Abstract
Recent applications of activation parameters variation approach to the elucidation of acyl-transfer mechanisms have led to further clarifications of structures of intermediates and transition states involved in the concerted and stepwise reaction pathways. Acyltransfer reactions in solution are reviewed with special emphasis of activation parameter variation ΔX‡ (X = H, S, G) with substituents in the nucleophile, acyl and leaving groups applying linear free energy relationships in order to evaluate the resultant δΔX‡ reaction constants. The use of internal enthalpy reaction constant δΔH‡ int as a mechanistic tool is stressed when one of the steps of the acyl-transfer reaction is the single rate-determining step.
Keywords: Acyl-transfer reactions, activation parameters, reaction mechanisms.
Current Organic Chemistry
Title:Activation Parameter Changes as a Mechanistic Tool in Acyl-Transfer Reactions in Solution
Volume: 18 Issue: 9
Author(s): Vladislav M. Vlasov
Affiliation:
Keywords: Acyl-transfer reactions, activation parameters, reaction mechanisms.
Abstract: Recent applications of activation parameters variation approach to the elucidation of acyl-transfer mechanisms have led to further clarifications of structures of intermediates and transition states involved in the concerted and stepwise reaction pathways. Acyltransfer reactions in solution are reviewed with special emphasis of activation parameter variation ΔX‡ (X = H, S, G) with substituents in the nucleophile, acyl and leaving groups applying linear free energy relationships in order to evaluate the resultant δΔX‡ reaction constants. The use of internal enthalpy reaction constant δΔH‡ int as a mechanistic tool is stressed when one of the steps of the acyl-transfer reaction is the single rate-determining step.
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Cite this article as:
Vlasov M. Vladislav, Activation Parameter Changes as a Mechanistic Tool in Acyl-Transfer Reactions in Solution, Current Organic Chemistry 2014; 18 (9) . https://dx.doi.org/10.2174/1385272819666140424234113
DOI https://dx.doi.org/10.2174/1385272819666140424234113 |
Print ISSN 1385-2728 |
Publisher Name Bentham Science Publisher |
Online ISSN 1875-5348 |
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