Theoretical study on the mechanism of N-heterocyclic carbene catalyzed transesterification reactions

Chun Liang Lai; Hon Man Lee; Ching Han Hu

doi:10.1016/j.tetlet.2005.07.046

Theoretical study on the mechanism of N-heterocyclic carbene catalyzed transesterification reactions

Chun Liang Lai, Hon Man Lee, Ching Han Hu

Research output: Contribution to journal › Article › peer-review

72 Scopus citations

Abstract

The mechanism of N-heterocyclic carbene (NHC) catalyzed transesterification reactions have been studied using density functional theory. Our study shows that the role of NHC is to assist proton transfer from alcohol to the carbonyl oxygen, forming the tetrahedral intermediate, which then decomposes to the acylated product. Our predicted activation energies are in fine agreement with the observed reaction rates. An alternative approach, which uses the tetrahedral intermediate as the transition state mimic, provides satisfactory predictions.

Original language	English (US)
Pages (from-to)	6265-6270
Number of pages	6
Journal	Tetrahedron Letters
Volume	46
Issue number	37
DOIs	https://doi.org/10.1016/j.tetlet.2005.07.046
State	Published - Sep 12 2005
Externally published	Yes

Keywords

Density functional theory
NHC
Transesterification

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tetlet.2005.07.046

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title = "Theoretical study on the mechanism of N-heterocyclic carbene catalyzed transesterification reactions",

abstract = "The mechanism of N-heterocyclic carbene (NHC) catalyzed transesterification reactions have been studied using density functional theory. Our study shows that the role of NHC is to assist proton transfer from alcohol to the carbonyl oxygen, forming the tetrahedral intermediate, which then decomposes to the acylated product. Our predicted activation energies are in fine agreement with the observed reaction rates. An alternative approach, which uses the tetrahedral intermediate as the transition state mimic, provides satisfactory predictions.",

keywords = "Density functional theory, NHC, Transesterification",

author = "Lai, {Chun Liang} and Lee, {Hon Man} and Hu, {Ching Han}",

note = "Funding Information: We gratefully acknowledge the financial support from the National Science Council of Taiwan, Republic of China. We also thank the National Center for High-performance Computing for computer time and facilities. Copyright: Copyright 2008 Elsevier B.V., All rights reserved.",

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AU - Lai, Chun Liang

AU - Lee, Hon Man

AU - Hu, Ching Han

N1 - Funding Information: We gratefully acknowledge the financial support from the National Science Council of Taiwan, Republic of China. We also thank the National Center for High-performance Computing for computer time and facilities. Copyright: Copyright 2008 Elsevier B.V., All rights reserved.

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N2 - The mechanism of N-heterocyclic carbene (NHC) catalyzed transesterification reactions have been studied using density functional theory. Our study shows that the role of NHC is to assist proton transfer from alcohol to the carbonyl oxygen, forming the tetrahedral intermediate, which then decomposes to the acylated product. Our predicted activation energies are in fine agreement with the observed reaction rates. An alternative approach, which uses the tetrahedral intermediate as the transition state mimic, provides satisfactory predictions.

AB - The mechanism of N-heterocyclic carbene (NHC) catalyzed transesterification reactions have been studied using density functional theory. Our study shows that the role of NHC is to assist proton transfer from alcohol to the carbonyl oxygen, forming the tetrahedral intermediate, which then decomposes to the acylated product. Our predicted activation energies are in fine agreement with the observed reaction rates. An alternative approach, which uses the tetrahedral intermediate as the transition state mimic, provides satisfactory predictions.

KW - Density functional theory

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KW - Transesterification

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Theoretical study on the mechanism of N-heterocyclic carbene catalyzed transesterification reactions

Abstract

Keywords

ASJC Scopus subject areas

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