Asymmetric Hydrogenation of α-Boryl Enamides Enabled by Nonbonding Interactions

Dongyang Fan, Jian Zhang, Yanhua Hu, Zhenfeng Zhang, Ilya D. Gridnev, Wanbin Zhang

Research output: Contribution to journalArticle

Abstract

The asymmetric hydrogenation of α-boryl enamides has been developed using a bisphosphine-rhodium catalyst. The chelate coordination of the amido group to rhodium and the nonbonding interactions between the substrate and the ligand play important roles to afford chiral α-amidoboronic esters with quantitative conversions, high chemoselectivity, and excellent enantioselectivity (92-99% ee). Computation of the catalytic cycle revealed selectivity both in the hydrogen activation and migratory insertion steps, equally contributing to the high enantioselectivity. In both cases, the nonbonding interactions provided by the Bpin group contributed significantly to the stabilization of the transition states in the lower energy pathway.

Original languageEnglish
Pages (from-to)3232-3240
Number of pages9
JournalACS Catalysis
Volume10
Issue number5
DOIs
Publication statusPublished - 2020 Mar 6

Keywords

  • asymmetric hydrogenation
  • nonbonding interaction
  • rhodium
  • α-aminoboronic acid
  • α-boryl enamides

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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