Short Enantioselective Total Syntheses of Cheloviolenes A and B and Dendrillolide C via Convergent Fragment Coupling Using a Tertiary Carbon Radical
Short Enantioselective Total Syntheses of Cheloviolenes A and B and Dendrillolide C via Convergent Fragment Coupling Using a Tertiary Carbon Radical
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DOI：
10.1021/acs.joc.7b02458
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发表时间：
2018-07-06
影响因子：
3.6
通讯作者：
Oyerman, Larry E.
中科院分区：
文献类型：
--
作者：
Garnsey, Michelle R.;Slutskyy, Yuriy;Oyerman, Larry E.
描述了用于对映选择性全合成一组重排海绵二萜类化合物的会聚片段偶联策略的开发，这些二萜类化合物含有顺式-2,8-二氧杂双环[3.3.0]辛烷-3-酮单元。关键的键断裂依赖于叔碳自由基和缺电子烯烃之间的后期片段偶联，以立体选择性和有效的方式结合两个环系统并形成两个新的立体中心，其中一个是四元的。该策略适用于三种重排海绵二萜类化合物、螯紫烯 A 和 B 以及树突内酯 C 的可扩展 14-15 步合成。
The development of a convergent fragment coupling strategy for the enantioselective total syntheses of a group of rearranged spongian diterpenoids that harbor the cis-2,8-dioxabicyclo[3.3.0]octan-3-one unit is described. The key bond disconnection relies on a late-stage fragment coupling between a tertiary carbon radical and an electron-deficient alkene to unite two ring systems and form two new stereocenters, one of which is quaternary, in a stereoselective and efficient manner. This strategy is applied toward scalable 14-15 step syntheses of three rearranged spongian diterpenoids, cheloviolenes A and B, and dendrillolide C.