Radical-Cation Vinylcyclopropane Rearrangements by TiO<sub>2</sub> Photocatalysis
Naoya Maeta, Hidehiro Kamiya, Yohei Okada
Abstract
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.
Topics & Concepts
NitromethanePhotocatalysisChemistryRadical ionPhotochemistryDensity functional theoryComputational chemistryOrganic chemistryIonCatalysisRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsSulfur-Based Synthesis Techniques