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Mayer, Robert J.; Ofial, Armin R. (2018): Intramolecular Hydrogen-Bonding Modulates the Nucleophilic Reactivity of Ammonium-Peroxycarboxylates. In: European Journal of Organic Chemistry, No. 43: pp. 6010-6017
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Abstract

The ammonium-peroxycarboxylic acid mesylates derived from gamma-aminobutyric acid, beta-alanine, and beta-piperidinopropionic acid were synthesized and characterized by spectroscopic methods and X-ray crystallography. To study the nucleophilic reactivities of the corresponding ammonium- and amino-peroxycarboxylates, the kinetics of their reactions with a series of benzhydrylium ions (Ar2CH+) were investigated in alkaline, aqueous solutions at 20 degrees C. Using sequential-mixing stopped-flow UV/Vis photometry, the rates of the reactions of the short-lived nucleophiles with Ar2CH+ were determined and analyzed by the linear free energy relationship lg k = s(N)(N + E) furnishing nucleophilicity parameters (N, s(N)) of the peroxycarboxylates. Quantum chemical calculations indicate that the reactivity of the zwitterionic ammonium-peroxycarboxylates is attenuated by intramolecular N-H center dot center dot center dot O hydrogen bonding.