Radical-Cation Vinylcyclopropane Rearrangements by TiO2 Photocatalysis.,The Journal of Organic Chemistry

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Radical-Cation Vinylcyclopropane Rearrangements by TiO2 Photocatalysis.
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-04-09 , DOI: 10.1021/acs.joc.0c00544
Naoya Maeta ₁ , Hidehiro Kamiya ₁ , Yohei Okada ₁

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Radical cation vinylcyclopropane rearrangements by TiO2 photocatalysis in lithium perchlorate/nitromethane solution are described. The reactions are triggered by oxidative single electron transfer, which is followed by immediate ring-opening of the cyclopropanes to generate distonic radical cations as unique reactive intermediates. This approach can also be applied to vinylcyclobutane, leading to the construction of six-membered rings. A stepwise mechanism via distonic radical cations is proposed based on preliminary mechanistic studies, which is supported by density functional theory calculations.

中文翻译：

TiO2光催化的自由基阳离子乙烯基环丙烷重排。

描述了在高氯酸锂/硝基甲烷溶液中通过TiO2光催化进行的自由基阳离子乙烯基环丙烷重排。该反应由氧化性单电子转移触发，然后环丙烷立即开环以生成作为唯一反应性中间体的二甲苯基阳离子。这种方法也可以应用于乙烯基环丁烷，从而构建六元环。在初步机理研究的基础上，提出了通过二阶自由基阳离子的逐步机理，并得到密度泛函理论计算的支持。

更新日期：2020-04-01

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