Rapid Ether and Alcohol C-O Bond Hydrogenolysis Catalyzed by Tandem High-Valent Metal Triflate plus Supported Pd Catalysts

The thermodynamically leveraged conversion of ethers and alcohols to saturated hydrocarbons is achieved efficiently with low loadings of homogeneous M(OTf)(n) + heterogeneous Pd tandem catalysts (M = transition metal; OTf = triflate; n = 4). For example, Hf(OTf)(4) mediates rapid endothermic ether reversible arrow alcohol and alcohol reversible arrow alkene equilibria, while Pd/C catalyzes the subsequent, exothermic alkene hydrogenation. The relative C-O cleavage rates scale as 30 degrees > 20 degrees > 1 degrees. The reaction scope extends to efficient conversion of biomass-derived ethers, such as THF derivatives, to the corresponding alkanes.