General Access to Concave-Substituted cis -Dioxabicyclo[3.3.0]octanones: Enantioselective Total Syntheses of Macfarlandin C and Dendrillolide A
General Access to Concave-Substituted cis -Dioxabicyclo[3.3.0]octanones: Enantioselective Total Syntheses of Macfarlandin C and Dendrillolide A
复制标题
凹取代顺式二氧杂双环[3.3.0]辛酮的通用方法：Macfarlandin C 和 Dendrillolide A 的对映选择性全合成
DOI：
10.1021/acs.joc.0c02273
复制
发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Overman, Larry E.
中科院分区：
文献类型：
--
作者：
Allred, Tyler K.;Dieskau, André P.;Zhao, Peng;Lackner, Gregory L.;Overman, Larry E.
描述了一种获取含有凹取代顺-2,8-二恶二环[3.3.0]辛烷-3- 1片段的重排海绵二萜家族的策略的演变。该方法涉及到一个叔碳自由基和一个缺电子双键的后期片段偶联，以高保真度形成邻近的四级和三级立体中心。立体选择性Mukaiyama水化反应是随后制备西斯-2,8-二氧杂环[3.3.0]辛烷-3- 1部分的关键步骤。该策略被用于(−)-macfarlandin C和(+)-dendrillolide a的对映选择性全合成。在(−)-macfarlandin C的构建过程中，开发了高效的对映纯四甲基二氢萘的构建。
The evolution of a strategy to access the family of rearranged spongian diterpenoids harboring a concave-substitutedcis-2,8-dioxabicyclo[3.3.0]octan-3-one fragment is described. The approach involves late-stage fragment coupling of a tertiary-carbon radical and an electron-deficient double bond to form vicinal quaternary and tertiary stereocenters with high fidelity. A stereoselective Mukaiyama hydration is the key step in the subsequent elaboration of thecis-2,8-dioxabicyclo[3.3.0]octan-3-one moiety. This strategy was utilized in enantioselective total syntheses of (−)-macfarlandin C and (+)-dendrillolide A. An efficient construction of enantiopure tetramethyloctahydronaphthalenes was developed during the construction of (−)-macfarlandin C.