Methanol is a potential hydrogen source and C1 synthon, which finds interesting applications in both chemical synthesis and energy technologies. The effective utilization of this simple alcohol in organic synthesis is of central importance and attracts scientific interest. Herein, we report a clean and cost‐competitive method with the use of methanol as both C1 synthon and H2 source for selective N‐methylation of amines by employing relatively cheap RuCl3.xH2O as a ligand‐free catalyst. This readily available catalyst tolerates various amines comprising electron‐deficient and electron‐donating groups and allows them to transform into corresponding N‐methylated products in moderate to excellent yields. In addition, few marketed pharmaceutical agents (e. g., venlafaxine and imipramine) were also successfully synthesized via late‐stage functionalization from readily available feedstock chemicals, highlighting synthetic value of this advanced N‐methylation reaction. Using this platform, we also attempted tandem reactions with selected nitroarenes to convert them into corresponding N‐methylated amines using MeOH under H2‐free conditions including transfer hydrogenation of nitroarenes‐to‐anilines and prepared drug molecules (e. g., benzocaine and butamben) as well as key pharmaceutical intermediates. We further enable one‐shot selective and green syntheses of 1‐methylbenzimidazole using ortho‐phenylenediamine (OPDA) and methanol as coupling partners.

Synthesis of ammonia via electrochemical reduction of nitrate is one of the most sustainable routes both for environmental protection as well as energy saving initiatives. However, this process is limited to the development of high-performance free-standing catalytic electrodes with improved selectivity and Faradaic efficiency. Herein, we report theory-guided designing and fabrication of free-standing non-noble metal (Mn, Fe, and Co)-doped copper oxide (CuO) electrodes by using a simple and scalable electrode preparation method. The density functional theory (DFT)-based calculations show that the doped-Co sites in the Cu surface facilitate the generation and supply of H+ to the adsorbed NO3 – during the reduction process; as a result, the Co–CuO catalyst displays higher selectivity toward nitrate reduction. The Co-doped Cu electrode (Co–CuO) delivers a higher NH3 yield (5492 μg cm–2) at a reduction potential of −0.91 V vs RHE while maintaining a Faradaic efficiency of >95%. The alloying of Co to the copper metal not only facilitates the proton donation to the adsorbed reactant (NO3 –) but also tunes the Cu d-center, resulting in the active site modulation responsible for the activation of catalysts.