Transition from p Radicals to s Radicals: Substituent-Tuned Cyclization of Hydrazonyl Radicals
Transition from p Radicals to s Radicals: Substituent-Tuned Cyclization of Hydrazonyl Radicals
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DOI：
10.1002/anie.201309918
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发表时间：
2014-03-17
影响因子：
16.6
通讯作者：
Han, Bing
中科院分区：
文献类型：
--
作者：
Duan, Xiao-Yong;Zhou, Neng-Neng;Han, Bing
肼基自由基的电子结构是已知的，然而，它们的σ-电子结构还没有报道。在此，我们表明，容易获得的，-和，-不饱和的N-三氯乙酰基和N-三氟乙酰基腙可以方便地转化为肼基σ自由基，随后在N-1或N-2原子进行5-exo-naphthyl自由基环化，分别形成吡唑啉和甲亚胺亚胺。
Hydrazonyl radicals are known for their -electronic structures; however, their sigma-electronic structures have not been reported as yet. Herein, we show that readily accessible ,- and ,-unsaturated N-trichloroacetyl and N-trifluoroacetyl hydrazones can be conveniently converted into hydrazonyl sigma radicals, which subsequently undergo 5-exo-trig radical cyclization at the N-1 or N-2 atom to form pyrazolines and azomethine imines, respectively.