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Published on: July 27, 2022
Asymmetric Induction with a Chiral Amine Catalyzed by a Ru-PNP Pincer Complex: Insight from Theoretical Investigation
Yangqiu Liu1, Xin Yue1, Longfei Li2
1State Key Laboratory of Chemical Resource Engineering, Institute of Computational Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China.
Abstract:
In this paper, the mechanism of asymmetric amination of a racemic alcohol with Ellman's sulfinamide and the origin of diastereoselectivity catalyzed by a Ru-PNP pincer complex were studied using density functional theory (DFT). The mechanism involves dehydrogenation of the racemic alcohol, C-N coupling, and hydrogen transfer from the catalyst to the in situ formed imine. The calculated results indicate that both the alcohol dehydrogenation and imine hydrogenation are stepwise. The hydride transfer from a Ru hydride complex to the imine is shown to be the chirality-determining step in the whole catalytic cycle. It was found that the diastereoselectivity mainly stems from the hydrogen bonding interactions between the oxygen atom of the sulfinyl moiety and the hydrogen atom of the NH group of the ligand.
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