title: Oxidative 1,2- and 1,3-alkyl shift processes: developments and applications in synthesis.
abstract: Oxidative 1,2- and 1,3- alkyl shifts mediated by a hypervalent iodine reagent were performed on simple and inexpensive phenol derivatives. These transpositions enable rapid redesign of the main aromatic skeleton to generate good yields of highly functionalized scaffolds containing a prochiral dienone system, a quaternary carbon center connected to as many as four sp(2) centers, and a carbonyl functionality or precursor. An efficient enantioselective version of this process resulting in the formation of a challenging quaternary carbon center is also described. The products represent the central cores of several natural products having important bioactivities. As an illustration of the potential of this method, we describe the rapid synthesis of several functionalized polycyclic systems as well as a formal synthesis of acetylaspidoalbidine, a hexacyclic alkaloid belonging to the Aspidosperma family.
authors.affiliation: Laboratoire de Méthodologie et Synthèse de Produits Naturels, Université du Québec à Montréal, C.P. 8888, Succ. Centre-Ville, Montréal, H3C 3P8 Quebec, Canada.
authors.forename: Kimiaka C
authors.initials: KC
authors.lastname: Guérard
authors.forename: Amandine
authors.initials: A
authors.lastname: Guérinot
authors.forename: Cloé
authors.initials: C
authors.lastname: Bouchard-Aubin
authors.forename: Marc-André
authors.initials: MA
authors.lastname: Ménard
authors.forename: Mathieu
authors.initials: M
authors.lastname: Lepage
authors.forename: Marc André
authors.initials: MA
authors.lastname: Beaulieu
authors.forename: Sylvain
authors.initials: S
authors.lastname: Canesi
mesh_terms: D030009:Aspidosperma / Q000737:chemistry; D026121:Indole Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D007455:Iodine / Q000737:chemistry*; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010636:Phenols / Q000737:chemistry*; D011083:Polycyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D026121:Indole Alkaloids; D010636:Phenols; D011083:Polycyclic Compounds; D007455:Iodine