Theoretical investigations of Rh-catalyzed asymmetric 1,4-addition to enones using planar-chiral phosphine-olefin ligands

Kyohei Kawashima, Takehiro Sato, Masamichi Ogasawara, Ken Kamikawa, Seiji Mori

研究成果: ジャーナルへの寄稿学術誌査読

1 被引用数 (Scopus)

抄録

Recently, planar-chiral phosphine-olefin ligands based on (η6-arene)chromium(0) and (η5-cyclopentadienyl)manganese(I), which are known as first- and second-generation, respectively, have been developed. These ligands were employed for Rh-catalyzed asymmetric 1,4-addition to enones. First-generation ligands involve high enantioselectivity for cyclic enones (>98% ee). Second-generation ligands involve high enantioselectivity for not only cyclic enones but also for acyclic enones (>98% ee). In this study, we have performed DFT calculations to investigate the origin of enantioselectivity. The theoretical values of enantioselectivities were found to be in good agreement with the experimental values obtained for a cyclic enone, 2-cyclopenten-1-one, using both the first- and second-generation ligands. Regarding an acyclic enone, 3-penten-2-one, it was found that the s-cis type decreases the enantioselectivity because the transition states in the s-cis type have a large steric repulsion. Energy decomposition analysis (EDA) and natural bond orbital (NBO) analysis indicate that it is important to study the orbital interactions in the transition states of the insertion step for the acyclic enone attacked from si-face with the second-generation ligand.

本文言語英語
ページ(範囲)113-118
ページ数6
ジャーナルJournal of Computational Chemistry
40
1
DOI
出版ステータス出版済み - 1月 5 2019
外部発表はい

!!!All Science Journal Classification (ASJC) codes

  • 化学 (全般)
  • 計算数学

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