Copper-Catalyzed, Ligand-Controlled N(sp)- or N(sp)-Selective Arylation of Cyanamides.

Cyanamides possess both nucleophilic and electrophilic centers, and their arylation reactions are known to proceed at N(sp) and C(sp) sites, leading to -aryl cyanamides or amidines. N(sp) selectivity has also been reported only in the presence of amines, thus leading to guanidines. Herein, we report a general copper-catalyzed ligand-controlled Chan-Lam-Evans arylation of cyanamides proceeding regioselectively at the N(sp) or N(sp) atoms and leading to either -aryl cyanamides or dissymmetric carbodiimides.