open access

https://hdl.handle.net/2115/90940

Substrate-Assisted Reductive Elimination Determining the Catalytic Cycle : A Theoretical Study on the Ni-Catalyzed 2,3-Disubstituted Benzofuran Synthesis via C-O Bond Activation

英語

2022-12-12

American Chemical Society

Organometallics

41(23)

3581-3588

2,3-Disubstituted benzofurans with potential for pharmaceutical applications are effectively synthesized by Ni complexes via intramolecular C-O bond activation. The reaction pathway for the full catalytic cycle has been investigated using density functional theory (DFT) calculations. The rate-determin-ing step is the reductive elimination of the product. A key result is that coordination to an alkynyl group of another substrate co-occurs with elimination, which not only improves thermodynamic stability of the product but also determines the reaction pathway of the catalytic cycle. The reductive elimination assisted by the solvent molecules or free ligand results in an endergonic reaction. This result is related to the enhancement of reductive elimination of C-C coupling products by the addition of olefins or alkynes and can be recognized as a self-cocatalytic effect of the substrate. The result adds another viewpoint in the design of catalytic reaction systems with effective catalytic cycles.

学術雑誌論文

Accepted Manuscript

This document is the Accepted Manuscript version of a Published Work that appeared in final form in [Organometallics], copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/articlesonrequest/AOR-MMAKNDVMUJVZ8UDDE6CC

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