Oxygen‐Controlled Catalysis by Vitamin B 12 ‐TiO 2 : Formation of Esters and Amides from Trichlorinated Organic Compounds by Photoirradiation

An oxygen switch in catalysis of the cobalamin derivative (B 12 )‐TiO 2 hybrid catalyst for the dechlorination of trichlorinated organic compounds has been developed. The covalently bound B 12 on the TiO 2 surface transformed trichlorinated organic compounds into an ester and amide by UV light irradiation under mild conditions (in air at room temperature), while dichlorostilbenes ( E and Z forms) were formed in nitrogen from benzotrichloride. A benzoyl chloride was formed as an intermediate of the ester and amide, which was detected by GC‐MS. The substrate scope of the synthetic strategy is demonstrated with a range of various trichlorinated organic compounds. A photo‐duet reaction utilizing the hole and conduction band electron of TiO 2 in B 12 ‐TiO 2 for the amide formation was also developed.