TY - JOUR
T1 - Theoretical Elucidation of Potential Enantioselectivity in a Pd-Catalyzed Aromatic C-H Coupling Reaction
AU - Nishimoto, Yoshio
AU - Kondo, Hiroki
AU - Yamaguchi, Kazuya
AU - Yokogawa, Daisuke
AU - Yamaguchi, Junichiro
AU - Itami, Kenichiro
AU - Irle, Stephan
N1 - Funding Information:
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.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/5/5
Y1 - 2017/5/5
N2 - 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.
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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U2 - 10.1021/acs.joc.6b02675
DO - 10.1021/acs.joc.6b02675
M3 - Article
C2 - 28398736
AN - SCOPUS:85019048612
SN - 0022-3263
VL - 82
SP - 4900
EP - 4906
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 9
ER -