Photocatalyzed oxidative cleavage of alkenes using CO₂ as an oxygen donor.

Abstract

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 (CO₂) 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 CO₂ under photocatalytic conditions, offering a sustainable platform for light-driven oxidative transformations.