School of Chemistry, University of Bristol, Bristol, BS8 1TS, United Kingdom.
Org Lett. 2020 Apr 3;22(7):2548-2552. doi: 10.1021/acs.orglett.0c00425. Epub 2020 Mar 16.
A new strategy is described for the direct conversion of unsaturated 3,5-dihydroxy-diarylheptanoids to dimeric products assembled on -2,8-dioxabicyclo[4.4.0]decane frameworks. The key atom-economical acid-mediated coupling creates 2 rings and 4 new stereocenters in a single-pot process. Oxygen-18 labeling studies are in accord with reactions proceeding via a cascade mechanism involving carbocationic intermediates. This approach enabled the concise total syntheses of analogues of the natural product blepharocalyxin D in 4 steps from simple starting materials.
本文描述了一种新策略，可直接将不饱和 3,5-二羟基二芳基庚烷转化为在 -2,8-二氧杂双环[4.4.0]癸烷骨架上组装的二聚产物。关键的原子经济性酸介导偶联在一锅法过程中形成 2 个环和 4 个新的立体中心。氧-18 标记研究与通过涉及碳阳离子中间体的级联机制进行的反应一致。该方法可从简单的起始原料出发，通过 4 步反应简洁地完成天然产物 blepharocalyxin D 的类似物的全合成。
