Catalytic Homogeneous Hydrogenation of CO to Methanol via Formamide

A novel amine-assisted route for low temperature homogeneous hydrogenation of CO to methanol is described. The reaction proceeds through the formation of formamide intermediates. The first amine carbonylation part is catalyzed by K3PO4. Subsequently, the formamides are hydrogenated in situ to methanol in the presence of a commercially available ruthenium pincer complex as a catalyst. Under optimized reaction conditions, CO (up to 10 bar) was directly converted to methanol in high yield and selectivity in the presence of H2 (70 bar) and diethylenetriamine. A maximum TON of 539 was achieved using the catalyst Ru-Macho-BH. The high yield, selectivity, and TONs obtained for methanol production at low reaction temperature (145 °C) could make this process an attractive alternative over the traditional high temperature heterogeneous catalysis.