Org Lett. 2020 Aug 21;22(16):6308-6312. doi: 10.1021/acs.orglett.0c02135. Epub 2020 Aug 4.
A convergent approach to assemble the fused BCDE tetracyclic framework of wortmannin is presented. This route features a very challenging Suzuki-Miyaura coupling to prepare the fully functionalized furan intermediate, a Negishi-type acylation to unite the two enantio-enriched fragments, and a subsequent hydrogen-atom-transfer-initiated 6- radical cyclization to install the central cyclohexadienone moiety, which establishes the C10 all-carbon quaternary stereocenter.
本文提出了一种汇聚的方法来构建渥曼青霉素的融合 BCDE 四环骨架。该路线的特点是采用极具挑战性的 Suzuki-Miyaura 偶联反应来制备全功能化的呋喃中间体、Negishi 型酰化反应来连接两个对映体富集的片段，以及随后的氢原子转移引发的 6-自由基环化反应来安装中环己二烯酮部分，从而建立了 C10 全碳季碳立体中心。
