title: Rapid ether and alcohol C-O bond hydrogenolysis catalyzed by tandem high-valent metal triflate + supported Pd catalysts.
abstract: 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 ⇌ alcohol and alcohol ⇌ alkene equilibria, while Pd/C catalyzes the subsequent, exothermic alkene hydrogenation. The relative C-O cleavage rates scale as 3° > 2° > 1°. The reaction scope extends to efficient conversion of biomass-derived ethers, such as THF derivatives, to the corresponding alkanes.
authors.affiliation: Department of Chemistry, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors.forename: Zhi
authors.initials: Z
authors.lastname: Li
authors.forename: Rajeev S
authors.initials: RS
authors.lastname: Assary
authors.forename: Abdurrahman C
authors.initials: AC
authors.lastname: Atesin
authors.forename: Larry A
authors.initials: LA
authors.lastname: Curtiss
authors.forename: Tobin J
authors.initials: TJ
authors.lastname: Marks
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D002384:Catalysis; D003198:Computer Simulation; D004987:Ethers / Q000737:chemistry*; D006865:Hydrogenation; D007854:Lead / Q000737:chemistry; D008698:Mesylates / Q000737:chemistry; D008670:Metals / Q000737:chemistry; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D013997:Time Factors
chemical_list: D000438:Alcohols; D004987:Ethers; D008698:Mesylates; D008670:Metals; D007854:Lead; D010165:Palladium; C012077:trifluoromethanesulfonic acid