Asymmetric Total Synthesis of Propindilactone G, Part 2: Enantioselective Construction of the Fully Functionalized BCDE Ring System
Asymmetric Total Synthesis of Propindilactone G, Part 2: Enantioselective Construction of the Fully Functionalized BCDE Ring System
复制标题
Propindilactone G 的不对称全合成，第 2 部分：全功能化 BCDE 环系统的对映选择性构建
DOI：
10.1002/asia.201600130
复制
发表时间：
2016
影响因子：
4.1
通讯作者：
Yang Zhen
中科院分区：
文献类型：
--
作者：
Zhang Jia-Jun;You Lin;Wang Yue-Fan;Li Yuan-He;Liang Xin-Ting;Zhang Bo;Yang Shou-Liang;Su Qi;Chen Jia-Hua;Yang Zhen
报道了丙二内酯G（A）的全功能化BCDE四环体系的对映选择性合成。为了实现这一目标，开发并应用了几种合成方法，包括：1）在Hayashi催化剂存在下的不对称Diels-Alder反应，用于合成光学纯的关键中间体3; 2）分子内Pauson-Khand反应（PKR），用于通过使用TMS取代的乙炔作为底物立体选择性合成在C13位具有全碳手性季中心的BCDE环;以及3）Pd催化的还原氢解，用于立体选择性合成完全官能化的BCDE四环系统。 本文开发的化学提供了对丙二内酯G（A）及其类似物的全合成的更好理解。
The enantioselective synthesis of the fully functionalized BCDE tetracyclic ring system of propindilactone G (A) is reported. Several synthetic methods were developed and applied to achieve this goal, including: 1) an asymmetric Diels–Alder reaction in the presence of Hayashi′s catalyst for the synthesis of optically pure key intermediate3; 2) an intramolecular Pauson–Khand reaction (PKR) for the stereoselective synthesis of the BCDE ring with an all‐carbon chiral quaternary center at the C13 position by using the TMS‐substituted acetylene as the substrate; and 3) Pd‐catalyzed reductive hydrogenolysis for the stereoselective synthesis of the fully functionalized BCDE tetracyclic ring system. The chemistry developed herein provided a greater understanding of the total synthesis propindilactone G (A) and its analogues.