Yuman Qin, Peng Ren, Jun Hu, Suman Pradhan, Thanh Huyen Vuong, Xiufang He, Lulu Alluhaibi, Nils Rockstroh, Susanna Monti, Giovanni Barcaro, Aleksander Jaworski, Piotr Kuśtrowski, Jabor Rabeah, Daniel Hohenberger, Sergey Bagnich, Anna Köhler, Josef Breu, Gianvito Vilé, Matthias Beller, Shoubhik Das
Oxidative cleavage of carbon-carbon double bonds often requires hazardous reagents and demanding conditions. In this study, we report a photocatalytic oxidative cleavage of alkenes using benign carbon dioxide (CO 2 ) as an oxygen donor, producing ketones or carboxylic acids at atmospheric pressure and room temperature. A robust iron-based heterogeneous photocatalyst facilitates oxygen transfer to form an epoxide intermediate that subsequently undergoes ring opening and carbon-carbon bond cleavage to yield the oxidative products with high selectivity. Comprehensive mechanistic studies combine time-resolved spectroscopy, isotope labeling, and in situ spectroscopic analyses with advanced quantum mechanical simulations. These results uncover fundamental principles of oxygen transfer from CO 2 under photocatalytic conditions, offering a sustainable platform for light-driven oxidative transformations.