Muséum National d'Histoire Naturelle, Molécules de Communication et Adaptation des Micro-organismes (UMR 7245 CNRS-MNHN), 57 rue Cuvier (CP 54), 75005 Paris, France.
Org Lett. 2012 Mar 2;14(5):1270-3. doi: 10.1021/ol300133x. Epub 2012 Feb 17.
A straightforward asymmetric synthesis of the cage oxygenated structure of (+)-harringtonolide has been accomplished for the first time. The key steps involved (i) a templated stereoselective IMDA reaction to build a highly functionalized cyclohexene ring D, (ii) functionalization of the cycloadduct, (iii) ring-closing metathesis providing the five-membered ring C, and finally (iv) a challenging one-step cascade cyclization of an epoxy-alcohol toward the target structure, whose mechanism was investigated.
首次实现了 (+)-海松醇内酯笼状含氧结构的直截了当的不对称合成。所涉及的关键步骤包括：(i) 模板立体选择性 IMDA 反应构建高度官能化的环己烯环 D，(ii) 环加成物的官能化，(iii) 提供五元环 C 的闭环复分解，最后 (iv) 向目标结构进行具有挑战性的一步级联环化环氧醇，其机制进行了研究。
