperature without any additives. DFT calculations provide a rationale towards the selective formation of these compounds, and revealed a complex mechanism that is able to reproduce with the help of microkinetic models the non-trivial dependence between the identity of the product and the nature of the substituents in the substrate.