Asymmetric Total Synthesis of (-)-Spirochensilide A, Part 1: Diastereoselective Synthesis of the ABCD Ring and Stereoselective Total Synthesis of 13(R)-Demethyl Spirochensilide A.
Asymmetric Total Synthesis of (-)-Spirochensilide A, Part 1: Diastereoselective Synthesis of the ABCD Ring and Stereoselective Total Synthesis of 13(R)-Demethyl Spirochensilide A.
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(-)-Spirochensilide A 的不对称全合成，第 1 部分：ABCD 环的非对映选择性合成和 13(R)-Demethyl Spirochensilide A 的立体选择性全合成。
DOI：
10.1021/acs.joc.0c02494
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发表时间：
2021-01
期刊：
影响因子：
--
通讯作者：
Zhen Yang
中科院分区：
文献类型：
--
作者：
Xin-Ting Liang;Bao-Chuan Sun;Chang Liu;Yuan-He Li;Nan Zhang;Qian-Qian Xu;Zhong-Chao Zhang;Yi-Xin Han;Jia-Hua Chen;Zhen Yang
描述了螺环甲硅烷酯ABCD环系统的一种简明的非对映选择性结构。该合成的关键步骤是通过半频哪醇重排反应立体选择性地构建带有两个邻位季手性中心的AB环体系和通过Co介导的Pauson-Khand反应形成基于螺环的双环CD环体系。这种化学反应导致了13（R）-去甲基螺环己内酯A的立体选择性合成，为首次不对称全合成（-）-螺环己内酯A铺平了道路。
A concise and diastereoselective construction of the ABCD ring system of spirochensilide A is described. The key steps of this synthesis are a semipinacol rearrangement reaction to stereoselectively construct the AB ring system bearing two vicinal quaternary chiral centers and a Co-mediated Pauson-Khand reaction to form the spiro-based bicyclic CD ring system. This chemistry leads to the stereoselective synthesis of 13(R)-demethyl spirochensilide A, paving the way for the first asymmetric total synthesis of (-)-spirochensilide A.