Autor según el artículo: Ricart, J. M. ; García-López, D.; Civit, M.; Vogels, C. ; Westcott, S. ; Fernández, E. ; Carbó, J.
Departamento: Química Física i Inorgànica
Autor/es de la URV: RICART PLA, JOSE MANUEL; García-López, D.; Civit, M.; Vogels, C. ; Westcott, S. ; FERNÁNDEZ GUTIÉRREZ, MARIA ELENA; CARBÓ MARTIN, JORGE JUAN
Palabras clave: selenoboration stereoselective anti-addition
Resumen: The stereoselective anti-addition of selenoboranes to α,β-acetylenic esters and amides was achieved in a transition metal-free context using catalytic amounts of PCy3. The reaction provides anti-3,4- selenoboration with concomitant delivery of α-vinyl selenides by protodeboronation with MeOH. Interestingly, in the absence of phosphine the selenoboration switches towards the formation of β-vinyl selenides. Theoretical calculations rationalize the regio- and stereoselectivity of the reaction by discovering a new mechanism for the anti-3,4-selenoboration. While the selenoborane is activated via the “push–pull” effect of B, the phosphine interacts with the β position of the alkynoate switching the polarity of the triple bond and favoring 1,3-selenoboration which provides the α-addition of the selenyl group. Then, the autocatalytic action of a second selenoborane reagent, which coordinates to the phosphorus ylide intermediate, determines the stereoselectivity and completes the catalytic process. Finally, the comparison of selenoborane reagents with diboranes and silaboranes, which have exhibited analogous reactivity, shows that the selenium moiety has a larger nucleophilic character favoring the performance of the reaction under mild conditions.
Grupo de investigación: Química Quàntica
Áreas temáticas: Química Química Chemistry
Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 2044-4753
Identificador del autor: 0000-0002-2610-5535; ; ; ; ; 0000-0001-9025-1791; 0000-0002-3945-6721
Fecha de alta del registro: 2019-01-25
Página final: 3628
Volumen de revista: 8
Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
Enlace a la fuente original: https://pubs.rsc.org/en/content/articlelanding/2018/CY/C7CY02295F#!divAbstract
Programa de financiación: plan; Excelencia; CTQ2016-80328-P plan; Excelencia; CTQ2014-52774-P altres; Grupos consolidados; 2014SGR199
URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
DOI del artículo: 10.1039/c7cy02295f
Entidad: Universitat Rovira i Virgili
Año de publicación de la revista: 2018
Página inicial: 3617
Tipo de publicación: Article Artículo Article