ARYLOXYMETHYL RADICAL CYCLIZATIONS MIMICKING BIOLOGICAL C-C BOND FORMATION TO METHOXY GROUPS
ARYLOXYMETHYL RADICAL CYCLIZATIONS MIMICKING BIOLOGICAL C-C BOND FORMATION TO METHOXY GROUPS
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DOI：
10.1039/p19920002313
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发表时间：
1992-09-21
期刊：
影响因子：
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通讯作者：
WHITING, DA
中科院分区：
文献类型：
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作者：
AHMADJUNAN, SA;WALKINGTON, AJ;WHITING, DA
提请注意的是一小群不同的天然产物，其生物合成是不寻常的，涉及形成O-杂环的C-C键形成芳族甲氧基，在净氧化和非氧化过程。研究表明，芳氧乙酸硫代异羟肟酸酯脱羧产生的芳氧甲基自由基会加成到富电子和贫电子的双键上，以5-exo、6-endo和6-exo方式环化，并且还取代区域选择性进入吡啶核，从而模拟生化过程，并形成一种有用的O-杂环合成新方法。生物合成机制进行了简要讨论。
Attention is drawn to a small group of diverse natural products whose biosynthesis is unusual in involving formation of O-heterocyclic rings by C-C bond formation to aromatic methoxy groups, in net oxidative and non-oxidative processes. It is shown that aryloxymethyl radicals, generated by decarboxylation of thiohydroxamate esters of aryloxyacetic acids, undergo addition to both electron rich and electron poor double bonds, cyclizing in 5-exo, 6-endo and 6-exo fashions, and also substitute regioselectivity into pyridinium nuclei, thus mimicking the biochemical processes, as well as forming a useful new synthetic approach to O-heterocycles. Biosynthetic mechanisms are briefly discussed.