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Updated: Aug 27, 2025

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs
Published on: January 17, 2020
Computational Study on the Co-Mediated Intramolecular Pauson-Khand Reaction of Fluorinated and Chiral N-Tethered
Jorge Escorihuela1, Lawrence M Wolf2
1Departamento de Química Orgánica, Facultad de Farmacia, Universitat de València, Av. Vicent Andrés Estellés s/n, 46100Burjassot, València, Spain.
Abstract:
The Co2(CO)8-mediated intramolecular Pauson-Khand reaction is an elegant approach to obtain cyclopentenone derivatives containing asymmetric centers. In this work, we employed density functional theory calculations at the M11/6-311+G(d,p) level of theory to investigate the mechanism and reactivity for the Pauson-Khand reaction of fluorinated and asymmetric N-tethered 1,7-enynes. The rate-determining step was found to be the intramolecular alkene insertion into the carbon-cobalt bond. The stereoselectivity of the alkene insertion step was rationalized by the different transition states showing the coordination of the alkene through the Re- and Si-face. The effects of different fluorine groups and steric effects on both the alkenyl and alkynyl moieties were also theoretically investigated.
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