Autor segons l'article: Faiges J; Biosca M; Pericàs MA; Besora M; Pàmies O; Diéguez M
Departament: Química Física i Inorgànica
Autor/s de la URV: Besora Bonet, Maria / Biosca Brull, Maria / Diéguez Fernández, Montserrat / Faiges Marcos, Jorge / Pamies Ollé, Oscar / Pericàs Brondo, Miquel Àngel
Paraules clau: Theoretical calculations Tetrasubstituted enones Tetrasubsituted olefins N-phosphine-oxazoline Mechanism Iridium catalysts Iridium Enones Asymmetric hydrogenation
Resum: 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.
Àrees temàtiques: 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
Adreça de correu electrònic de l'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 de l'autor: 0000-0002-9116-6318 0000-0002-6656-5827 0000-0002-2352-8508 0000-0002-8450-0656
Data d'alta del registre: 2024-11-02
Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
Enllaç font original: https://onlinelibrary.wiley.com/doi/10.1002/anie.202315872
URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
Referència a l'article segons font original: Angewandte Chemie (International Ed. Print). 63 (9): e202315872-e202315872
Referència 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 de l'article: 10.1002/anie.202315872
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2024
Tipus de publicació: Journal Publications