Visible light-mediated Smiles rearrangements and annulations of non-activated aromatics
Connor A. Lawson, Andrew P. Dominey, Glynn D. Williams, John A. Murphy
Abstract
We report the first examples of radical cation Smiles rearrangements. A series of aryloxy alkylamines underwent spontaneous reaction, with the amino group displacing the ipso-alkoxy group through substitution, at ambient temperature and under photoactivation by visible light in the presence of an acridinium catalyst (5 mol%). The study was extended to 3-(2-methoxyphenyl)propan-1-amine derivatives, which lack an appropriate ipso leaving group. Here, efficient cyclisations resulted in displacement of the methoxy group and formation of tetrahydroquinolines.
Topics & Concepts
ChemistrySmiles rearrangementAlkoxy groupAmine gas treatingGroup (periodic table)CatalysisLeaving groupPhotochemistryMedicinal chemistryVisible spectrumStereochemistryOrganic chemistryAlkylOptoelectronicsPhysicsRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsSulfur-Based Synthesis Techniques