Deoxydehydration Of Polyols Research Articles

Interparticle Hydrogen Spillover in Enhanced Catalytic Reactions.

Interparticle hydrogen spillover is the phenomenon of H migration over different catalyst particles, which should be a physical mixture of at least two solid catalysts. In this review, we analyze examples of enhanced catalysis based on interparticle (reverse) hydrogen spillover. Simple physical mixtures of powdered catalysts containing metal catalysts of H2 dissociation/recombination and solid catalysts with active sites for substrate activation significantly enhance catalytic reactions. These reactions include aromatic hydrogenation, CO2 methanation, and the deoxydehydration of polyols, aromatization of lower paraffins, and direct coupling of benzene and alkanes. The acceleration effect and proposed reaction pathway of each example involving interparticle (reverse) hydrogen spillover are summarized. Simple reaction systems comprising physical mixtures of at least two powdery solid catalysts should enable unique catalysis in the future with the aid of interparticle (reverse) hydrogen spillover.

Oxo-Rhenium-Catalyzed Deoxydehydration of Polyols with Hydroaromatic Reductants

Several dihydroaromatic compounds are shown to be effective reducing agents in the oxo-metal-catalyzed deoxydehydration of diols and polyols to produce olefins and the corresponding arenes. NH4ReO4 and MeReO3 are active catalysts for the reactions. The most effective of the hydroaromatic reductants is indoline, which is oxidized to indole. Yields for a variety of diols and polyols range from 35% to 99%. Two hydrogen donors, 1,3-cyclohexadiene and dihydroanthracene, engage in tandem DODH/cycloaddition reactions. Competition experiments show that indoline is more reactive than representative alcohols in H-transfer. Indoline is shown to reduce MeReO3 to MeReO2 via an isolable adduct, MeReO3(indoline) (4), which has been structurally characterized and is suggested to be an intermediate in the catalytic DODH process.

Deoxydehydration of polyols.

The development of sustainable chemical processes for the conversion of highly oxygenated biomass feedstocks to chemical products requires efficient and selective processes for partial oxygen removal and refunctionalization. Here we review the development of the deoxydehydration (DODH) reaction, which converts vicinal diols (glycols) to olefins. Uncatalyzed deoxygenative eliminations were first established. The catalyzed DODH reactions have largely employed oxo-rhenium catalysts and a variety of reductants, including PR₃, dihydrogen, sulfite, and alcohols. A variety of glycol and biomass-derived polyol substrates undergo the DODH reaction in moderate to good efficiency, regioselectively, and stereoselectively. Observations regarding selectivity, mechanistic probes, and computational studies support the general operation of a catalytic process involving three basic stages: glycol condensation to an M-glycolate, reduction of the oxo-metal, glycol condensation to produce a metal-glycolate, and alkene extrusion from the reduced metal-glycolate. Recent practical developments include the discovery of non-precious V- and Mo-oxo DODH catalysis.