Selective Functionalization of 2-Amino-Azoles with Methanol and Ethanol Using a Pincer-(NHC)Mn(I) Complex

Developing a general approach for the functionalization of coordinating heteroaromatic amines with alcohol is challenging. Here, we designed an efficient protocol using a pincer-NHC carbene-based Mn(I) complex for the selective <i>N</i>-alkylation of 2-aminoazole molecules with ethanol and methanol. This methodology is versatile and applicable to the coupling of a wide range of alcohols, including methanol, ethanol, aryl alcohols, and both acyclic and cyclic aliphatic alcohols, with various 2-aminoazoles, aminopyridine, and aminoquinoline derivatives, to provide diverse monoalkylated compounds in good to excellent yields. The utility of this catalytic protocol was successfully extended by synthesizing several bioactive molecules and the gram-scale synthesis. Various control experiments and density functional theory (DFT) calculations were performed to investigate the reaction pathway.