BF3•OEt2 Catalyzed S-H insertion reactions of α-diazo imidamides and substituted thioureas / thiosemicarbazones / cyclic thioamides were demonstrated to furnish the corresponding S-H insertion products. This method features wide substrate...

A novel synthetic method for the formation of thiazolo[4,5‐b]indol‐2‐amines from α‐diazoimidamides and mono‐substituted thioureas in the presence of a catalytic amount of boron trifluoride etherate and camphorsulfonic acid under mild conditions was demonstrated. This methodology has a wide‐ranging scope of α‐diazoimidamides and mono‐substituted thioureas, amenable for upscaling experiments and further transformation.