Hydrogenation of Organic Molecules via Direct Mechanocatalysis

Abstract

Mechanochemical hydrogenation of unsaturated C-C and C-O, as well as N-O and C-X bonds is successfully achieved without the use of solvents, ligands, or catalyst powders via ball milling. A variety of catalysts are electroplated onto the walls of the milling vessel, allowing for simple recycling and reuse of the catalytic material. Hydrogen gas is directly introduced into the milling vessel, eliminating the need for hydrogen donor compounds which contribute to waste production and suboptimal atom economy. This approach enables the quantitative hydrogenation of unsaturated carbon-carbon bonds, achieving near-complete conversion within just 20 minutes at ambient temperature and pressures as low as 1.5 bar. Carbonyls, nitro groups, and organohalides were converted within reaction times of up to 12 hours. Mechanistic investigations suggest the reaction to be following established mechanisms for hydrogenation. Finally, chemoselective hydrogenation of various reducible functional groups was explored, demonstrating the versatility and efficiency of this solvent-free mechanochemical approach with simple catalyst recycling for hydrogenation reactions.