English   español  
Por favor, use este identificador para citar o enlazar a este item: http://hdl.handle.net/10261/112593
Compartir / Impacto:
Estadísticas
Add this article to your Mendeley library MendeleyBASE
Citado 11 veces en Web of Knowledge®  |  Pub MebCentral Ver citas en PubMed Central  |  Ver citas en Google académico
Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL
Exportar otros formatos: Exportar EndNote (RIS)Exportar EndNote (RIS)Exportar EndNote (RIS)
Título

A DFT-based analysis of the gold-catalyzed cycloisomerization of 1-siloxy 1,5-enynes to cyclohexadienes

Autor Soriano, Elena ; Marco-Contelles, José
Fecha de publicación 2012
EditorAmerican Chemical Society
Citación Journal of Organic Chemistry 77: 6231-6238 (2012)
ResumenIn this work, we present a deep theoretical study on the intriguing and unexpected gold-catalyzed cycloisomerization of siloxy enynes to cyclohexadienes. To this end, we have evaluated the electronic and steric properties for three types of alkynyl substituents along the reaction paths and the implications on the evolution through divergent, competitive pathways. For an alkynyl -OR substituent, the results strongly suggest a polarization of the π electrons along the delocalized C2-C1-O system in the key cyclopropyl-carbene intermediate, which is enhanced by the bulkiness of the R group. The results reproduce the experimental observations in excellent agreement and provide interesting and useful clues for predicting the effects of the alkynyl substituent on the nature of the key intermediate and, hence, on the reactivity mode and selectivity. © 2012 American Chemical Society.
URI http://hdl.handle.net/10261/112593
DOI10.1021/jo301057j
Identificadoresdoi: 10.1021/jo301057j
issn: 0022-3263
e-issn: 1520-6904
Aparece en las colecciones: (IQOG) Artículos
Ficheros en este ítem:
Fichero Descripción Tamaño Formato  
accesoRestringido.pdf15,38 kBAdobe PDFVista previa
Visualizar/Abrir
Mostrar el registro completo
 



NOTA: Los ítems de Digital.CSIC están protegidos por copyright, con todos los derechos reservados, a menos que se indique lo contrario.