Autor según el artículo: Faiges J; Biosca M; Pericàs MA; Besora M; Pàmies O; Diéguez M
Departamento: Química Física i Inorgànica
Autor/es de la URV: Besora Bonet, Maria / Biosca Brull, Maria / Diéguez Fernández, Montserrat / Faiges Marcos, Jorge / Pamies Ollé, Oscar / Pericàs Brondo, Miquel Àngel
Palabras clave: Theoretical calculations Tetrasubstituted enones Tetrasubsituted olefins N-phosphine-oxazoline Mechanism Iridium catalysts Iridium Enones Asymmetric hydrogenation
Resumen: Asymmetric hydrogenation (AH) of tetrasubstituted olefins generating two stereocenters is still an open topic. There are only a few reports on the AH of tetrasubstituted olefins with conjugated functional groups, while this process can create useful intermediates for the subsequent elaboration of relevant end products. Most of the tetrasubstituted olefins successfully submitted to AH belong to a small number of functional classes; remarkably, the AH of tetrasubstituted acyclic enones still represents an unsolved challenge. Herein, we disclose a class of air-stable Ir-P,N catalysts, prepared in three steps from commercially available amino alcohols, that can hydrogenate, in minutes, a wide range of electronically and sterically diverse acyclic tetrasubstituted enones (including exocyclic ones) with high yields and high enantioselectivities. The factors responsible for the excellent selectivities were elucidated by combining deuterogenation experiments and theoretical calculations. The calculations indicated that the reduction follows an IrI/IrIII mechanism, in which enantioselectivity is controlled in the first migratory insertion of the hydride to the most electrophilic olefinic Cβ and the formation of the hydrogenated product via reductive elimination takes place prior to the coordination of dihydrogen and the subsequent oxidative addition. The potential of the new catalytic systems is demonstrated by the derivatization of hydrogenation products.© 2023 Wiley-VCH GmbH.
Áreas temáticas: Química Medicina ii Medicina i Materiais Interdisciplinar General medicine General chemistry Farmacia Engenharias ii Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Astronomia / física
Direcció de correo del autor: maria.biosca@urv.cat miquelangel.pericas@urv.cat maria.besora@urv.cat jorge.faiges@urv.cat oscar.pamies@urv.cat montserrat.dieguez@urv.cat
Identificador del autor: 0000-0002-9116-6318 0000-0002-6656-5827 0000-0002-2352-8508 0000-0002-8450-0656
Fecha de alta del registro: 2024-11-02
Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
Enlace a la fuente original: https://onlinelibrary.wiley.com/doi/10.1002/anie.202315872
URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
Referencia al articulo segun fuente origial: Angewandte Chemie (International Ed. Print). 63 (9): e202315872-e202315872
Referencia de l'ítem segons les normes APA: Faiges J; Biosca M; Pericàs MA; Besora M; Pàmies O; Diéguez M (2024). Unlocking the Asymmetric Hydrogenation of Tetrasubstituted Acyclic Enones. Angewandte Chemie (International Ed. Print), 63(9), e202315872-e202315872. DOI: 10.1002/anie.202315872
DOI del artículo: 10.1002/anie.202315872
Entidad: Universitat Rovira i Virgili
Año de publicación de la revista: 2024
Tipo de publicación: Journal Publications