Radical-Mediated Distal Ipso-Migration of O/S-Containing Heteroaryls and DFT Studies for Migratory Aptitude
Huihui Zhang, Luyao Kou, Dong Chen, Meishan Ji, Xiaoguang Bao, Xinxin Wu, Chen Zhu
Abstract
Herein we describe an efficient distal ipso-migration of O- and S-containing heteroaryls and the radical heteroarylation of unactivated alkenes. The migration is triggered by various fluoroalkyl radicals, leading to valuable multifunctionalized ketones. The comparisons of migratory aptitude for O-/S-containing heteroaryls are comprehensively investigated. The origin of the chemoselective migration could be partially attributed to the discrepancy in the energy level of the LUMO of each heteroaryl group.
Topics & Concepts
ChemistryAptitudeRadicalMedicinal chemistryStereochemistryOrganic chemistryPsychologyDevelopmental psychologyRadical Photochemical ReactionsFluorine in Organic ChemistrySulfur-Based Synthesis Techniques