Unexpected medium effect on the mechanism for aminolysis of aryl phenyl carbonates in acetonitrile and H2O: transition-state structure in the catalytic pathway

Abstract

Upward curvature in the kinetic plots of pseudo first-order rate constants (kobsd) vs. [amine] for the aminolysis of aryl phenyl carbonates (5a–5j) in MeCN demonstrates that these reactions proceed via a zwitterionic tetrahedral intermediate (T±) that partitions between catalyzed and uncatalyzed routes to give the products. Yukawa–Tsuno plots for the reactions of 5a–5j with piperidine result in excellent linear correlations with ρY = 4.82 and r = 0.47 for the uncatalyzed reaction versus ρY = 2.21 and r = 0.21 for the catalyzed reaction. Brønsted plots for reactions of 4-(ethoxycarbonyl)-phenyl phenyl carbonate (5f) with a series of cyclic secondary amines exhibit excellent linear correlations with βnuc = 0.87 and 0.58 for the uncatalyzed and catalyzed reactions, respectively. The ΔH‡ and ΔS‡ values are 0.92 kcal/mol and –50.1 cal/mol K, respectively, for the catalyzed reaction of 5f with piperidine. Deuterium kinetic isotope effects found for reactions of 5f with piperidine/deuterated piperidine are 0.84 (uncatalyzed) and 1.42 (catalyzed). Multi-parameter analysis supports a concerted catalytic pathway involving a six-membered cyclic transition state rather than a traditionally accepted stepwise pathway with an anionic intermediate. The current unexpected results, where T± is the essential central intermediate in this aminolysis, contrast with previous calculation studies that deemed T± unstable in gas phase or MeCN.