Mechanistic studies clarifying how chiral primary amines control the stereochemistry of vinylogous processes are rare. We report a density functional theory (DFT) computational study for the comprehension of the reaction mechanism of the vinylogous atroposelective desymmetrization of N-(2-t-butylaryl)maleimide catalyzed by 9-amino(9-deoxy)epi-quinine. Our results illustrate how the origin of the atroposelectivity was realized by the catalyst through steric and dispersion interactions. The role of N-Boc-l-Ph-glycine was crucial for the formation of a closed transition-state geometry and the activation of both reaction partners.

Tampellini N., Righi P., Bencivenni G. (2021). Computational Investigation on the Origin of Atroposelectivity for the Cinchona Alkaloid Primary Amine-Catalyzed Vinylogous Desymmetrization of N-(2- t-Butylphenyl)maleimides. JOURNAL OF ORGANIC CHEMISTRY, 86(17), 11782-11793 [10.1021/acs.joc.1c01235].

Computational Investigation on the Origin of Atroposelectivity for the Cinchona Alkaloid Primary Amine-Catalyzed Vinylogous Desymmetrization of N-(2- t-Butylphenyl)maleimides

Righi P.
Secondo
;
Bencivenni G.
Ultimo
2021

Abstract

Mechanistic studies clarifying how chiral primary amines control the stereochemistry of vinylogous processes are rare. We report a density functional theory (DFT) computational study for the comprehension of the reaction mechanism of the vinylogous atroposelective desymmetrization of N-(2-t-butylaryl)maleimide catalyzed by 9-amino(9-deoxy)epi-quinine. Our results illustrate how the origin of the atroposelectivity was realized by the catalyst through steric and dispersion interactions. The role of N-Boc-l-Ph-glycine was crucial for the formation of a closed transition-state geometry and the activation of both reaction partners.
2021
Tampellini N., Righi P., Bencivenni G. (2021). Computational Investigation on the Origin of Atroposelectivity for the Cinchona Alkaloid Primary Amine-Catalyzed Vinylogous Desymmetrization of N-(2- t-Butylphenyl)maleimides. JOURNAL OF ORGANIC CHEMISTRY, 86(17), 11782-11793 [10.1021/acs.joc.1c01235].
Tampellini N.; Righi P.; Bencivenni G.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/854789
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