A DFT Study on the NHC-Catalyzed Reaction of Enals with Aminoacrylates: Mechanism, Regioselectivity, and Stereoselectivity DOI
Yan Li, Junjie Xiao,

Yanlong Kang

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

DFT (M06-2X) calculations were used to study the NHC-catalyzed [3 + 3] cycloaddition of enals with aminoacrylates. The catalytic cycle begins binding NHC enal. Subsequent intramolecular proton transfer generates Breslow intermediate. This intermediate undergoes an oxidative reaction, leading formation acyl azolium intermediate, which further reacts other substrate aminoacrylate via a new C–C bond formation. step determines stereoselectivity current and re-face addition mode S-configuration is predominant. Afterward, sequential protonation, deprotonation, cyclization form six-membered cyclic upon elimination affords final product dihydropyridinone. computed enantiomeric excess (99.1% ee) in very good agreement experimentally reported value (99% ee). origin enantioselectivity traced stronger LP···π interactions between favored S-congurational transition state.

Language: Английский

A DFT Study on the NHC-Catalyzed Reaction of Enals with Aminoacrylates: Mechanism, Regioselectivity, and Stereoselectivity DOI
Yan Li, Junjie Xiao,

Yanlong Kang

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

DFT (M06-2X) calculations were used to study the NHC-catalyzed [3 + 3] cycloaddition of enals with aminoacrylates. The catalytic cycle begins binding NHC enal. Subsequent intramolecular proton transfer generates Breslow intermediate. This intermediate undergoes an oxidative reaction, leading formation acyl azolium intermediate, which further reacts other substrate aminoacrylate via a new C–C bond formation. step determines stereoselectivity current and re-face addition mode S-configuration is predominant. Afterward, sequential protonation, deprotonation, cyclization form six-membered cyclic upon elimination affords final product dihydropyridinone. computed enantiomeric excess (99.1% ee) in very good agreement experimentally reported value (99% ee). origin enantioselectivity traced stronger LP···π interactions between favored S-congurational transition state.

Language: Английский

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