Vinylcyclopropane-Cyclopentene (VCP-CP) Rearrangement Enabled by Pyridine-Assisted Boronyl Radical Catalysis
Ting Li, Lanfeng Wei, Zhijun Wang, Xinyu Zhang, Jinbo Yang, Yu Wei, Pengfei Li, Liang Xu
Abstract
An unprecedented VCP-CP (vinylcyclopropane-cyclopentene) rearrangement approach has been established herein by virtue of the pyridine-boronyl radical catalyzed intramolecular ring expansions. This metal-free radical pathway harnesses readily available catalysts and unactivated vinylcyclopropane starting materials, providing an array of cyclopentene derivatives chemoselectively under relatively mild conditions. Mechanistic studies support the idea that the boronyl radical engages in the generation of allylic/ketyl radical species, thus inducing the ring opening of cyclopropanes and the following intramolecular cyclization processes.
Topics & Concepts
CyclopenteneChemistryIntramolecular forceAllylic rearrangementRing (chemistry)RadicalPyridineRadical cyclizationKetylCatalysisCombinatorial chemistryMedicinal chemistryStereochemistryOrganic chemistryCatalytic C–H Functionalization MethodsCyclopropane Reaction MechanismsOrganoboron and organosilicon chemistry