A Metal-Free Amination of Benzoxazoles – The First Example of an Iodide-Catalyzed Oxidative Amination of Heteroarenes

An efficient transition-metal-free amination of benzoxazoles has been developed. With catalytic amounts of tetrabutylammoniumiodide (TBAI), aqueous solutions of H(2)O(2) or TBHP as co-oxidant and under mild reaction conditions, highly desirable 2-aminobenzoxazoles were isolated in excellent yields of up to 93%. First mechanistic experiments indicate the in situ iodination of the secondary amine as the putative mode of activation.