title: Theoretical Elucidation of Potential Enantioselectivity in a Pd-Catalyzed Aromatic C-H Coupling Reaction.
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.
authors.affiliation: Department of Chemistry, Graduate School of Science, Nagoya University , Nagoya 464-8602, Japan.
authors.forename: Yoshio
authors.identifier: 0000-0001-5581-4712
authors.initials: Y
authors.lastname: Nishimoto
authors.affiliation: Department of Chemistry, Graduate School of Science, Nagoya University , Nagoya 464-8602, Japan.
authors.forename: Hiroki
authors.initials: H
authors.lastname: Kondo
authors.affiliation: Department of Chemistry, Graduate School of Science, Nagoya University , Nagoya 464-8602, Japan.
authors.forename: Kazuya
authors.initials: K
authors.lastname: Yamaguchi
authors.affiliation: Department of Chemistry, Graduate School of Science, Nagoya University , Nagoya 464-8602, Japan.|Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University , Nagoya 464-8602, Japan.
authors.forename: Daisuke
authors.identifier: 0000-0002-7574-0965
authors.initials: D
authors.lastname: Yokogawa
authors.affiliation: Department of Chemistry, Graduate School of Science, Nagoya University , Nagoya 464-8602, Japan.
authors.forename: Junichiro
authors.identifier: 0000-0002-3896-5882
authors.initials: J
authors.lastname: Yamaguchi
authors.affiliation: Department of Chemistry, Graduate School of Science, Nagoya University , Nagoya 464-8602, Japan.|Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University , Nagoya 464-8602, Japan.|JST ERATO, Itami Molecular Nanocarbon Project, Nagoya University , Nagoya 464-8602, Japan.
authors.forename: Kenichiro
authors.identifier: 0000-0001-5227-7894
authors.initials: K
authors.lastname: Itami
authors.affiliation: Department of Chemistry, Graduate School of Science, Nagoya University , Nagoya 464-8602, Japan.|Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University , Nagoya 464-8602, Japan.
authors.forename: Stephan
authors.identifier: 0000-0003-4995-4991
authors.initials: S
authors.lastname: Irle