Theoretical Elucidation of Potential Enantioselectivity in a Pd-Catalyzed Aromatic C-H Coupling Reaction

Yoshio Nishimoto; Hiroki Kondo; Kazuya Yamaguchi; Daisuke Yokogawa; Junichiro Yamaguchi; Kenichiro Itami; Stephan Irle

doi:10.1021/acs.joc.6b02675

Theoretical Elucidation of Potential Enantioselectivity in a Pd-Catalyzed Aromatic C-H Coupling Reaction

Yoshio Nishimoto, Hiroki Kondo, Kazuya Yamaguchi, Daisuke Yokogawa, Junichiro Yamaguchi, Kenichiro Itami, Stephan Irle

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

The mechanism of an aromatic C-H coupling reaction between heteroarenes and arylboronic acids using a Pd catalyst was theoretically and experimentally investigated. We identified the C-B transmetalation as the rate-determining step. The (S)-catalyst-reactant complex was found to be stabilized by hyperconjugation between π-orbitals on the tolyl group and the S-O σ* antibonding orbital in the catalyst ligand. Our findings suggest routes for the design of new, improved Pd catalysts with higher stereoselectivity.

Original language	English
Pages (from-to)	4900-4906
Number of pages	7
Journal	Journal of Organic Chemistry
Volume	82
Issue number	9
DOIs	https://doi.org/10.1021/acs.joc.6b02675
State	Published - May 5 2017
Externally published	Yes

Funding

The authors thank Prof. Odile Eisenstein for helpful discussions and the Research Center for Computational Science, Okazaki, Japan, for providing computational resources. Y.N. was supported by a Research Fellowship of the Japan Society for Promotion of Science for Young Scientists (DC1). Y.N. and H.K. thank IGER Program in Green Natural Sciences, Nagoya University for a fellowship. S.I. acknowledges partial support by a CREST grant from JST.

Funders	Funder number
Japan Society for Promotion of Science for Young Scientists
Japan Society for the Promotion of Science	15J04509, 15K05385, 16H04148
Japan Science and Technology Agency
Core Research for Evolutional Science and Technology
Nagoya University

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abstract = "The mechanism of an aromatic C-H coupling reaction between heteroarenes and arylboronic acids using a Pd catalyst was theoretically and experimentally investigated. We identified the C-B transmetalation as the rate-determining step. The (S)-catalyst-reactant complex was found to be stabilized by hyperconjugation between π-orbitals on the tolyl group and the S-O σ* antibonding orbital in the catalyst ligand. Our findings suggest routes for the design of new, improved Pd catalysts with higher stereoselectivity.",

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AU - Kondo, Hiroki

AU - Yamaguchi, Kazuya

AU - Yokogawa, Daisuke

AU - Yamaguchi, Junichiro

AU - Itami, Kenichiro

AU - Irle, Stephan

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AB - The mechanism of an aromatic C-H coupling reaction between heteroarenes and arylboronic acids using a Pd catalyst was theoretically and experimentally investigated. We identified the C-B transmetalation as the rate-determining step. The (S)-catalyst-reactant complex was found to be stabilized by hyperconjugation between π-orbitals on the tolyl group and the S-O σ* antibonding orbital in the catalyst ligand. Our findings suggest routes for the design of new, improved Pd catalysts with higher stereoselectivity.

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Theoretical Elucidation of Potential Enantioselectivity in a Pd-Catalyzed Aromatic C-H Coupling Reaction

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