A Hydrogen Bond Rationale for the Enantioselective beta-Alkenylboration of Enones Catalyzed by O-Monoacyltartaric Acids

DFT calculations suggest that O-monoacyl L-tartaric acids catalyze the asymmetric conjugate alkenylboration of enones through transition structures that are stabilized by hydrogen-bonding interactions. Formation of a fivemembered acyloxyborane is proposed. The hydrogen of the free carboxy group deri...

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Detalles Bibliográficos
Autores: Grimblat, Nicolas, Sugiura, Masaharu, Pellegrinet, Silvina Carla
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2014
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/6071
Acceso en línea:http://hdl.handle.net/11336/6071
Access Level:acceso abierto
Palabra clave:Asymmetric Conjugate Alkenylboration
Organocatalysis
Dft Calculations
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
Descripción
Sumario:DFT calculations suggest that O-monoacyl L-tartaric acids catalyze the asymmetric conjugate alkenylboration of enones through transition structures that are stabilized by hydrogen-bonding interactions. Formation of a fivemembered acyloxyborane is proposed. The hydrogen of the free carboxy group derived from the catalyst interacts with the carbonyl group of the cyclic acyloxyborane, stabilizing the transition structure and reducing the flexibility of the system. Additional stabilizing nonclassical CH···O hydrogen-bond interactions seem to determine the observed enantioselectivity.