Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, E-12071 Castellón, Spain.
J Org Chem. 2010 Mar 5;75(5):1775-8. doi: 10.1021/jo9027038.
A stereoselective synthesis of the cytotoxic 14-membered macrolide aspergillide A has been performed. The preparation of a cis-2,6-disubstituted tetrahydropyran ring via stereoselective reduction of an intermediate cyclic hemiacetal was one key feature of the synthesis. The macrocyclic lactone ring was created by means of a ring-closing metathesis (RCM), whereby the new C=C bond displayed exclusively the undesired Z configuration. Conversion to the required E configuration was achieved via photochemical isomerization.
已完成具有细胞毒性的 14 元大环内酯 Aspergillide A 的立体选择性合成。通过对中间环状半缩醛进行立体选择性还原制备顺式-2,6-二取代四氢吡喃环是该合成的一个关键特征。通过闭环复分解反应（RCM）形成大环内酯环，其中新的 C=C 键仅呈现不需要的 Z 构型。通过光化学异构化将其转化为所需的 E 构型。
