An efficient catalytic system for the alkylation of amines with either alcohols or amines under mild conditions has been developed, using cyclometallated iridium complexes as catalysts. The method has broad substrate scope, allowing for the synthesis of a diverse range of secondary and tertiary amines with good to excellent yields. By controlling the ratio of substrates, both mono- and bis-alkylated amines can be obtained with high selectivity. In particular, methanol can be used as the alkylating reagent, affording N-methylated products selectively. A strong solvent effect is observed for the reaction.

Aryl radicals, generated by Ru‐catalyzed photolytic cleavage of diaryliodonium salt, undergo efficient coupling with arenes and hetarenes to afford a wide range of biaryls.

Aryl radicals produced by irradiation of diaryliodonium salts with visible light under the catalysis of [Ru(bpy) 3 ] 2+ undergo coupling with a wide range of arenes and heteroarenes, affording various biaryls through direct C-H arylation at room temperature.

Conditions. -Aryl amines and aryldiamines as well as primary and secondary acyclic and cyclic amines are N-alkylated with benzylic, primary and secondary alkyl alcohols including methanol. Adjustment of the amount of alcohol used allows for the selective mono or dialkylation, respectively. The new method can also be applied in the cross--coupling of amines. The utility of the method is also demonstrated in the synthesis of pharmacologically relevant Piribedil (XXI) which is employed in the treatment of Parkinson's disease. -(ZOU, Q.; WANG, C.; SMITH, J.; XUE, D.; XIAO*, J.; Chem. -Eur. J. 21 (2015) 27, 9656-9661, http://dx.