Copper‐Mediated Cross‐Dehydrogenative Coupling Reaction of Pyrrole and Indole Derivatives with Thiols

Abstract A copper‐mediated C(sp 2 )−H thiolation of pyrrole and indole derivatives with commercially available thiols utilizing a removable monodentate directing group is described. This protocol tolerated a broad range of functional groups and provided the thiolated products in 40 %–97 % yields. Furthermore, the synthetic utility of this protocol was demonstrated by the late‐stage functionalization of bioactive tryptophan peptide. Preliminary mechanistic studies indicated that a Cu(II)/Cu(III) reaction model is most likely to be involved in this C−H thiolation.