title: New insights into the mechanism and an expanded scope of the Fe(III)-mediated vinblastine coupling reaction.
abstract: A definition of the scope of aromatic substrates that participate with catharanthine in an Fe(III)-mediated coupling reaction, an examination of the key structural features of catharanthine required for participation in the reaction, and the development of a generalized indole functionalization reaction that bears little structural relationship to catharanthine itself are detailed. In addition to providing insights into the mechanism of the Fe(III)-mediated coupling reaction of catharanthine with vindoline suggesting the reaction conducted in acidic aqueous buffer may be radical mediated, the studies provide new opportunities for the preparation of previously inaccessible vinblastine analogs and define powerful new methodology for the synthesis of indole-containing natural and unnatural products.
authors.affiliation: Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
authors.forename: Hiroaki
authors.initials: H
authors.lastname: Gotoh
authors.forename: Justin E
authors.initials: JE
authors.lastname: Sears
authors.forename: Albert
authors.initials: A
authors.lastname: Eschenmoser
authors.forename: Dale L
authors.initials: DL
authors.lastname: Boger
mesh_terms: D005290:Ferric Compounds / Q000737:chemistry*; D015394:Molecular Structure; D014747:Vinblastine / Q000737:chemistry*; D014748:Vinca Alkaloids / Q000737:chemistry
chemical_list: D005290:Ferric Compounds; D014748:Vinca Alkaloids; D014747:Vinblastine; C017836:catharanthine