Production of Alcohols from Olefins via One-Pot Tandem Hydroformylation–Acetalization–Hydrogenolysis over Bifunctional Catalyst Merging Ru^III–P Complex and Ru^III Lewis Acid

A novel three-step tandem hydroformylation–acetalization–hydrogenolysis was first proposed to produce alcohols (derivatives) from olefins, and the developed unique Ru­(III)-complex [<b>Ru­(III)-L2</b>] ligated by the ionic diphosphine (<b>L2</b>) proved efficient toward this tandem reaction. In <b>Ru­(III)-L2</b>, the strong π-acceptor nature of <b>L2</b> guaranteed Ru-center remaining in +3 valence state without redox reaction. Hence, <b>Ru­(III)-L2</b> was able to behave as a bifunctional catalyst merging Ru^III–P complex and Ru^III Lewis acid, which acted not only as a transition metal catalyst responsible for hydroformylation of olefins and hydrogenolysis of (hemi)­acetals but also as a Ru³⁺ Lewis acid in charge of acetalization of aldehydes [to form (hemi)­acetals]. The easily performed acetalization served as a bridge step to get through the pathway from aldehydes to alcohols instead of the direct hydrogenation