Catalytic Asymmetric Total Synthesis of (−)-Galanthamine and (−)-Lycoramine†
Lei Li
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191 (China)
These authors contributed equally to this work.
Search for more papers by this authorQiao Yang
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191 (China)
These authors contributed equally to this work.
Search for more papers by this authorDr. Yuan Wang
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191 (China)
Search for more papers by this authorCorresponding Author
Prof. Yanxing Jia
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191 (China)
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191 (China)Search for more papers by this authorLei Li
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191 (China)
These authors contributed equally to this work.
Search for more papers by this authorQiao Yang
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191 (China)
These authors contributed equally to this work.
Search for more papers by this authorDr. Yuan Wang
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191 (China)
Search for more papers by this authorCorresponding Author
Prof. Yanxing Jia
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191 (China)
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191 (China)Search for more papers by this authorWe are grateful to the National Natural Science Foundation of China (Nos. 21402003, and 21290183) for their financial support.
Graphical Abstract
How gallant: The catalytic asymmetric total synthesis of both (−)-galanthamine and (−)-lycoramine were achieved by using a conceptually new strategy. Two metal-catalyzed reactions were used as the key steps, and include a palladium-catalyzed intramolecular Larock annulation reaction and enantioselective conjugate addition reaction catalyzed by a ScIII/N,N′-dioxide complex. Boc=tert-butoxycarbonyl, TES=triethylsilyl.
Abstract
The catalytic asymmetric total syntheses of (−)-galanthamine (1) and (−)-lycoramine (2) have been achieved by using a conceptually new strategy featuring two metal-catalyzed reactions as the key steps. A new method for the construction of 3,4-fused benzofurans has been developed through a palladium-catalyzed intramolecular Larock annulation reaction, which was successfully applied to the construction of the ABD tricyclic skeleton of 1 and 2. To achieve the asymmetric synthesis of 1 and 2, a ScIII/N,N′-dioxide complex was used to catalyze the enantioselective conjugate addition of 3-alkyl-substituted benzofuranone to methyl vinyl ketone for the construction of a chiral quaternary carbon center.
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