Insights into the Mechanism of an Allylic Arylation Reaction via Photoredox-Coupled Hydrogen Atom Transfer

Despite widespread use as a synthetic method, the precise mechanism and kinetics of photoredox coupled hydrogen atom transfer (HAT) reactions remain poorly understood. This results from a lack of detailed kinetic information as well as the identification of side reactions and products. In this report, a mechanistic study of a prototypical tandem photoredox/HAT reaction coupling cyclohexene and 1,4-dicyanobenzene (DCB) using an Ir(ppy)(3) photocatalyst and thiol HAT catalyst is reported. Through a combination of electrochemical, photochemical, and spectroscopic measurements, key unproductive pathways and side products are identified and rate constants for the main chemical steps are extracted. The reaction quantum yield was found to decline rapidly over the course of the reaction. An unreported cyanohydrin side product was identified and thought to play a key role as a proton acceptor in the reaction. Transient absorption spectroscopy (TAS) and quantum chemical calculations suggested a reaction mechanism that involves radical addition of the nucleophilic DCB radical anion to cyclohexene, with cooperative HAT occurring as the final step to regenerate the alkene. Kinetic modeling of the reaction, using rate constants derived from TAS, demonstrates that the efficiency of the reaction is limited by parasitic absorption and unproductive quenching between excited Ir(ppy)(3) and the cyanohydrin photoproduct.

Automated summary

Despite the widespread use of photoredox coupled hydrogen atom transfer (HAT) reactions, the precise mechanism and kinetics are poorly understood. This report presents a mechanistic study of a prototypical tandem photoredox/HAT reaction coupling cyclohexene and 1,4-dicyanobenzene using an Ir(ppy)(3) photocatalyst and thiol HAT catalyst. Key unproductive pathways and side products were identified, with the reaction efficiency being limited by parasitic absorption and unproductive quenching.