Affiliation:
1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospekt 47, 119911 Moscow, Russia
Abstract
The mechanism of the recently reported catalyzed asymmetric hydrogenation of enyne 1 catalyzed by the Co-(R,R)-QuinoxP* complex was studied by DFT. Conceivable pathways for the Co(I)-Co(III) mechanism were computed together with a Co(0)-Co(II) catalytic cycle. It is commonly assumed that the exact nature of the chemical transformations taking place along the actually operating catalytic pathway determine the sense and level of enantioselection of the catalytic reaction. In this work, two chemically different mechanisms reproduced the experimentally observed perfect stereoselection of the same handedness. Moreover, the relative stabilities of the transition states of the stereo induction stages were controlled via exactly the same weak disperse interactions between the catalyst and the substrate.
Subject
Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Computer Science Applications,Spectroscopy,Molecular Biology,General Medicine,Catalysis
Reference74 articles.
1. Hartwig, J. (2009). Organotransition Metal Chemistry: From Bonding to Catalysis, University Science Books. [1st ed.].
2. Barton, A. (2022). Organometallic Transition Metal Catalysis: A Hostic Approach to Understanding and Predicting Their Mechanisms, Lulu.
3. Jacobsen, E.N., Pfalz, A., and Yamamoto, H. (1999). Hydrogenation of Functionalized Carbon-Carbon Double Bonds, Springer.
4. Mechanism of Stereoselectivity of Asymmetric Hydrogenation;Halpern;Science,1982
5. Asymmetric Hydrogenation of Methyl-(Z)-α-acetamidocinnamate Catalyzed by {1,2-Bis((phenyl-o-anisoyl)phosphino)ethane}rhodium(I): Kinetics, Mechanism, and Origin of Enantioselection;Landis;J. Am. Chem. Soc.,1987
Cited by
2 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献