title: Catalytic enantioselective and divergent total synthesis of (+)-10-oxocylindrocarpidine, (+)-cylindrocarpidine, (-)-N-acetylcylindrocarpinol, and (+)-aspidospermine.
abstract: The catalytic enantioselective and divergent total syntheses of Aspidosperma alkaloids (+)-10-oxocylindrocarpidine 7, (+)-cylindrocarpidine 1, (-)-N-acetylcylindrocarpinol 6, and (+)-aspidospermine 8 have been accomplished in 11 steps from a common precursor (15) on the basis of a highly concise route. The route features three metal-catalyzed reactions, including the key Pd-catalyzed decarboxylative asymmetric allylation of carbazolones developed in our laboratory. Our syntheses, using a combination of C-H activation, enantioselective catalysis, and collective synthesis, represent the first total synthesis of 10-oxocylindrocarpidine and the first asymmetric total synthesis of cylindrocarpidine and N-acetylcylindrocarpinol.
authors.affiliation: Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, School of Chemical Science and Technology, Yunnan University , Kunming 650091, People's Republic of China.
authors.forename: Xiao-Lei
authors.initials: XL
authors.lastname: Shen
authors.forename: Rui-Rui
authors.initials: RR
authors.lastname: Zhao
authors.forename: Ming-Jie
authors.initials: MJ
authors.lastname: Mo
authors.forename: Fang-Zhi
authors.initials: FZ
authors.lastname: Peng
authors.forename: Hong-Bin
authors.initials: HB
authors.lastname: Zhang
authors.forename: Zhi-Hui
authors.initials: ZH
authors.lastname: Shao
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D030009:Aspidosperma / Q000737:chemistry*; D002384:Catalysis; D026121:Indole Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D011804:Quinolines / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: C000592394:10-oxocylindrocarpidine; D000470:Alkaloids; D026121:Indole Alkaloids; C000592396:N-acetylcylindrocarpinol; D011804:Quinolines; C000592395:cylindrocarpidine; C091896:aspidospermine