1. Anionic Polycyclization Entry to Tricycles Related to Quassinoids and Terpenoids: A Stereocontrolled Total Synthesis of (+)-Cassaine
- Author
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Pierre Deslongchamps, Pierre-Yves Caron, and K. Ravindar
- Subjects
Anions ,Stereochemistry ,Cyclohexane Monoterpenes ,Crystallography, X-Ray ,010402 general chemistry ,01 natural sciences ,chemistry.chemical_compound ,Alkaloids ,Humans ,Biological Products ,Natural product ,Nonsteroidal ,Quassins ,Bicyclic molecule ,Terpenes ,010405 organic chemistry ,Cassaine ,Organic Chemistry ,Total synthesis ,Stereoisomerism ,Combinatorial chemistry ,Terpenoid ,0104 chemical sciences ,chemistry ,Cyclization ,Abietanes ,Monoterpenes ,Quassinoid ,Sodium-Potassium-Exchanging ATPase ,Enone - 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.
- Published
- 2014
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