Tuning reactivity and chemoselectivity in electron transfer initiated cyclization reactions: Applications to carbon-carbon bond formation
Tuning reactivity and chemoselectivity in electron transfer initiated cyclization reactions: Applications to carbon-carbon bond formation
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DOI：
10.1021/ja029139v
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发表时间：
2003-03-05
影响因子：
15
通讯作者：
Floreancig, PE
中科院分区：
文献类型：
--
作者：
Seiders, JR;Wang, LJ;Floreancig, PE
在这篇通讯中，我们证明了我们的电子转移引发的环化反应的范围可以通过利用同型酶醚的氧化势与其自由基的中解苯碳-碳键离解能之间的关系来显着扩大。通过降低电子载体的氧化电位和苯基碳-碳键离解能，我们可以在温和的非光化学条件下引发反应。芳烃氧化的选择性和温和的反应条件使得各种富电子烯烃作为亲核基团，以优异的效率形成碳-碳键。
In this communication, we demonstrate that the scope of our electron transfer initiated cyclization reaction can be significantly broadened by exploiting the relationship between the oxidation potentials of homobenzylic ethers and the mesolytic benzylic carbon−carbon bond dissociation energies of their radical cations. By lowering the oxidation potential of the electrophore and the benzylic carbon−carbon bond dissociation energy, we can initiate reactions under mild, nonphotochemical conditions. The selectivity of the arene oxidation and the mild reaction conditions allow a variety of electron-rich olefins to serve as nucleophilic groups to form carbon−carbon bonds with excellent efficiency.