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Thiols,as common sulfurating reagents,[1] have numerous drawbacks,such as metal poisoning,unpleasant odor,and apt oxidation,which impede their applications.To overcome these disadvantages,Na2S2O3 has been successfully used for introducing sulfur atom.We show here efficient and mild methods for constructing various C-S[2] bonds under metal-catalyzed or photo-catalyzed conditions.