Author, as appears in the article.: Franchino A; Martí À; Echavarren AM
Department: Química Analítica i Química Orgànica
URV's Author/s: ECHAVARREN PABLOS, ANTONIO / Martí Zaragoza, Àlex
Keywords: Chiral bronsted acid transfer hydrogenation phosphoric-acid noncovalent interactions metal catalysis ligands hydroalkoxylation highly substituted furans gold complexes
Abstract: A new strategy for enantioselective transition-metal catalysis is presented, wherein a H-bond donor placed on the ligand of a cationic complex allows precise positioning of the chiral counteranion responsible for asymmetric induction. The successful implementation of this paradigm is demonstrated in 5-exo-dig and 6-endo-dig cyclizations of 1,6-enynes, combining an achiral phosphinourea Au(I) chloride complex with a BINOL-derived phosphoramidate Ag(I) salt and thus allowing the first general use of chiral anions in Au(I)-catalyzed reactions of challenging alkyne substrates. Experiments with modified complexes and anions, 1H NMR titrations, kinetic data, and studies of solvent and nonlinear effects substantiate the key H-bonding interaction at the heart of the catalytic system. This conceptually novel approach, which lies at the intersection of metal catalysis, H-bond organocatalysis, and asymmetric counterion-directed catalysis, provides a blueprint for the development of supramolecularly assembled chiral ligands for metal complexes.
Thematic Areas: Química Materiais Interdisciplinar General chemistry Farmacia Engenharias iv Engenharias iii Engenharias ii Colloid and surface chemistry Ciências biológicas ii Ciências biológicas i Ciências agrárias i Ciência de alimentos Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Biochemistry Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: antoniomaria.echavarren@urv.cat alex.marti@estudiants.urv.cat
Author identifier: 0000-0002-6418-7930
Record's date: 2024-01-13
Papper version: info:eu-repo/semantics/publishedVersion
Link to the original source: https://pubs.acs.org/doi/10.1021/jacs.1c11978
Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Journal Of The American Chemical Society. 144 (8): 3497-3509
APA: Franchino A; Martí À; Echavarren AM (2022). H-Bonded Counterion-Directed Enantioselective Au(I) Catalysis. Journal Of The American Chemical Society, 144(8), 3497-3509. DOI: 10.1021/jacs.1c11978
Article's DOI: 10.1021/jacs.1c11978
Entity: Universitat Rovira i Virgili
Journal publication year: 2022
Publication Type: Journal Publications
Repositori URV