Intramolecular Hydrogen-Bonding Modulates the Nucleophilic Reactivity of Ammonium-Peroxycarboxylates

Mayer, Robert J. und Ofial, Armin R. (2018): Intramolecular Hydrogen-Bonding Modulates the Nucleophilic Reactivity of Ammonium-Peroxycarboxylates. In: European Journal of Organic Chemistry, Nr. 43: S. 6010-6017

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.

• Dokumententyp: Zeitschriftenartikel
• Fakultät: Chemie und Pharmazie > Department Chemie
• Themengebiete: 500 Naturwissenschaften und Mathematik > 540 Chemie
• ISSN: 1434-193X
• Sprache: Englisch