Hydroarylation of Arenes via Reductive Radical-Polar Crossover
Autumn R. Flynn, Kelly A. McDaniel, Meredith E. Hughes, David B. Vogt, Nathan T. Jui
Abstract
A photocatalytic system for the dearomative hydroarylation of benzene derivatives has been developed. Using a combination of an organic photoredox catalyst and an amine reductant, this process operates through a reductive radical-polar crossover mechanism where aryl halide reduction triggers a regioselective radical cyclization event, followed by anion formation and quenching to produce a range of complex spirocyclic cyclohexadienes. This light-driven protocol functions at room temperature in a green solvent system (aq. MeCN) without the need for precious metal-based catalysts or reagents or the generation of stoichiometric metal byproducts.
Topics & Concepts
ChemistryCatalysisReagentPhotochemistryReductive eliminationBenzenePhotocatalysisRegioselectivityHalideArylQuenching (fluorescence)StoichiometryAmine gas treatingCombinatorial chemistryRadical ionAryl halideSolventOrganic chemistryIonAlkylQuantum mechanicsPalladiumPhysicsFluorescenceRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsSulfur-Based Synthesis Techniques