Artículo
Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes
Autor/es | Romero Arenas, Antonio
Hornillos, Valentín Iglesias Sigüenza, Francisco Javier Fernández Fernández, Rosario Fátima López Serrano, Joaquín Ros, Abel Lassaletta, José M. |
Departamento | Universidad de Sevilla. Departamento de Química orgánica |
Fecha de publicación | 2020 |
Fecha de depósito | 2022-12-12 |
Publicado en |
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Resumen | A highly regio-, diastereo-, and enantioselective, scalable Ir-catalyzed hydroarylation of electron-rich acyclic and tensioned cyclic olefins with heterobiaryls is described. The reaction of acyclic vinyl ethers, dihydrofuran, ... A highly regio-, diastereo-, and enantioselective, scalable Ir-catalyzed hydroarylation of electron-rich acyclic and tensioned cyclic olefins with heterobiaryls is described. The reaction of acyclic vinyl ethers, dihydrofuran, and norbornenes with a variety of aryl isoquinoline, quinazoline, and picoline derivatives takes place with simultaneous installation of central and axial chirality, reaching complete branched/linear or exo/endo ratios and excellent diastereo- and enantiomeric excesses when in situ formed [IrI/Tol-SDP] or [IrI/Tol-BINAP] complexes are used as the catalysts. Deuterium labeling experiments and a comprehensive computational study suggest that, despite fast double bond migratory insertion into Ir-H, the reaction proceeds through a modified Chalk-Harrod mechanism, starting with selectivity-determining insertion into Ir-CAryl. The regioselectivity is controlled by the electron-donating alkoxy group, whereas diastereo- and enantioselectivity have a complex origin, which depend on the relative orientation of the alkoxy group and the establishment of adequate π-πinteractions between the biaryl and the phosphine. |
Agencias financiadoras | Ministerio de Ciencia e Innovación (MICIN). España Junta de Andalucía |
Identificador del proyecto | CTQ2013-48164-C2-1-P
CTQ2013-48164-C2-2-P CTQ2016-75193-P RYC-2013-12585 RYC-2017-22294 2012/FQM 10787 |
Cita | Romero Arenas, A., Hornillos, V., Iglesias Sigüenza, F.J., Fernández Fernández, R.F., López Serrano, J., Ros, A. y Lassaletta, J.M. (2020). Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes. Journal of the American Chemical Society, 142 (5), 2628-2639. https://doi.org/10.1021/jacs.9b12858. |
Ficheros | Tamaño | Formato | Ver | Descripción |
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Ir-Catalyzed Atroposelective.pdf | 5.135Mb | [PDF] | Ver/ | |