title: Anionic polycyclization entry to tricycles related to quassinoids and terpenoids: a stereocontrolled total synthesis of (+)-cassaine.
abstract: A full account of our anionic polycyclization approach to access highly functionalized tricycles related to quassinoids and terpenoids from several optically active bicyclic enone systems and Nazarov reagents is presented. (+)-Carvone is the only chiral source used to fix the entire stereochemistry of all of the tricycles, and the stereochemical outcome of this process was unambiguously determined by X-ray crystallographic analysis. The utility of this strategy was demonstrated by the stereocontrolled construction of advanced tricycles related to the highly potent anticancer natural product bruceantin, a member of quassinoid family, and the total synthesis of the cardioactive terpenoid (+)-cassaine, a nonsteroidal inhibitor of Na(+)-K(+)-ATPase.
authors: Département de Chimie, Faculté des Sciences et de Génie, Pavillon Alexandre-Vachon, Université Laval , 1045 avenue de la Médecine, Québec, Québec G1V 0A6, Canada.
authors: Kontham
authors: K
authors: Ravindar
authors: Pierre-Yves
authors: PY
authors: Caron
authors: Pierre
authors: P
authors: Deslongchamps
mesh_terms: D045784:Abietanes; D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry*; D000838:Anions / Q000737:chemistry*; D001688:Biological Products; D018360:Crystallography, X-Ray; D003500:Cyclization; D000081005:Cyclohexane Monoterpenes; D006801:Humans; D039821:Monoterpenes / Q000737:chemistry*; D036702:Quassins / Q000737:chemistry* / Q000494:pharmacology; D000254:Sodium-Potassium-Exchanging ATPase / Q000037:antagonists & inhibitors / Q000737:chemistry; D013237:Stereoisomerism; D013729:Terpenes / Q000737:chemistry*
chemical_list: D045784:Abietanes; D000470:Alkaloids; D000838:Anions; D001688:Biological Products; D000081005:Cyclohexane Monoterpenes; D039821:Monoterpenes; D036702:Quassins; D013729:Terpenes; C006923:carvone; D000254:Sodium-Potassium-Exchanging ATPase; C010696:cassaine; C002550:bruceantin