Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes
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 pic...
| Autores: | , , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2020 |
| País: | España |
| Institución: | Universidad de Sevilla (US) |
| Repositorio: | idUS. Depósito de Investigación de la Universidad de Sevilla |
| OAI Identifier: | oai:idus.us.es:11441/140355 |
| Acceso en línea: | https://hdl.handle.net/11441/140355 https://doi.org/10.1021/jacs.9b12858 |
| Access Level: | acceso abierto |
| Sumario: | 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. |
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