Reactions of Oximate α-Nucleophiles with Esters: Evidence from Solvation Effects for Substantial Decoupling of Desolvation and Bond Formation
- 1 July 2002
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (30) , 8766-8767
- https://doi.org/10.1021/ja020379k
Abstract
This communication is concerned with deviations from linearity in Brønsted-type nucleophilicity plots as indicators of changes in transition-state structures, in particular as related to solvational effects. Increasing dimethyl sulfoxide (DMSO) content of DMSO-water mixtures removes the leveling off observed in Brønsted type plots of the reaction of p-nitrophenylacetate (PNPA) with oximate alpha-nucleophiles. This is interpreted as due to virtually complete decoupling between desolvation of the oxyanion nucleophile and bond formation in the rate-determining transition state (solvational imbalance).Keywords
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