Maeta Naoya, Kamiya Hidehiro, Okada Yohei
Department of Chemical Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588, Japan.
J Org Chem. 2020 May 15;85(10):6551-6566. doi: 10.1021/acs.joc.0c00544. Epub 2020 Apr 9.
Radical cation vinylcyclopropane rearrangements by TiO 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.
描述了在高氯酸锂/硝基甲烷溶液中通过TiO光催化进行的自由基阳离子乙烯基环丙烷重排反应。这些反应由氧化单电子转移引发，随后环丙烷立即开环，生成独特的反应性中间体——张力自由基阳离子。该方法也可应用于乙烯基环丁烷，从而构建六元环。基于初步的机理研究提出了一种通过张力自由基阳离子的逐步机理，密度泛函理论计算支持了这一机理。
