The carbon tetrabromide mediated oxidative carbon-nitrogen bond formation of 2-aminopyridines or 2-aminopyrimidines with β-keto esters or 1,3-diones, leading to a variety of complex imidazo[1,2-α]pyridines or imidazo[1,2-α]pyrimidines, is reported. The reactions were realized under mild and metal-free conditions.