Unified synthesis of quinone sesquiterpenes based on a radical decarboxylation and quinone addition reaction
Unified synthesis of quinone sesquiterpenes based on a radical decarboxylation and quinone addition reaction
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DOI：
10.1021/ja027517q
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发表时间：
2002-10-16
影响因子：
15
通讯作者：
Theodorakis, EA
中科院分区：
文献类型：
--
作者：
Ling, TT;Poupon, E;Theodorakis, EA
本文描述了几种醌倍半萜的统一合成。该策略的关键是一种新的自由基加成反应，该反应允许完全取代的双环核16连接到单取代的醌10上。加成产物15可以是。进一步官能化，得到在醌单元具有高度氧化的天然产物。醌加成反应的特征在于优异的化学选择性，仅在共轭和未取代的双键处发生，以及区域选择性，强烈地受到位于醌环上的杂原子的共振效应的影响。这些特征已成功地应用于Avarol（1）、Avarone（2）、甲氧基Avarones（4，5）、ilimaquinone（6）和smenospongidine（7）的合成，从而证明了该新方法的合成价值。
A unified synthesis of several quinone sesquiterpenes is described herein. Essential to this strategy is a novel radical addition reaction that permits the attachment of a fully substituted bicyclic core 16 to a variably substituted quinone 10. The addition product 15 can be. further functionalized, giving access to natural products with a high degree of oxygenation at the quinone unit. The quinone addition reaction is characterized by excellent chemoselectivity, taking place only at conjugated and unsubstituted double bonds, and regioselectivity, being strongly influenced by the resonance effect of heteroatoms located on the quinone ring. These features were successfully applied to the synthesis of avarol (1), avarone (2), methoxyavarones (4, 5), ilimaquinone (6), and smenospongidine (7), thereby demonstating the synthetic value of this new method.