Formation and Rearrangement of Homoserine Depsipeptides and Depsiproteins in the [alpha]-Ketoacid-Hydroxylamine Ligation with 5-Oxaproline

The primary products of the chemical ligation of [alpha]-ketoacids and 5-oxaproline peptides are esters, rather than the previously reported amides. The depsipeptide product rapidly rearranges to the amide in basic buffers. The formation of esters sheds light on possible mechanisms for the typeII KAHA ligations and opens an avenue for the chemical synthesis of depsiproteins.