DFT Study on the Stereoisomeric Effect of Amino-acid Side Chain on the Formation of Penta-coordinate Phosphorus Carboxylic-phosphoric Mixed Anhydride

摘要

N-phosphorylamino-acids can self-catalyze and self-assemble into polypeptides and polynuleotides under mild condition. Both experimental and theoretical studies have shown that a pentacoordinate phosphorus intermolecular mixed carboxylic-phosphoric anhydride (IMCPA) is formed as the common intermediate in these reactions. In this paper, the mechanism of the formation of stereoisomeric penta-coordinate intermediates through different stereochemical reaction pathway is studied at B3LYP/6-311＋G(d,p) level. The results show that amino-acid side chains have an obvious effect on the stereochemical specificity of the IMCPAs formation from N-phosphorylamino-acids.