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Qin, Yuman ; Ren, Peng ; Hu, Jun ; Pradhan, Suman ; Vuong, Thanh Huyen ; He, Xiufang ; Alluhaibi, Lulu ; Rockstroh, Nils ; Monti, Susanna ; Barcaro, Giovanni ; Jaworski, Aleksander ; Kuśtrowski, Piotr ; Rabeah, Jabor ; Hohenberger, Daniel ; Bagnich, Sergey ; Köhler, Anna ; Breu, Josef ; Vilé, Gianvito ; Beller, Matthias ; Das, Shoubhik:
Photocatalyzed oxidative cleavage of alkenes using CO₂ as an oxygen donor.
In: Science.
Bd. 392
(2026)
.
- eaed6068.
ISSN 1095-9203
DOI: https://doi.org/10.1126/science.aed6068
Volltext
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. Slicing through carbon-carbon double bonds is a job for strong oxidants. Typical reagents include ozone and high-valent metal oxides. Carbon dioxide is essentially the thermodynamic opposite of those oxidants and conventionally reacts at the carbon rather than either oxygen. Remarkably, Qin et al. nonetheless found that a heterogeneous iron photocatalyst can break alkenes into ketones and acids using the oxygen from carbon dioxide. Hydrogen donation by chloroform assists the process, which appears to occur through an epoxide intermediate. —Jake S. Yeston