Studies related to the relative thermodynamic stability of C-terminal peptidyl esters of O-hydroxy thiophenol: Emergence of a doable strategy for non-cysteine ligation applicable to the chemical synthesis of glycopeptides

A pathway has been devised, wherein a phenolic ester of a C-terminal peptide is ligated with an N-terminal peptide through two consecutive acyl migrations. In the first transacylation, the C-terminus is transferred from a phenol to a newly liberated ortho-thiol function. Subsequently, the acyl group is transported to a proximal benzylamine through a six-membered transition state. Copyright © 2006 American Chemical Society.