Graphene oxide as a catalyst for the diastereoselective transfer hydrogenation in the synthesis of prostaglandin derivatives

[EN] Modification of GO by organic molecules changes its catalytic activity in the hydrogen transfer from i-propanol to enones, affecting the selectivity to allyl alcohol and diastereoselectivity to the resulting stereoisomers. It is noteworthy the system does not contain metals and is recyclable.Coman, SM.; Podolean, I.; Tudorache, M.; Cojocaru, B.; Parvulescu, VI.; Puche Panadero, M.; García Gómez, H. (2017). Graphene oxide as a catalyst for the diastereoselective transfer hydrogenation in the synthesis of prostaglandin derivatives. Chemical Communications. 53(74):10271-10274. doi:10.1039/c7cc05105kS1027110274537

N-Doped graphene as a metal-free catalyst for glucose oxidation to succinic acid

[EN] N-Containing graphenes obtained either by simultaneous amination and reduction of graphene oxide or by pyrolysis of chitosan under an inert atmosphere have been found to act as catalysts for the selective wet oxidation of glucose to succinic acid. Selectivity values over 60% at complete glucose conversion have been achieved by performing the reaction at 160 degrees C and 18 atm O-2 pressure for 20 h. This activity has been attributed to graphenic-type N atoms on graphene. The active N-containing graphene catalysts were used four times without observing a decrease in conversion and selectivity of the process. A mechanism having tartaric and fumaric acids as key intermediates is proposed.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa, Grapas and CTQ2015-69153-CO2-R1) and Generalitat Valenciana (Prometeo 2013-014) is gratefully acknowledged. Prof. Simona M. Coman kindly acknowledges UEFISCDI for financial support (project PN-II-PT-PCCA-2013-4-1090, Nr. 44/2014). Cristina Bucur acknowledges Core Programme, Project PN-480103/2016.Rizescu, C.; Podolean, I.; Albero-Sancho, J.; Parvulescu, VI.; Coman, SM.; Bucur, C.; Puche Panadero, M.... (2017). N-Doped graphene as a metal-free catalyst for glucose oxidation to succinic acid. Green Chemistry. 19(8):1999-2005. https://doi.org/10.1039/C7GC00473GS19992005198Alonso, D. M., Wettstein, S. G., & Dumesic, J. A. (2012). Bimetallic catalysts for upgrading of biomass to fuels and chemicals. Chemical Society Reviews, 41(24), 8075. doi:10.1039/c2cs35188aCherubini, F. (2010). The biorefinery concept: Using biomass instead of oil for producing energy and chemicals. Energy Conversion and Management, 51(7), 1412-1421. doi:10.1016/j.enconman.2010.01.015Christensen, C. H., Rass-Hansen, J., Marsden, C. C., Taarning, E., & Egeblad, K. (2008). The Renewable Chemicals Industry. 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Magnetic Fe@Y Composites as Efficient Recoverable Catalysts for the Valorization of the Recalcitrant Marine Sulfated Polysaccharide Ulvan

Magnetic Fe@Y composites (carbon-coated magnetic iron nanoparticles incorporated in zeolite Y) with 5-8 wt % Fe were synthesized and characterized. Overall acidity of the samples ranged between 2.0 and 2.47 mmol/g and is mostly attributed to Lewis acid sites. The obtained materials were proven to catalyze the hydrolysis of the marine sulfated polysaccharide ulvan with high conversion rates. The distribution of the reaction products depended on the reaction conditions and the concentration of ulvan. The catalytic property-catalytic performance correlations clearly showed that the acid zeolite Y is the active phase for the hydrolysis of ulvan, while the iron nanoparticles enable the catalyst separation in a magnetic field. Under oxygen pressure, the selectivity was completely changed to favor succinic acid production. All Fe@Y composites were recycled 10 times with no change in their catalytic performance after recovery via a simple magnetic separation and washing with water. Copyright © 2019 American Chemical Society

From Glucose Direct to Succinic Acid: an Optimized Recyclable Bi-functional Ru@MNP-MWCNT Catalyst

[EN] Ru@MNP-MWCNT catalysts were obtained via functionalization of nanostructured carbon-based carriers (ie, MWCNT) with base molecules (ie, 2-aminophenol and ethylenediamine) followed by the complexation with RuCl3. These structures demonstrated a highly efficient behavior for the selective wet oxidation of levulinic acid and glucose to succinic acid. However, to ensure an easy recovery and high recyclability the MWCNTs nanotubes were modified by incorporation of super-paramagnetic Fe3O4 nanoparticles into porous structure. Besides the catalytic performances the resulted composites showed a good mechanical resistance.Authors are gratefully to Giuliana Aquilanti and Luca Olivi, Elettra Sincrotrone Trieste, S.S. 14km 163,5, Area Science Park, 34149 Basovizza-Trieste, Italy for XANES measurements. Vasile I. Parvulescu kindly acknowledges UEFISCDI for financial support (project PN-III-P4-ID-PCE-2016-0146, Nr. 121/2017Podolean, I.; Cojocaru, B.; García Gómez, H.; Teodorescu, C.; Parvulescu, VI.; Coman, SM. (2018). From Glucose Direct to Succinic Acid: an Optimized Recyclable Bi-functional Ru@MNP-MWCNT Catalyst. Topics in Catalysis. 61(18-19):1866-1876. https://doi.org/10.1007/s11244-018-1012-4S186618766118-1

Chiral supported ionic liquid phase (CSILP) catalysts for greener asymmetric hydrogenation processes

Chiral supported ionic liquid phase (CSILP) catalysts were prepared by physical adsorption (within highly porous carbons or mesoporous silica) of Ir, Ru and Rh complexes as IrCl(COD)-(S,S)-BDPP, [IrCl-(S)-BINAP]2, RuCl(p-cymene)[(S,S)-Ts-DPEN], RuOTf(p-cymene)[(S,S)-Ts-DPEN], [Rh(COD)(S,S)-DIPAMP][BF4], and [Rh(COD)(R,R)-Me-DuPHOS][BF4]. For the syntheses of CSILP catalysts [EMIM][NTf2],[BMIM][BF4] and [BMIM][PF6] ionic liquids were used. Comparative homogeneous and heterogeneous experiments were carried out using the asymmetric hydrogenation of double C N and C C bonds in trimethylindolenine, 2-methylquinoline and dimethylitaconate, respectively. The conversion and enantioselectivity was found to depend on the nature of the complex (metal and ligand), the immobilization method used, nature of the ionic liquid, nature of the support and the experimental conditions

Catalytic transformation of the marine polysaccharide ulvan into rare sugars, tartaric and succinic acids

The green macroalga Ulva rigida represents a promising feedstock for biorefinary due to its fast growth and cosmopolitan distribution. The main component of the cell walls of U. rigida is a sulfated glucuronorhamnan polysaccharide known as ulvan. Herein it was found that due to the high (hydrogen)sulfate group content of ulvan, hydrothermal autohydrolysis at 130 °C renders a high percentage of rhamnose (78–79 % recovery from the initial content in the raw material), a rare sugar of high added value. In addition, acid catalysis by a triflate-based graphene oxide under oxygen-free conditions at 180 °C affords moderate amounts of tartaric acid (24–26 %). The same triflate-based graphene oxide catalyst under oxygen pressure yields remarkably high percentages of succinic acid (65 %). The catalyst preserves its activity for at least five consecutive reuses. © 2020 Elsevier B.V

Catalytic transformation of the marine polysaccharide ulvan into rare sugars, tartaric and succinic acids

The green macroalga Ulva rigida represents a promising feedstock for biorefinary due to its fast growth and cosmopolitan distribution. The main component of the cell walls of U. rigida is a sulfated glucuronorhamnan polysaccharide known as ulvan. Herein it was found that due to the high (hydrogen)sulfate group content of ulvan, hydrothermal autohydrolysis at 130 °C renders a high percentage of rhamnose (78–79 % recovery from the initial content in the raw material), a rare sugar of high added value. In addition, acid catalysis by a triflate-based graphene oxide under oxygen-free conditions at 180 °C affords moderate amounts of tartaric acid (24–26 %). The same triflate-based graphene oxide catalyst under oxygen pressure yields remarkably high percentages of succinic acid (65 %). The catalyst preserves its activity for at least five consecutive reuses.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa SEV2016-0683, RTI2018-890237-CO2-R1) and Generalitat Valenciana (Prometeo 2017−083) is gratefully acknowledged. Vasile I. Parvulescu kindly acknowledges UEFISCDI for financial support (project PN-III-P4-ID-PCE-2016-0146, Nr. 121/2017)

Impact of SCILL catalysts for the S-S coupling of thiols to disulfides

SCILL catalysts are active and selective for the S–S coupling of thiols to the corresponding disulfides showing a significantly increased stability.</p