English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Zendy Plus

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Zendy Tools

Zendy Open

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.

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