GLYCINE-SELECTIVE ALPHA-CARBON-NITROGEN BOND-CLEAVAGE OF DIPEPTIDES BY NICKEL PEROXIDE

Nickel peroxide selectively cleaves the alpha-carbon-nitrogen bond of glycine residues in dipeptide derivatives to give the corresponding am ides. The glycine selectivity is attributable to preferential complexa tion of the reactant residue to nickel peroxide and subsequent reactio n via a stable alpha-centred glycyl radical. The oxidation process ser ves as a chemical model for peptidylglycine alpha-amidating monooxygen ase (PAM) and, in addition, may have potential for the synthesis of al pha,beta-didehydro amino acid residues within peptides. (C) 1997 Elsev ier Science Ltd.