B-Catalyzed Carbonylation of Carbon Tetrahalides: Using a Broad Range of Visible Light to Access Diverse Carbonyl Compounds.

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 CCl, CBr, and CBrF with nucleophiles, such as amines and alcohols, using a B-Mg/TiO 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 S2 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.