Advancing nitrate radical chemistry through electro-assisted photocatalytic cleavage of olefins

The photocatalytic oxidative cleavage of olefins represents a sustainable route to carbonyl compounds under mild conditions and with high atom economy. While in photocatalytic domains nitrate radicals have emerged as effective mediators for this transformation, current methodologies rely on stoichiometric silver ions as sacrificial electron scavengers, a limitation that compromises cost-efficiency and environmental sustainability. In this work, we demonstrate the selective oxidative cleavage of styrene using an electro-assisted photocatalytic (EA@PC) system, wherein an externally applied bias replaces the function of silver, enabling in situ nitrate radical generation without the need for sacrificial reagents. This strategy achieves comparable efficiency to silver-based systems while mitigating their drawbacks, representing a more scalable and environmentally compatible platform for nitrate radical-mediated oxidative transformations and advancing the practical applicability of heterogeneous photocatalysis in synthetic chemistry. A sustainable electro-assisted photocatalytic system is presented for the oxidative cleavage of styrene, leveraging nitrate radicals without relying on sacrificial additives. This approach achieves high efficiency through the synergistic design of nanostructured photoanodes and reactor configuration, offering an example of a viable pathway for green synthesis of carbonyl compounds from olefins.