Mechanistic study of NHC-catalyzed oxidative N <i>vs</i>. O chemoselective acylation of aldehydes with alkanolamines

Sang, Yuan; Joseph, Ojo; Yuan, Hai-Yan; Zhang, Jing-Ping

doi:10.1039/d4nj00189c

New J. Chem.

2024

DOI: 10.1039/d4nj00189c

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Mechanistic study of NHC-catalyzed oxidative N vs. O chemoselective acylation of aldehydes with alkanolamines

Yuan Sang,

Ojo Joseph,

Hai-Yan Yuan

et al.

Abstract: The possible catalytic mechanism was proposed and studied comprehensively at the M062X/6-31G(d,p) level of theory for a reported chemoselective intermolecular SN2 nucleophilic substitution of aldehydes with alkanoamine. The calculated results...

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A DFT Study on the NHC-Catalyzed Reaction of Enals with Aminoacrylates: Mechanism, Regioselectivity, and Stereoselectivity

Li,

Xiao,

Kang

et al. 2024

J. Phys. Chem. A

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

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A DFT Study on the NHC-Catalyzed Reaction of Enals with Aminoacrylates: Mechanism, Regioselectivity, and Stereoselectivity

Li,

Xiao,

Kang

et al. 2024

J. Phys. Chem. A

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show abstract

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Mechanistic study of NHC-catalyzed oxidative N vs. O chemoselective acylation of aldehydes with alkanolamines

Abstract: The possible catalytic mechanism was proposed and studied comprehensively at the M062X/6-31G(d,p) level of theory for a reported chemoselective intermolecular SN2 nucleophilic substitution of aldehydes with alkanoamine. The calculated results...

Cited by 1 publication

References 67 publications

A DFT Study on the NHC-Catalyzed Reaction of Enals with Aminoacrylates: Mechanism, Regioselectivity, and Stereoselectivity

A DFT Study on the NHC-Catalyzed Reaction of Enals with Aminoacrylates: Mechanism, Regioselectivity, and Stereoselectivity

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