Department of Chemistry, University of Kansas, Lawrence, Kansas 66045, United States.
J Org Chem. 2011 Jun 3;76(11):4358-70. doi: 10.1021/jo2003506. Epub 2011 Apr 29.
The first synthesis of dolabelide C (1), a cytotoxic marine macrolide, is reported utilizing a phosphate tether-mediated approach. Bicyclic phosphates (S,S,S(P))-5 and (R,R,R(P))-5 serve as the central building blocks for the construction of two major 1,3-anti-diol subunits in 1 through selective cleavage pathways, regioselective olefin reduction, and cross-metathesis. Overall, phosphate-mediated processes provided copious amounts of both major subunits allowing for a detailed RCM macrocyclization study to the 24-membered macrolactone 1.
首次报道了利用磷酸酯键介导的方法合成具有细胞毒性的海洋大环内酯 dolabelide C（1）。双环磷酸酯（S,S,S(P))-5 和 (R,R,R(P))-5 可作为构建 1 中两个主要的 1,3-anti-二醇结构单元的核心构建块，通过选择性裂解途径、区域选择性烯烃还原和交叉复分解反应实现。总之，磷酸酯介导的过程提供了大量的两个主要的结构单元，从而可以对 24 元大环内酯 1 进行详细的 RCM 大环化研究。
