Visible-light-driven organic synthesis is a green and sustainable method for producing fine chemicals and is highly desirable at both laboratory and industrial scales. In this study, we developed a broad-range (including the red region) visible-light-driven carbonylation of CCl4, CBr4, and CBr3F with nucleophiles, such as amines and alcohols, using a B12-Mg2+/TiO2 hybrid catalyst. Carbonyl molecules such as ureas, carbamates, carbonate esters, and carbamoyl fluorides were synthesized with high selectivity and efficiency under mild conditions. Diffuse reflectance UV-vis spectroscopy, femtosecond time-resolved diffuse reflectance spectroscopy, and density functional theory calculations revealed the reaction mechanism is a combination of SN2 and single-electron transfer. This is a rare example of a low-energy, red-light-driven photocatalysis, which has been a highly desired organic reaction in recent years. We believe that this study provides a general platform to access diverse carbonyl molecules and could promote photocatalytic carbonylation reactions on a pilot scale.
Keywords: Carbonylation; Dual Catalysis; Photocatalyst; Visible Light; Vitamin B12.
© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.