Copper-catalyzed cascade click/nucleophilic substitution reaction to access fully substituted triazolyl-organosulfurs

Although Cu(I)-catalyzed electrophilic interrupted click reaction where 5-cuprate-triazole is trapped by various electrophiles in inter- or intramolecular manner has been well-documented, highly reactive electrophiles are still required to avoid the parasitic protonation for electrophilic interrupted click reaction. Herein, we developed a novel cascade click/nucleophilic substitution reaction to access 4-heterofunctionalized fully substituted triazolyl-organosulfurs using thiocyanates as both leaving groups and organosulfur precursors. 33 examples are showed to demonstrate the structural diversity through the synthesis of fully substituted triazolyl-organosulfurs including triazolyl-thiocyanates, triazolyl-sulfinylcyanides, triazolyl-thioethers, triazolyl-thiols and triazolyl-disulfides from internal thiocyanatoalkynes.