Total Synthesis and Structural Revision of Monocillin VII
Total Synthesis and Structural Revision of Monocillin VII
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DOI：
10.1021/acs.orglett.9b02075
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发表时间：
2019-08-02
期刊：
影响因子：
5.2
通讯作者：
Mohapatra, Debendra K.
中科院分区：
文献类型：
--
作者：
Mallampudi, N. Arjunreddy;Srinivas, Beduru;Mohapatra, Debendra K.
以已知的手性纯环氧化物为起始原料，经16个最长的线性序列，首次实现了大环内酯monocillin VII及其C-10'差向异构体的不对称全合成。本合成突出了大环内酯的形成，涉及在De Brabander条件下的炔-二钴羰基络合物，然后是意想不到的区域选择性水合。不对称全合成导致天然产物C10'构型的修正和绝对构型的重新分配。
The first asymmetric total synthesis of macrolactone monocillin VII and its C-10' epimer was achieved starting from a known chiral pure epoxide in 16 longest linear sequences. The present synthesis highlights the macrolactone formation involving an alkyne-dicobalt carbonyl complex under De Brabander's conditions followed by an unexpected regioselective hydration. The asymmetric total synthesis resulted in the revision of the configuration at C10' and reassignment of the absolute configuration of the natural product.