N , N '-Dimethylurea as an efficient ligand for the synthesis of pharma-relevant motifs through Chan-Lam cross-coupling strategy.

,'-Dimethylurea (DMU) is introduced as a ligand to aid the Chan-Lam -arylation of primary amides, amines, and 3-aminophenols with arylboronic acids and its ester derivative as the arylating associate. The developed methodology is catalyzed by Cu and its complexation with DMU brings about efficient synthesis of -arylated anilines, 3-aminophenols, and primary amides in moderate to good yields (50-90%). The [Cu(OAc)(DMU)] complex is synthesized and characterized by single crystal structure elucidation. The catalyst is cheap, free from prior synthesis of a metal complex, provides chemoselectivity towards the -arylation of 3-aminophenols, and is suitable for mono-arylation of primary amides. The synthetic utility of the methodology is tested in the post-modification of two active pharmaceutical ingredients (APIs). The developed catalytic system extends the scope of ,'-dimethylurea as an auxiliary in inexpensive and versatile Cu catalysis.