title: A multitasking vanadium-dependent chloroperoxidase as an inspiration for the chemical synthesis of the merochlorins.
abstract: The vanadium-dependent chloroperoxidase Mcl24 was discovered to mediate a complex series of unprecedented transformations in the biosynthesis of the merochlorin meroterpenoid antibiotics. In particular, a site-selective naphthol chlorination is followed by an oxidative dearomatization/terpene cyclization sequence to build up the stereochemically complex carbon framework of the merochlorins in one step. Inspired by the enzyme reactivity, a chemical chlorination protocol paralleling the biocatalytic process was developed. These chemical studies led to the identification of previously overlooked merochlorin natural products.
authors.affiliation: Center for Marine Biotechnology and Biomedicine, Scripps Institution of Oceanography, University of California San Diego, La Jolla, CA 92093 (USA) http://scrippsscholars.ucsd.edu/bsmoore.
authors.forename: Stefan
authors.initials: S
authors.lastname: Diethelm
authors.forename: Robin
authors.initials: R
authors.lastname: Teufel
authors.forename: Leonard
authors.initials: L
authors.lastname: Kaysser
authors.forename: Bradley S
authors.initials: BS
authors.lastname: Moore
mesh_terms: D055162:Biocatalysis; D002711:Chloride Peroxidase / Q000378:metabolism*; D003500:Cyclization; D010084:Oxidation-Reduction; D054830:Sesterterpenes / Q000096:biosynthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D054830:Sesterterpenes; C573231:merochlorin A; C576411:merochlorin B; C418625:vanadium chloroperoxidase; D002711:Chloride Peroxidase
keywords: biomimetic synthesis; chlorine; enzymes; oxidation; vanadium