Total synthesis of aculeatin A via double intramolecular oxa-Michael addition of secondary/tertiary alcohols.
Total synthesis of aculeatin A via double intramolecular oxa-Michael addition of secondary/tertiary alcohols.
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DOI：
10.1021/jo4026868
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发表时间：
2014-01
期刊：
影响因子：
--
通讯作者：
Hongliang Yao;Liyan Song;Rongbiao Tong
中科院分区：
文献类型：
--
作者：
Hongliang Yao;Liyan Song;Rongbiao Tong
以已知的炔11为起始原料，通过苯酚氧化脱芳构化、仲/叔醇的双分子内oxa-Michael加成和酮的化学选择性和立体选择性还原，经8-10步反应，以约10%的总收率，以外消旋和对映选择性的方式合成了单一螺环异构体aculeatin A。新的合成策略大大加快了获得有效的抗原动物aculeatin A，6-epi-aculeatin D，及其类似物。
A new synthetic strategy was developed for a concise total synthesis of aculeatin A as a single spiroisomer in both racemic and enantioselective fashions in 8-10 steps with ∼10% overall yield from the known alkyne 11, featuring phenol oxidative dearomatization, double intramolecular oxa-Michael addition of secondary/tertiary alcohols, and chemo- and stereoselective reduction of ketone. The new synthetic strategy greatly expedites the access to the potent antiprotozoal aculeatin A, 6-epi-aculeatin D, and their analogues.