Glycine-selective α-carbon-nitrogen bond cleavage of dipeptides by nickel peroxide

Abstract

Nickel peroxide selectively cleaves the α-carbon-nitrogen bond of glycine residues in dipeptide derivatives to give the corresponding amides. The glycine selectivity is attributable to preferential complexation of the reactant residue to nickel peroxide and subsequent reaction via a stable α-centred glycyl radical. The oxidation process serves as a chemical model for peptidylglycine α-amidating monooxygenase (PAM) and, in addition, may have potential for the synthesis of α,β-didehydro amino acid residues within peptides.