Org Lett. 2019 Aug 2;21(15):5952-5956. doi: 10.1021/acs.orglett.9b02075. Epub 2019 Jul 23.
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.
从一种已知的手性纯环氧化物出发，通过 16 步最长线性序列，首次实现了大环内酯单胞菌素 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配合物，随后是意想不到的区域选择性水合反应。不对称全合成导致 C10' 构型的修订，并重新分配了天然产物的绝对构型。
