Amit Biswas, Simon Kolb, Swagata Sil, Debashis Manna, Sebastian H. Röttger, Anex Jose, Daniel B. Werz, Swadhin K. Mandal
The valorization of greenhouse gases CO 2 and N 2 O into value-added chemicals has recently become a critical area of research. While the utilization of CO 2 gives quick access to important carboxylic acid building blocks, N 2 O is able to act as an oxygen-transfer reagent that allows the formation of carbon–oxygen and heteroatom–oxygen bonds. No metal-free catalytic system has yet been described that is able to react with both gases. Additionally, the metal-free catalytic activation of N 2 O is unprecedented in the literature. Relying on our previously established multi-PET catalysis that makes use of a BOIMPY dye, we were able to identify a single catalytic platform that allows reactions of both gases under super-reducing photochemical conditions. In this work, we report reactions between either CO 2 or N 2 O and (poly)arenes, aryl halides, olefins, sulfides, and phosphines and present a thorough mechanistic investigation to understand the pathways leading to the described products. We found that N 2 O is indeed catalytically activated by a nonmetal catalyst for the first time employing our system. We mention that the enclosed methodology can be utilized to react with abundant CO 2 or N 2 O; however, it will not mitigate climate change.