A major difference between cyanamides and thiocyanates is the philicity of the two heteroatoms. The facile loss of the acidic hydrogen of cyanamides renders the internal nitrogen highly nucleophilic and enables attack to the electrophilic aryne without further activation (Scheme 1).8 Contrary to nitrogen in cyanamides, the sulfur in thiocyanates is rather positively polarized9 and is not able to undergo a nucleophilic attack on the aryne without further activation. Therefore, we tried to combine aryne chemistry10 with a Pd-catalyzed activation of aryl thiocyanates.