Reactions of substituted aspirins with amino acids

Abstract

Acyl transfers are key reactions in biology and in the laboratory. In biological systems they are involved in energy transport, in the assembly of complex molecules and in the mechanisms of efficient action of many hydrolytic enzymes. We report a mechanistic and calculational study of the selective N‐acylation reactions of amino acids by substituted aspirins, under mild conditions, in water at 25 °C. The acetylated amino‐acid products of the reactions were identified by nuclear magnetic resonance, and the reaction steps were studied by density functional theory. Copyright © 2012 John Wiley & Sons, Ltd.

Pivotal role of intramolecular catalysis in the selective acetylation of alkyl amines

“…Although intramolecular catalysis is efficient and frequently observed in enzyme catalysis and in biomimetic models which include the reactions of amides and carboxylic and phosphate esters, it is less explored in synthetic preparations. In this regard, it has been shown that N ‐acetylaminoacids can be conveniently prepared using aspirin as the acetylating agent of amino acids in aqueous medium . Here, we demonstrate that the related 3‐acetoxy‐2‐naphthoic acid (3Ac) can be employed in the selective acetylation of primary amines in ethanol.…”