Autor segons l'article: Ricart, J. M. ; García-López, D.; Civit, M.; Vogels, C. ; Westcott, S. ; Fernández, E. ; Carbó, J.
Departament: Química Física i Inorgànica
Autor/s de la URV: RICART PLA, JOSE MANUEL; García-López, D.; Civit, M.; Vogels, C. ; Westcott, S. ; FERNÁNDEZ GUTIÉRREZ, MARIA ELENA; CARBÓ MARTIN, JORGE JUAN
Paraules clau: selenoboration stereoselective anti-addition
Resum: 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.
Grup de recerca: Química Quàntica
Àrees temàtiques: Química Química Chemistry
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 2044-4753
Identificador de l'autor: 0000-0002-2610-5535; ; ; ; ; 0000-0001-9025-1791; 0000-0002-3945-6721
Data d'alta del registre: 2019-01-25
Pàgina final: 3628
Volum de revista: 8
Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
Enllaç font original: https://pubs.rsc.org/en/content/articlelanding/2018/CY/C7CY02295F#!divAbstract
Programa de finançament: plan; Excelencia; CTQ2016-80328-P plan; Excelencia; CTQ2014-52774-P altres; Grupos consolidados; 2014SGR199
URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
DOI de l'article: 10.1039/c7cy02295f
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2018
Pàgina inicial: 3617
Tipus de publicació: Article Artículo Article