Development of a Ruthenium/Phosphite Catalyst System for Domino Hydroformylation–Reduction of Olefins with Carbon Dioxide

An efficient domino ruthenium‐catalyzed reverse water‐gas‐shift (RWGS)‐hydroformylation‐reduction reaction of olefins to alcohols is reported. Key to success is the use of specific bulky phosphite ligands and triruthenium dodecacarbonyl as the catalyst. Compared to the known ruthenium/chloride system, the new catalyst allows for a more efficient hydrohydroxymethylation of terminal and internal olefins with carbon dioxide at lower temperature. Unwanted hydrogenation of the substrate is prevented. Preliminary mechanism investigations uncovered the homogeneous nature of the active catalyst and the influence of the ligand and additive in individual steps of the reaction sequence.