Natural Science Foundation of China [21072161, 21302157]; National Basic Research Program of China (973 Program) [2012CB821600]; Program for Changjiang Scholars and Innovative Research Team in University (PCSIRT); Fundamental Research Funds for the Central Universities ; An efficient and practical method for the construction of 2-aryl- and 2-alkyl-substituted benzothiazoles via a copper-catalyzed redox condensation process between benzothiazoles and aldehydes or benzylic alcohols has been developed. The reaction proceeded under mild reaction conditions using environmentally benign tert-butyl hydroperoxide (TBHP) as the oxidant. A reaction mechanism involving the ring-opening of benzothiazoles initiated by the attack of acyl radical on the thiazole ring and intramolecular condensation is proposed based on the isolation of an anilide disulfide intermediate. (C) 2014 Elsevier Ltd. All rights reserved.