Results
Title

B<sub>12</sub>‐Catalyzed Carbonylation of Carbon Tetrahalides: Using a Broad Range of Visible Light to Access Diverse Carbonyl Compounds.

Authors

Shichijo, Keita; Tanaka, Miho; Kametani, Yohei; Shiota, Yoshihito; Fujitsuka, Mamoru; Shimakoshi, Hisashi

Abstract

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.

Subjects

REFLECTANCE spectroscopy; DENSITY functional theory; VISIBLE spectra; VITAMIN B12; ORGANIC synthesis; CARBONYLATION

Publication

Chemistry - A European Journal, 2025, Vol 31, Issue 2, p1

ISSN

0947-6539

Publication type

Academic Journal

DOI

10.1002/chem.202403663