Artículo
AuI-Catalyzed Hydroalkynylation of Haloalkynes
Autor/es | García Fernández, Pedro David
Iglesias Sigüenza, Francisco Javier Rivero Jerez, Paula S. Díez Martín, Elena Gómez Bengoa, Enrique Fernández Fernández, Rosario Fátima Lassaletta, José M. |
Departamento | Universidad de Sevilla. Departamento de Química orgánica |
Fecha de publicación | 2020 |
Fecha de depósito | 2022-11-29 |
Publicado en |
|
Resumen | The AuI-catalyzed reaction between terminal alkynes and aromatic haloalkynes proceeds through divergent pathways depending on the nature of the catalyst counteranion. Thus, cationic complexes containing strongly basic NHC ... The AuI-catalyzed reaction between terminal alkynes and aromatic haloalkynes proceeds through divergent pathways depending on the nature of the catalyst counteranion. Thus, cationic complexes containing strongly basic NHC ligands and noncoordinating anions such as BArF4 catalyze the cis haloalkynylation of the terminal alkyne, whereas introduction of a weakly basic triflate counteranion results in the stereoselective hydroalkynylation of the haloalkyne, yielding haloenyne products in good yields and complete trans selectivity. Experimental and computational studies suggest that the hydroalkynylation reaction takes place via nucleophilic attack of the terminal alkyne to the C2 carbon of the activated haloalkyne, assisted by a concerted proton abstraction by the triflate, and that the protodeauration is the turnover-limiting step, in agreement with an observed primary kinetic isotope effect. |
Agencias financiadoras | Ministerio de Economia, Industria y Competitividad (MINECO). España Junta de Andalucía |
Identificador del proyecto | PID2019-106358GB-C21
PID2019-106358GB-C22 P18-FR-3531 P18-FR-644 US-1262867 |
Cita | García Fernández, P.D., Iglesias Sigüenza, F.J., Rivero Jerez, P.S., Díez Martín, E., Gómez Bengoa, E., Fernández Fernández, R.F. y Lassaletta, J.M. (2020). AuI-Catalyzed Hydroalkynylation of Haloalkynes. Journal of the American Chemical Society, 142 (37), 16082-16089. https://doi.org/10.1021/jacs.0c07951. |
Ficheros | Tamaño | Formato | Ver | Descripción |
---|---|---|---|---|
Au-I-Catalyzed.pdf | 2.977Mb | [PDF] | Ver/ | |