Abstract
Recent applications of theoretical and physical approaches to the elucidation of acyl-transfer mechanisms have led to further clarifications of structures of intermediates and transition states involved in the stepwise reaction paths. Gas-phase acyl-transfer reactions, both experimental and theoretical, are surveyed, in which factors conductive to the stepwise path are discussed. Aminolysis reactions of carbonyl and thiocarbonyl esters in solution are reviewed with special emphasis of transition state variation with substituents in the nucleophile, acyl and leaving groups applying Marcus theory, Bell-Evans-Palanyi principle, principle of microscopic reversibility, DFTFukui function, reactivity-selectivity principle, natural bond orbital analysis and More OFerrall-Jencks diagram etc. The use of cross-interaction constants as a mechanistic tool is stressed.
Keywords: acyl-transfer reactions, bond orbital analysis, cross-interaction constants, mechanistic tool
Current Organic Chemistry
Title: Theoretical and Physical Aspects of Stepwise Mechanisms in Acyl-Transfer Reactions
Volume: 8 Issue: 7
Author(s): Ikchoon Lee and Dae Dong Sung
Affiliation:
Keywords: acyl-transfer reactions, bond orbital analysis, cross-interaction constants, mechanistic tool
Abstract: Recent applications of theoretical and physical approaches to the elucidation of acyl-transfer mechanisms have led to further clarifications of structures of intermediates and transition states involved in the stepwise reaction paths. Gas-phase acyl-transfer reactions, both experimental and theoretical, are surveyed, in which factors conductive to the stepwise path are discussed. Aminolysis reactions of carbonyl and thiocarbonyl esters in solution are reviewed with special emphasis of transition state variation with substituents in the nucleophile, acyl and leaving groups applying Marcus theory, Bell-Evans-Palanyi principle, principle of microscopic reversibility, DFTFukui function, reactivity-selectivity principle, natural bond orbital analysis and More OFerrall-Jencks diagram etc. The use of cross-interaction constants as a mechanistic tool is stressed.
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Cite this article as:
Lee Ikchoon and Sung Dong Dae, Theoretical and Physical Aspects of Stepwise Mechanisms in Acyl-Transfer Reactions, Current Organic Chemistry 2004; 8 (7) . https://dx.doi.org/10.2174/1385272043370753
DOI https://dx.doi.org/10.2174/1385272043370753 |
Print ISSN 1385-2728 |
Publisher Name Bentham Science Publisher |
Online ISSN 1875-5348 |
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