The first azacyclopentenyl carbinyl radical isomerizations (ACCRI): independent use of steric and electronic (polarization) effects as gating elements.
The first azacyclopentenyl carbinyl radical isomerizations (ACCRI): independent use of steric and electronic (polarization) effects as gating elements.
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第一个氮杂环戊烯基羰基自由基异构化（ACCRI）：独立使用空间和电子（极化）效应作为门控元件。
DOI：
10.1021/ja029426z
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发表时间：
2003
期刊：
影响因子：
--
通讯作者：
Johnston,JeffreyN
中科院分区：
文献类型：
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作者：
Viswanathan,Rajesh;Mutnick,Daniel;Johnston,JeffreyN
氮杂环戊烯基卡宾自由基异构化的第一个例子是在一系列对映体富含2-取代吲哚的化合物中描述的，这是一种在杂环和天然产物化学中广泛存在的亚结构。通过亚胺在芳基自由基环化为甲亚胺氮的过程中对映体浓缩(Ee)的不同损失来鉴定异构化。对环取代基的空间和电子性质的独立修饰揭示了对这些变量的全部敏感性，并最终将这些效应的使用定义为门控元件。文中还给出了1，4-氨基转移通过异构化机理实现的例子。标题异构化与已在化学和生物环境中研究过的氮杂环丙基卡宾自由基异构化进行了类比。
The first examples of the azacyclopentenyl carbinyl radical isomerization are described within a series of enantiomerically enriched 2-substituted indolines, a substructure found extensively in both heterocyclic and natural product chemistry. The isomerization was identified by the varying loss of enantiomeric enrichment (ee) of imines during aryl radical cyclizations to azomethine nitrogen. Independent modification of the steric and electronic nature of the ring substituents revealed the full spectrum of sensitivity to these variables and ultimately defined the use of these effects as gating elements. An example is also given in which a 1,4-amino group transfer is effected via the isomerization mechanism. Analogies are drawn between the title isomerization and the azacyclopropyl carbinyl radical isomerization that has been studied in both chemical and biological contexts.