Zn(II)-Catalyzed Selective -Alkylation of Amines with Alcohols Using Redox Noninnocent Azo-Aromatic Ligand as Electron and Hydrogen Reservoir.

We report a sustainable and eco-friendly approach for selective -alkylation of various amines by alcohols, catalyzed by a well-defined Zn(II)-catalyst, Zn()Cl (), bearing a tridentate arylazo scaffold. A total of 57 -alkylated amines were prepared in good to excellent yields, out of which 17 examples are new. The Zn(II)-catalyst shows wide functional group tolerance, is compatible with the synthesis of dialkylated amines via double -alkylation of diamines, and produces the precursors in high yields for the marketed drugs tripelennamine and thonzonium bromide in gram-scale reactions. Control reactions and DFT studies indicate that electron transfer events occur at the azo-chromophore throughout the catalytic process, which shuttles between neutral azo, one-electron reduced azo-anion radical, and two-electron reduced hydrazo forms acting both as electron and hydrogen reservoir, enabling the Zn(II)-catalyst for -alkylation reaction.