General Strategy for Improving the Quantum Efficiency of Photoredox Hydroamidation Catalysis.

The quantum efficiency in photoredox catalysis is the crucial determinant of energy intensity and, thus, is intrinsically tied to the sustainability of the overall process. Here, we track the formation of different transient species of a catalytic photoredox hydroamidation reaction initiated by the reaction of an Ir(III) photoexcited complex with 2-cyclohexen-1-yl(4-bromophenyl)carbamate. We find that the back reaction between the amidyl radical and Ir(II) photoproducts generated from the quenching reaction leads to a low quantum efficiency of the system. Using transient absorption spectroscopy, all of the rate constants for productive and nonproductive pathways of the catalytic cycle have been determined, enabling us to establish a kinetically competent equilibrium involving the crucial amidyl radical intermediate that minimizes its back reaction with the Ir(II) photoproduct. This strategy of using an off-pathway equilibrium allows us to improve the overall quantum efficiency of the reaction by a factor of 4. Our results highlight the benefits from targeting the back-electron transfer reactions of photoredox catalytic cycles to lead to improved energy efficiency and accordingly improved sustainability and cost benefits of photoredox synthetic methods.