Synthesis of resveratrol tetramers via a stereoconvergent radical equilibrium.
Synthesis of resveratrol tetramers via a stereoconvergent radical equilibrium.
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DOI：
10.1126/science.aaj1597
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发表时间：
2016-12-09
期刊：
影响因子：
--
通讯作者：
Stephenson CR
中科院分区：
文献类型：
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作者：
Keylor MH;Matsuura BS;Griesser M;Chauvin JR;Harding RA;Kirillova MS;Zhu X;Fischer OJ;Pratt DA;Stephenson CR
在活性自由基聚合合成有机材料中，持久性自由基已成为不可缺少的一部分。然而，它们用于合成小分子的例子很少。在这篇文章中，我们报道了持续自由基和苯二酚甲醚中间体在白藜芦醇四聚体nepalensinol B和vateriaphenol C的合成中的应用。异常弱的碳-碳键的自发断裂和重建使得外消旋物质能够进行立体收敛的氧化二聚反应，这种转化可能与这些天然产物的生物发生相一致。白藜芦醇高阶低聚物的有效合成将促进阐明其作用机制所需的生物学研究(S)。
Persistent free radicals have become indispensable in the synthesis of organic materials by living radical polymerization. However, examples of their use in the synthesis of small molecules are rare. Herein, we report the application of persistent radical and quinone methide intermediates to the synthesis of the resveratrol tetramers nepalensinol B and vateriaphenol C. The spontaneous cleavage and reconstitution of exceptionally weak carbon-carbon bonds has enabled a stereoconvergent oxidative dimerization of racemic materials in a transformation that likely coincides with the biogenesis of these natural products. The efficient synthesis of higher-order oligomers of resveratrol will facilitate the biological studies necessary to elucidate their mechanism(s) of action.