Catalytic epoxypolyene cyclization via radicals:: Highly diastereoselective formal synthesis of puupehedione and 8-epi-puupehedione
Catalytic epoxypolyene cyclization via radicals:: Highly diastereoselective formal synthesis of puupehedione and 8-epi-puupehedione
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DOI：
10.1055/s-2006-933139
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发表时间：
2006-04-04
期刊：
影响因子：
2
通讯作者：
Justicia, J
中科院分区：
文献类型：
--
作者：
Gansäuer, A;Rosales, A;Justicia, J
本文描述了一种催化和高立体选择性地合成海洋天然产物普培二酮(1)及其生物活性更高的8-同分异构体的通用构筑单元的方法。我们的方法以铜催化的环氧法尼醇乙酸酯的烯丙基取代反应和钛茂催化的通过自由基的环氧多烯的非对映选择性环化反应为特征。1和2的正式合成是通过对所需的苯并二氢吡喃单元进行高度非对映选择性的环封闭来完成的。
A catalytic and highly stereoselective synthesis of a common building block for the marine natural product puupehedione (1) and its biologically more active 8-epimer is described. Our approach features a copper-catalyzed allylic substitution reaction of epoxyfarnesyl acetate and a diastereoselective titanocene-catalyzed epoxypolyene cyclization via radicals. The formal syntheses of 1 and 2 are completed by highly diastereoselective ring closures to the required benzodihydropyran units.