Activation Parameter Changes as a Mechanistic Tool in Acyl-Transfer Reactions in Solution
Vladislav M. Vlasov
Affiliation: N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Lavrentjev Ave., 9.
Keywords: Acyl-transfer reactions, activation parameters, reaction mechanisms.
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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