title: Total synthesis of optically active lycopladine A by utilizing diastereoselective protection of carbonyl group in a 1,3-cyclohexanedione derivative.
abstract: We successfully synthesized two enantiomers of bicyclic enones, (7R,7aR)- and (7S,7aS)-9, from the hemiacetal 2a, which we first synthesized from the symmetrical diketone 1a via diastereoselective carbon-oxygen bond formation between one of the carbonyl groups and the chiral alcohol on the C2 side chain in a 2,2-disubstituted 1,3-cycloalkanedione derivative. We also report the total synthesis of natural (+)-lycopladine A [(+)-6] from (7R,7aR)-9 and the formal synthesis of unnatural (-)-lycopladine A [(-)-6] from (7S,7aS)-9.
authors.affiliation: Graduate School of Pharmaceutical Sciences, Tohoku University, Aoba-ku, Sendai, Japan. hiroya@mail.pharm.tohoku.ac.jp
authors.forename: Kou
authors.initials: K
authors.lastname: Hiroya
authors.forename: Yoshihiro
authors.initials: Y
authors.lastname: Suwa
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Ichihashi
authors.forename: Kiyofumi
authors.initials: K
authors.lastname: Inamoto
authors.forename: Takayuki
authors.initials: T
authors.lastname: Doi
mesh_terms: D003512:Cyclohexanones / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D055620:Optical Phenomena; D012717:Sesquiterpenes / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D003512:Cyclohexanones; D007659:Ketones; D012717:Sesquiterpenes; C520065:lycopladine A; C004636:1,3-cyclohexanedione