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...
| Autores: | , , |
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| Formato: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2014 |
| País: | Argentina |
| Recursos: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/6071 |
| Acesso em linha: | http://hdl.handle.net/11336/6071 |
| Access Level: | acceso abierto |
| Palavra-chave: | Asymmetric Conjugate Alkenylboration Organocatalysis Dft Calculations https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Resumo: | 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. |
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