Glutathionein the Biosynthesis of Glutazoline Teredinibactins

Teredinibactins are β-resorcyclic thiazoline dipeptides synthesized by <i>Teredinibacter turnerae</i> T7901, a bacterial symbiont of shipworms in the sea. Through feeding studies, we show that the thiazoline moiety is made from glutathione and its metabolites in a noncanonical pathway, for which we suggest the name “glutazoline”. Mimicking the biosynthetic reaction, we synthesized both natural and unnatural teredinibactins. The results expand the scope of biological and chemical approaches to aromatic azoline conjugates.