Modular Design of Pyridine-Based Acyl-Transfer Catalysts

Abstract

Derivatives of 3,4-diaminopyridine have been synthesized and studied as catalysts for acyl-transfer reactions. The design of these catalysts is guided by the stability of their acetyl intermediates as determined through theoretical calculations at the B3LYP/6-311 + G(d,p)//B3LYP/6-31G(d) level of theory. The most promising catalysts have been synthesized through a three- to five-step synthesis starting from 3,4-diaminopyridine. The catalytic activity has been determined for the acylation of 1-ethynylcyclohexanol with acetic anhydride at 23 °C and with isobutyric anhydride at 40 °C. For both reactions, the catalytic activity depends dramatically on the substitution pattern of the diaminopyridines. Best results are obtained with catalysts containing alkyl substituents at both amine nitrogens.

catalysis - nucleophilic pyridines - acylation - alcohols

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