Total Syntheses of Bisdehydroneostemoninine and Bisdehydrostemoninine by Catalytic Carbonylative Spirolactonization.

Total Syntheses of Bisdehydroneostemoninine and Bisdehydrostemoninine by Catalytic Carbonylative Spirolactonization.
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DOI:
10.1002/anie.201809114
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发表时间:
2018-11-12
期刊:
Angewandte Chemie (International ed. in English)
影响因子:
--
通讯作者:
Dai M
Dai M
中科院分区:
其他
文献类型:
--
作者:
Ma K;Yin X;Dai M

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The first total syntheses of stemona alkaloids bisdehydroneostemoninine and bisdehydrostemoninine in racemic forms have been achieved. The synthetic strategy features a novel palladium-catalyzed carbonylative spirolactonization of hydroxycyclopropanol 8 to rapidly build the oxaspirolactone moiety and a Lewis acid-promoted tandem Friedel-Crafts cyclization and lactonization of 13 to form the 5-7-5 tricyclic core of the target stemona alkaloids. The first total syntheses of stemona alkaloids bisdehydroneostemoninine and bisdehydrostemoninine were reported. The synthesis features a novel palladium-catalyzed carbonylative spirolactonization to rapidly build their oxaspirolactone moiety and a Lewis acid-promoted tandem Friedel-Crafts cyclization and lactonization to form the 5-7-5 tricyclic core of the target stemona alkaloids.
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