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The design of an "H"‐shaped reactor has been studied to satisfy the possibility of using a triphasic medium to transform d‐glucose into 5‐hydroxymethylfurfural (HMF) by a hybrid catalytic process using an immobilized glucose isomerase, allowing the isomerization of D‐glucose to d‐fructose, and a heterogeneous chemical catalyst to catalyze the dehydration of d‐fructose to HMF. The various parameters influencing the transport of d‐fructose within the reactor were studied, namely the difference in pH between the two aqueous phases, the agitation and the quantity of 3,4‐DCPBA/Aliquat336® used to extract and transport continuously the d‐fructose. The pH discrepancy, which must be between 5.0 and 5.5, turns out to be the real driving force behind the extraction of D‐fructose. The D‐Fru/3,4‐DCPBA molar ratio of 1/0.25 allowed the transport of more than 80 % of the D‐fructose initially present and shows that the same molecule of 3,4‐DCPBA is involved at least twice in the transport of D‐fructose and that the 3,4‐DCPBA/Aliquat336® couple performs a turnover within the organic phase. Finally, a HMF production yield of 30.9 % and an isomerization yield of 79.1 % were obtained, illustrating the shift in the isomerization equilibrium made possible by a D‐fructose extraction yield of 96.8 %. [ABSTRACT FROM AUTHOR]

Upon reaction with copper(I), peri-halo naphthyl phosphines readily form peri-bridged naphthyl phosphonium salts. The reaction works with alkyl, aryl and amino substituents at phosphorus, with iodine, bromine and chlorine as a halogen. It proceeds under mild conditions and is quantitative, despite the strain associated with the resulting 4-membered ring structure and the naphthalene framework. The transformation is amenable to catalysis. Under optimized conditions, the peri-iodo naphthyl phosphine 1-I is converted into the corresponding peri-bridged naphthyl phosphonium salt 2b in only 5 minutes at room temperature using 1 mol% of CuI. Based on DFT calculations, the reaction is proposed to involve a Cu(I)/Cu(III) cycle made of P-coordination, C–X oxidative addition and P–C reductive elimination. This copper-catalyzed route gives a general and efficient access to peri-bridged naphthyl phosphonium salts for the first time. Reactivity studies could thus be initiated and the possibility to insert gold into the strained P–C bond was demonstrated. It leads to (P,C)-cyclometallated gold(III) complexes. According to experimental observations and DFT calculations, two mechanistic pathways are operating: (i) direct oxidative addition of the strained P–C bond to gold,(ii) backward-formation of the peri-halo naphthyl phosphine (by C–P oxidative addition to copper followed by C–X reductive elimination), copper to gold exchange and oxidative addition of the C–X bond to gold. Detailed analysis of the reaction profiles computed theoretically gives more insight into the influence of the nature of the solvent and halogen atom, and provides rationale for the very different behaviour of copper and gold in this chemistry. [ABSTRACT FROM AUTHOR]

The mechanism of ring-opening of [epsilon]-caprolactone by methanol catalyzed by trifluoromethane and methane sulfonic acids is analyzed, where the sulfonic acid has behaved as a bifunctional catalyst. The ring-opening has involved the cleavage of the endo C-O bond of the tetrahedral intermediate with concomitant proton transfer, where the sulfonic acid has acted as a proton shuttle via its acidic hydrogen atom and basic oxygen atoms.

Abstract: The peri‐iodo naphthyl phosphine 1 reacts with CuI to give the peri‐bridged phosphonio‐naphthalene 2, which has been fully characterized (multi‐nuclear NMR, MS, XRD). The outcome of the reaction differs markedly from that observed with gold. A two‐step pathway involving P‐assisted C−I oxidative addition to copper, followed by P−C reductive elimination is shown to be energetically feasible by DFT calculations. [ABSTRACT FROM AUTHOR]

A series of Ru-(Mn-M)OX catalysts (M: Al, Ti, Zr, Zn) prepared by co-precipitation were investigated in the hydrogenolysis of xylitol in water to ethylene glycol, propylene glycol and glycerol at 200 °C and 60 bar of H2. The catalyst promoted with Al, Ru-(Mn-Al)OX, showed superior activity (57 h-1) and a high global selectivity to glycols and glycerol of 58% at 80% xylitol conversion. In comparison, the catalyst prepared by loading Ru on (Mn-Al)OX, Ru/(Mn-Al)OX was more active (111 h-1) but less selective (37%) than Ru-(Mn-Al)OX. Characterization of these catalysts by XRD, BET, CO2-TPD, NH3-TPD and TEM showed that Ru/(Mn-Al)OX contained highly dispersed and uniformly distributed Ru particles and fewer basic sites, which favored decarbonylation, epimerization and cascade decarbonylation reactions instead of retro-aldol reactions producing glycols. The hydrothermal stability of Ru-(Mn-Al)OX was improved by decreasing the xylitol/catalyst ratio, which decreased the formation of carboxylic acids and enabled recycling of the catalyst, with a very low deactivation. [ABSTRACT FROM AUTHOR]

The aqueous-phase hydrogenolysis of xylitol into glycols over Ru/C was performed in the presence and absence of a wide range of concentrations of Ca(OH)2 to investigate the reaction pathway. Without base, epimerization and cascade decarbonylation were the predominant reactions with high selectivities to C5 and C4 alditols and light alkanes at full conversion. Glycol production was obtained by the addition of Ca(OH)2 to promote the retro-aldol reaction. It competed with reactions without base and became the main reaction for a OH−/ xylitol molar ratio Rmol(OH/xylitol) of 0.13, and high selectivities to glycols (56 %) and glycerol (16 %) were observed. However, lactate was a byproduct at up to 27 % with a high base amount ( Rmol(OH/xylitol)=0.68). Bifunctional Ru/metal oxide/C catalysts (metal: Zn, Sn, Mn, Sr, W) were synthesized and were able to cleave the C−C bond into glycols without a base promoter. The 3.1 wt %Ru/MnO(4.5 %)/C catalyst was the most active (220 h−1) with reasonable selectivity to glycols (22 %) and glycerol (10 %) and a low production of lactate (<1 %). Nevertheless, metal oxide leaching of the catalyst was observed likely because of the production of traces of lactate. [ABSTRACT FROM AUTHOR]

Through biomass valorization, sugars can become a major carbon resource for the production of fuels and chemicals by using catalysis. Hybrid catalysis, a direct combination of biocatalysis and chemocatalysis, may yield innovative solutions. 5-Hydroxymethylfurfural (5-HMF) is a platform molecule derived from glucose, for which fructose is a key intermediate. To overcome the thermodynamic enzymatic equilibrium between glucose and fructose, two methodologies based on hybrid catalysis are described herein. In the first method, the glucose isomerase and fructose-to-5-HMF dehydration chemocatalysts are simultaneously implemented in a multiphasic way to imply the complexation and transport of fructose. The second method proposes a route through sorbitol, obtained by the hydrogenation of glucose. Sorbitol is then enzymatically converted into fructose, whereas regeneration of the cofactor is performed in situ with an organometallic complex as a chemocatalyst. [ABSTRACT FROM AUTHOR]

Only a few catalytic transformations can be efficiently catalyzed by both homogeneous or heterogeneous technologies, with short olefin oligomerization promoted by a nickel-based catalysts among them. Homogeneous and heterogeneous catalysis are often opposed in terms of activity, active-site description or recyclability, traditionally mentioned as 'homogeneous versus. heterogeneous'. Unlike previous studies, we propose to emphasize the similarities between both catalysis by comparing industrially representative results obtained in continuous flow-mode under similar mild conditions. A detailed analysis of both primary products of olefins oligomerization, and a set of secondary products obtained in experimental assays completed with recently published results of DFT calculations prompted us to postulate a common mechanistic pathway for nickel-catalyzed ethylene oligomerization. Heterogeneous metallic ethylene oligomerization, for which nickel active sites identification has indeed long been under debate, seems to follow the Cossee-Arlman mechanism, well accepted as major mechanism in the homogeneous counterpart. This analysis allowed us to design an unprecedented heterogeneous catalyst active for ethylene and butene oligomerization. [ABSTRACT FROM AUTHOR]

Polycaprolactone/polytrimethylenecarbonate copolymers of differentmicrostructures have been prepared in toluene solution under mildconditions by controlled ring-opening polymerization of ε-caprolactoneand trimethylene carbonate with methanesulfonic acid as catalyst.Sequential addition of the monomers led to the formation of well-defineddi- and tri-block copolymers, demonstrating the ability of the catalyticsystem to cross-propagate. Simultaneous copolymerization yielded gradientcopolymers as a result of the different copolymerization reactivityratios and absence of undesirable redistribution reactions. DSC analysesshowed a noticeable impact of the copolymer microstructure on thethermal properties. [ABSTRACT FROM AUTHOR]

Upon reaction with copper(i), peri-halo naphthyl phosphines readily form peri-bridged naphthyl phosphonium salts. The reaction works with alkyl, aryl and amino substituents at phosphorus, with iodine, bromine and chlorine as a halogen. It proceeds under mild conditions and is quantitative, despite the strain associated with the resulting 4-membered ring structure and the naphthalene framework. The transformation is amenable to catalysis. Under optimized conditions, the peri-iodo naphthyl phosphine 1-I is converted into the corresponding peri-bridged naphthyl phosphonium salt 2b in only 5 minutes at room temperature using 1 mol% of CuI. Based on DFT calculations, the reaction is proposed to involve a Cu(i)/Cu(iii) cycle made of P-coordination, C-X oxidative addition and P-C reductive elimination. This copper-catalyzed route gives a general and efficient access to peri-bridged naphthyl phosphonium salts for the first time. Reactivity studies could thus be initiated and the possibility to insert gold into the strained P-C bond was demonstrated. It leads to (P,C)-cyclometallated gold(iii) complexes. According to experimental observations and DFT calculations, two mechanistic pathways are operating: (i) direct oxidative addition of the strained P-C bond to gold,(ii) backward-formation of the peri-halo naphthyl phosphine (by C-P oxidative addition to copper followed by C-X reductive elimination), copper to gold exchange and oxidative addition of the C-X bond to gold. Detailed analysis of the reaction profiles computed theoretically gives more insight into the influence of the nature of the solvent and halogen atom, and provides rationale for the very different behaviour of copper and gold in this chemistry.

The peri-iodo naphthyl phosphine 1 reacts with CuI to give the peri-bridged phosphonio-naphthalene 2, which has been fully characterized (multi-nuclear NMR, MS, XRD). The outcome of the reaction differs markedly from that observed with gold. A two-step pathway involving P-assisted C-I oxidative addition to copper, followed by P-C reductive elimination is shown to be energetically feasible by DFT calculations., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The mechanism of ring-opening of ε-caprolactone by methanol catalyzed by trifluoromethane and methane sulfonic acids has been studied computationally at the DFT level of theory. For both elementary steps, the sulfonic acid was predicted to behave as a bifunctional catalyst. The nucleophilic addition proceeds via activation of both the monomer and the alcohol. The ring-opening involves the cleavage of the endo C-O bond of the tetrahedral intermediate with concomitant proton transfer. In both cases, the sulfonic acid acts as a proton shuttle via its acidic hydrogen atom and basic oxygen atoms. The computed activation barriers are consistent with the relatively fast polymerizations observed experimentally at room temperature with both catalysts.