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DFT Studies on the Carboxylation of the C−H Bond of Heteroarenes by Copper(I) Complexes
journal contribution
posted on 2023-05-17, 11:14 authored by Alireza AriafardAlireza Ariafard, Zarkoob, F, Batebi, H, Stranger, R, Brian YatesBrian YatesIn this study, we have used density functional theory to identify a new mechanism for the formation of carboxylate compounds from heteroarenes, such as benzoxazole, in the presence of copper catalysts. This new mechanism involves the formation of a carbene intermediate that is indirectly stabilized by the electron-releasing copper. This intermediate carbene can isomerize to the experimentally observed resting state of the catalytic cycle, but it is the intermediate carbene itself that has the greater reactivity toward CO2 and that leads to the final carboxylate product via a lower-energy pathway. Our findings demonstrate the importance of considering metal-stabilized carbenes in such reactions. Our findings also suggest that this carbene intermediate can act as a nucleophile in other organometallic reactions.
Funding
Australian Research Council
History
Publication title
OrganometallicsVolume
30Issue
22Pagination
6218-6224ISSN
0276-7333Department/School
School of Natural SciencesPublisher
American Chemical SocietyPlace of publication
Washington, USARights statement
Copyright 2011 American Chemical SocietyRepository Status
- Restricted