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oai:recercat.cat:2072/5216832024-12-20T17:54:30Zcom_2072_300912com_2072_4427col_2072_301309

H‑Bonded Counterion-Directed Enantioselective Au(I) Catalysis Franchino, Allegra Martí, Àlex Echavarren, Antonio M. 54 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. 2022-02-09 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion http://hdl.handle.net/2072/521683 https://doi.org/10.1021/jacs.1c11978 eng MCIN/AEI/10.13039/501100011033 (Grants PID2019-104815GB-I00 and CEX2019-000925-S) Horizon 2020 Marie Skłodowska-Curie COFUND Postdoctoral Fellowship 754510 to A.F. Advanced Grant 835080 Grant 2017 SGR 1257 and FI Fellowship to À.M. You have selected the Attribution-NonCommercial-NoDerivatives 4.0 International License. This license is permanently located at http://creativecommons.org/licenses/by-nc-nd/4.0/. info:eu-repo/semantics/openAccess 3497 p. application/pdf RECERCAT (Dipòsit de la Recerca de Catalunya)