title: An improved total synthesis of (+)-macroline and alstonerine as well as the formal total synthesis of (-)-talcarpine and (-)-anhydromacrosalhine-methine.
abstract: An intramolecular Pd-catalyzed alpha-vinylation process is described. This cyclization has been employed for the enantiospecific total synthesis of gram quantities of both (+)-macroline 3 and the macroline equivalent 4. This sequence is compared to the enolate-driven cross-coupling process. The intermediate 4 was also converted into (-)-alstonerine 1 via modification of an intramolecular Tsuji-Wacker oxidation. This sequence resulted in an improved total synthesis of (-)-talcarpine 5 and (-)-anhydromacrosalhine-methine 6 as well.
authors.affiliation: Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, USA.
authors.forename: Xuebin
authors.initials: X
authors.lastname: Liao
authors.forename: Hao
authors.initials: H
authors.lastname: Zhou
authors.forename: Jianming
authors.initials: J
authors.lastname: Yu
authors.forename: James M
authors.initials: JM
authors.lastname: Cook
mesh_terms: D026121:Indole Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D013237:Stereoisomerism
chemical_list: D026121:Indole Alkaloids; C510442:alstonerine; C522023:anhydromacrosalhine-methine; C522024:talcarpine