Catalytic Activity of Mono- and Bimetallic Rhodium(I) and Iridium(I) Complexes Bearing Carbon-Ether-Carbon (COC) Ligand for the Intramolecular Cyclization of 4-Pentynoic Acid
Boddaert, Hugo; Tolley, Lewis C.; Mejuto, Carmen; González, Ainhoa; Martín, Marta; Sola, Eduardo; Fernández, Israel; Karhu, Aino J.; Bezuidenhout, Daniela I.; Guisado-Barrios, Gregorio (2024-09-18)
John Wiley & Sons
18.09.2024
H. Boddaert, L. C. Tolley, C. Mejuto, A. González, M. Martín, E. Sola, I. Fernández, A. J. Karhu, D. I. Bezuidenhout, G. Guisado-Barrios, Eur. J. Org. Chem. 2024, 27, e202400670. https://doi.org/10.1002/ejoc.202400670.
https://creativecommons.org/licenses/by-nc-nd/4.0/
© 2024 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.
https://creativecommons.org/licenses/by-nc-nd/4.0/
© 2024 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.
https://creativecommons.org/licenses/by-nc-nd/4.0/
Julkaisun pysyvä osoite on
https://urn.fi/URN:NBN:fi:oulu-202411186779
https://urn.fi/URN:NBN:fi:oulu-202411186779
Tiivistelmä
Abstract
The catalytic performance of a series of mono- and bimetallic Ir(I) and Rh(I) complexes bearing the (COC) bis-triazolylidene ligand, coordinated in a bridging or chelating fashion, was evaluated in the cyclization of 4-pentynoic acid. The chelated mononuclear cationic complex [Ir(cod)(COC)]PF6 (cod=1,5-cyclooctadiene; COC=biscarbene ether) displayed the highest reaction rate for 4-pentynoic acid to form γ-methyl-ene-γ-butyrolactone (5-methylenedihydrofuran-2(3H)-one). Density Functional Theory calculations were carried out to rationalize the reaction mechanism which proceeds in three steps, namely coordination of the alkyne to the active catalyst followed by intramolecular cyclization and final reductive elimination. Its catalytic performance was further assessed against different substituted 4-pentynoic acid derivatives.
The catalytic performance of a series of mono- and bimetallic Ir(I) and Rh(I) complexes bearing the (COC) bis-triazolylidene ligand, coordinated in a bridging or chelating fashion, was evaluated in the cyclization of 4-pentynoic acid. The chelated mononuclear cationic complex [Ir(cod)(COC)]PF6 (cod=1,5-cyclooctadiene; COC=biscarbene ether) displayed the highest reaction rate for 4-pentynoic acid to form γ-methyl-ene-γ-butyrolactone (5-methylenedihydrofuran-2(3H)-one). Density Functional Theory calculations were carried out to rationalize the reaction mechanism which proceeds in three steps, namely coordination of the alkyne to the active catalyst followed by intramolecular cyclization and final reductive elimination. Its catalytic performance was further assessed against different substituted 4-pentynoic acid derivatives.
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- Avoin saatavuus [38841]
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