Enantioselective Addition of Remote Alkyl Radicals to Double Bonds by Photocatalytic Proton-Coupled Electron Transfer (PCET) Deconstruction of Unstrained Cycloalkanols
Noelia Salaverri, Benedetta Carli, Sergio Díaz‐Tendero, Leyre Marzo, José Alemán
Abstract
Herein, we report the enantioselective addition of remote alkyl radicals, generated from the ring opening of unstrained cycloalkanols by a proton-coupled electron transfer (PCET) process, to 2-acyl imidazoles previously coordinated to a rhodium-based chiral Lewis acid. High yields and enantioselectivites up to 99% are achieved in 1 h. Mechanistic investigations support the formation of the remote alkyl radical by a PCET process, and theoretical studies explain the observed stereochemistry in the addition step.
Topics & Concepts
ChemistryAlkylEnantioselective synthesisElectron transferProton-coupled electron transferRadicalPhotochemistryPhotocatalysisChiral Lewis acidProtonLewis acids and basesRhodiumRing (chemistry)CatalysisOrganic chemistryQuantum mechanicsPhysicsRadical Photochemical ReactionsCO2 Reduction Techniques and CatalystsCatalytic C–H Functionalization Methods