Artículo
A Dynamic Kinetic Asymmetric Heck Reaction for the Simultaneous Generation of Central and Axial Chirality
Autor/es | Carmona, José A.
Hornillos, Valentín Ramírez López, Pedro Ros Lao, Abel Iglesias Sigüenza, Francisco Javier Gómez-Bengoa, Enrique Fernández Fernández, Rosario Fátima Lassaletta Simón, José María |
Departamento | Universidad de Sevilla. Departamento de Química orgánica |
Fecha de publicación | 2018 |
Fecha de depósito | 2019-02-01 |
Publicado en |
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Premios | Premio Anual Publicación Científica Destacada de la US. Facultad de Química |
Resumen | A highly diastereo- and enantioselective, scalable Pd-catalyzed dynamic kinetic asymmetric Heck reaction of heterobiaryl sulfonates with electron-rich olefins is described. The coupling of 2,3-dihydrofuran or N-boc protected ... A highly diastereo- and enantioselective, scalable Pd-catalyzed dynamic kinetic asymmetric Heck reaction of heterobiaryl sulfonates with electron-rich olefins is described. The coupling of 2,3-dihydrofuran or N-boc protected 2,3-dihydropyrrole with a variety of quinoline, quinazoline, phthalazine, and picoline derivatives takes place with simultaneous installation of central and axial chirality, reaching excellent diastereo- and enantiomeric excesses when in situ formed [Pd0/DM-BINAP] was used as the catalyst, with loadings reduced down to 2 mol % in large scale reactions. The coupling of acyclic, electron-rich alkenes can also be performed using a [Pd0/Josiphos ligand] to obtain axially chiral heterobiaryl α-substituted alkenes in high yields and enantioselectivities. Products from Boc-protected 2,3-dihydropyrrole can be easily transformed into N,N ligands or appealing axially chiral, bifunctional proline-type organocatalysts. Computational studies suggest that a β-hydride elimination is the stereocontrolling step, in agreement with the observed stereochemical outcome of the reaction. |
Identificador del proyecto | CTQ2016-76908-C2-1-P
CTQ2016-76908-C2-2-P CTQ2016-78083-P RYC-2013-12585 2012/FQM 10787 1800511201 291780 |
Cita | Carmona, J.A., Hornillos, V., Ramírez López, P., Ros Lao, A., Iglesias Sigüenza, F.J., Gómez-Bengoa, E.,...,Lassaletta Simón, J.M. (2018). A Dynamic Kinetic Asymmetric Heck Reaction for the Simultaneous Generation of Central and Axial Chirality. Journal of the American Chemical Society, 140 (35), 11067-11075. |
Ficheros | Tamaño | Formato | Ver | Descripción |
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10.1021_jacs.8b05819.pdf | 9.441Mb | [PDF] | Ver/ | Versión post-print |