title: First enantiospecific total synthesis of the important biogenetic intermediates, (+)-polyneuridine and (+)-polyneuridine aldehyde, as well as 16-epi-vellosimine and macusine A.
abstract: The first enantiospecific total synthesis of the alkaloids 16-epi-vellosimine (1), (+)-polyneuridine (2), (+)-polyneuridine aldehyde (3), and macusine A (4) is reported. The key oxidation was accomplished with the Corey-Kim reagent to provide the important biogenetic intermediates, 16-epi-vellosimine (1) and polyneuridine aldehyde (3), the latter of which is required for the conversion of the sarpagan skeleton into the ajmalan system in the biosynthesis of quebrachidine. [reaction: see text].
authors.affiliation: Department of Chemistry & Biochemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, USA.
authors.forename: Wenyuan
authors.initials: W
authors.lastname: Yin
authors.forename: Jun
authors.initials: J
authors.lastname: Ma
authors.forename: Felix M
authors.initials: FM
authors.lastname: Rivas
authors.forename: James M
authors.initials: JM
authors.lastname: Cook
mesh_terms: D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry; D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D026121:Indole Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: C518016:16-epi-vellosimine; D000447:Aldehydes; D000470:Alkaloids; D026121:Indole Alkaloids; C518014:polyneuridine; C518013:polyneuridine aldehyde; C518015:macusine A