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

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