Issue 41, 2021

A phosphine-free Mn(i)-NNS catalyst for asymmetric transfer hydrogenation of acetophenone: a theoretical prediction

Abstract

The density functional theory (DFT) method was employed to investigate the reaction mechanism of the hydrogen activation and asymmetric transfer hydrogenation (ATH) of acetophenone catalyzed by a well-defined phosphine-free Mn(I)-NNS complex. The calculation results indicate that the Mn-NNS complex has potential high catalytic hydrogenation activity. Meanwhile, the hydrogen transfer step of this reaction is proposed to be a concerted but asynchronous process, and the hydride transfer precedes proton transfer. This work also pointed out that the stereoselectivity of ATH catalyzed by the Mn(I)-NNS complex mainly originates from the noncovalent interaction between the substrate and the catalyst. Additionally, the catalytic activities of Mn-NNS complexes with different X ligands (X = CO, Cl, H, OMe, NCMe, CCMe, and CHCHMe) were compared, and the calculated total reaction energy barriers were all viable, which indicates that these Mn-NNS complexes show higher C[double bond, length as m-dash]O bond hydrogenation activity under mild conditions. This theoretical study predicts that the reactions catalyzed by complexes with H and NCMe ligands exhibit high stereoselectivity with enantiomeric excess (ee) values of 97% and 93%, respectively.

Graphical abstract: A phosphine-free Mn(i)-NNS catalyst for asymmetric transfer hydrogenation of acetophenone: a theoretical prediction

Supplementary files

Article information

Article type
Paper
Submitted
20 Jul 2021
Accepted
13 Sep 2021
First published
14 Sep 2021

Dalton Trans., 2021,50, 14738-14744

A phosphine-free Mn(I)-NNS catalyst for asymmetric transfer hydrogenation of acetophenone: a theoretical prediction

Y. Zhao, L. Zhang, M. Pu and M. Lei, Dalton Trans., 2021, 50, 14738 DOI: 10.1039/D1DT02410H

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements