Hydrogenation and transfer hydrogenation of d-fructose catalyzed by dichlorotris (triphenylphosphine) ruthenium (II)
TL;DR: In this article, RuCl 2 (PPh 3 ) 3 was used as a catalyst for the transfer hydrogenation of fructose to mannitol and glucitol in an inert atmosphere.
About: This article is published in Journal of Molecular Catalysis.The article was published on 1993-05-10. It has received 14 citations till now. The article focuses on the topics: Noyori asymmetric hydrogenation & Transfer hydrogenation.
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TL;DR: Past and present developments in hydrogenolysis reactions are highlighted, with special emphasis on the direct utilization of cellulosic feedstocks, to bridge currently available technologies and future biomass-based refinery concepts.
Abstract: In view of the diminishing oil resources and the ongoing climate change, the use of efficient and environmentally benign technologies for the utilization of renewable resources has become indispensible. Therein, hydrogenolysis reactions offer a promising possibility for future biorefinery concepts. These reactions result in the cleavage of C-C and C-O bonds by hydrogen and allow direct access to valuable platform chemicals already integrated in today's value chains. Thus, hydrogenolysis bears the potential to bridge currently available technologies and future biomass-based refinery concepts. This Review highlights past and present developments in this field, with special emphasis on the direct utilization of cellulosic feedstocks.
735 citations
TL;DR: In this paper, the Hydrogenolyse eine vielversprechende Reaktion fur zukunftige Bioraffineriekonzepte dar.
Abstract: Angesichts begrenzter Reserven fossiler Rohstoffe und einem Voranschreiten des Klimawandels werden effiziente und umweltfreundliche Technologien zur Nutzbarmachung erneuerbarer Rohstoffe unerlasslich. Dabei stellt die Hydrogenolyse eine vielversprechende Reaktion fur zukunftige Bioraffineriekonzepte dar. Sie resultiert in einer C-C- und C-O-Bindungsspaltung mit Wasserstoff und erlaubt einen direkten Zugang zu nutzlichen Plattformchemikalien, die bereits heute Teil der Wertschopfungsketten der chemischen Industrie sind. Aus diesem Grund birgt die Hydrogenolyse das Potential, existierende Wertschopfungsketten und zukunftige Bioraffineriekonzepte zu verbinden. Dieser Aufsatz stellt vorausgegangene und aktuelle Entwicklungen in diesem Bereich mit besonderem Augenmerk auf der direkten Umsetzung von Cellulose als Rohstoffe dar.
119 citations
TL;DR: In this paper, the authors report several types of potential metals (rhodium and ruthenium) carbonyl complexes of functionalized phosphine-chalcogen donors ligands like P-X (X = O, S, Se) and their catalytic applications.
57 citations
TL;DR: In this article, the reaction of P,S-chelating diphosphane ligands [bis(2-diphenylphosphanylphenyl)ether monosulfide] with [Ru(CO) 2 Cl 2 ] n in a 1:1 molar ratio affords two new ruthenium(II) complexes.
Abstract: The reaction of P,S-chelating diphosphane ligands [bis(2-diphenylphosphanylphenyl)ether monosulfide] (a) and [9,9-dimethyl-4,5-bis(diphenylphosphanyl)xanthene monosulfide] (b) with [Ru(CO) 2 Cl 2 ] n in a 1:1 molar ratio affords two new ruthenium(II) complexes of the type [Ru(CO) 2 Cl 2 (P∩S)] (1a, 1b), where P∩S = a, b. The compounds are characterized by elemental analyses, mass spectrometry, thermal studies, and IR and NMR spectroscopy, together with single-crystal X-ray structure determination of bis(2-diphenylphosphanylphenyl)ether (DPEphos), a, 1a, and 1b. The ruthenium atom in both 1a and 1b occupies the center of a slightly distorted octahedral environment formed by a P atom, an S atom, two Cl atoms, and two CO groups. The crystal structures of a and 1a highlights an interesting feature, in which the P(2)-P(1)-S(1) spatial angle (ca. 174.7°) in free ligand a is reduced to around 46° upon complexation, which indicates a very high flexibility of the angle. Complex 1a also exhibits some hemilabile behavior in solution because of its flexible ligand backbone, while ligand b in complex 1b remains rigid in solution. Complexes 1a and 1b are thermally stable up to about 300 °C and show high catalytic activities in the transfer hydrogenation of aldehydes and ketones to the corresponding alcohols. The highest conversion (about 99 %) with the corresponding TOF value of about 1000 h -1 was obtained for 1a in the case of benzaldehyde. The catalytic efficiency of 1a is found to be much higher than 1b, which might result from the hemilabile behavior of ligand a.
34 citations
TL;DR: Inulin, a polysaccharide containing one d-glucose and 10 to 50 d-fructose units, when hydrolysed and hydrogenated in a one-pot approach, would be an attractive d-mannitol feedstock.
Abstract: Inulin, a polysaccharide containing one d -glucose and 10 to 50 d -fructose units, when hydrolysed and hydrogenated in a one pot approach, would be an attractive d -mannitol feedstock. For this purpose, the hydrogenation was studied with fructose as a model compound, using a water soluble, homogeneous catalyst. This catalyst contains ruthenium as the active metal, and trisulfonated triphenylphosphine (TPPTS, P(m-C6H4SO3Na)3), as the ligand. The effects of temperature, pressure, catalyst/substrate and ligand/metal ratios on the activity and selectivity were investigated. The reaction was shown to be homogeneously catalysed, despite the formation of some ruthenium particles at higher temperatures (>90°C), and the active complex was studied with 1 H and 31 P NMR. Addition of HCl or salts (NaCl, Nal and CaCl2) increased the selectivity to d -glucitol and the catalytic activity. Upon deuterogenation of fructose with H2 in D2O, D was built in only at the 2-position.
33 citations
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TL;DR: In this article, the interaction of triphenylphosphine, -arsine and -stibine with hydrated ruthenium trichloride in methanol leads to a variety of complexes such as [RuCl2(PPh3)4], [RuCL2(SbPh3]3], RuCl3(Pph3)2CH3OH, [RuC2(CPh3As, Ph3Sb, pyridine etc., with a carbonyl-containing solution] and the corresponding brom
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TL;DR: In this article, a mixture of glucose and fructose was found to undergo quantitative transfer hydrogenation yielding equal amounts of gluconic acid and of hexitols (mannitol and sorbitol).
Abstract: Equimolar mixtures of glucose and fructose were found to undergo quantitative transfer hydrogenation yielding equal amounts of gluconic acid and of hexitols (mannitol and sorbitol). The oxidationreduction occurs in aqueous alkaline medium under nitrogen at room temperature in the presence of Pt/C or Rh/C as the catalyst. Other group VIII metals did not give satisfactory results. Both a stirred batch and a continuous flow column reactor have been applied. The influence of several reaction variables has been studied, leading to the conclusion that the rate-limiting step ist the dehydrogenation reaction of glucose into gluconic acid and chemisorbed hydrogen. Subsequently, the latter is quickly consumed by coadsorbed fructose under formation of mannitol and sorbitol (in the ratio of 1.5. – 1.9: 1). Alkaline degradation products are found to be of minor importance at temperatures ≦ 25°C.
Katalytische Wasserstoffubertragung in Glucose-Fructosesirupen in alkalischer Losung. Es wurde festgestellt, das aquimolekulare Mischungen von Glucose und Fructose einer quantitativen Wasserstoffubertragung unterliegen, die zu gleichen Mengen Gluconsaure und Hexitolen (Mannitol und Sorbitol) fuhren. Die Oxidation-Reduktion tritt in wasrigem alkalischem Medium unter Stickstoffatmosphare bei Raumtemperatur in Gegenwart von Pt/C oder Rh/C als Katalysatoren auf. Andere Metalle der VIII. Gruppe fuhrten nicht zu befriedigenden Ergebnissen. Fur die Versuche wurden sowohl ein Batch-Reaktor mit Ruhreinrichtung als auch ein kontinuierlicher Durchflus-Saulenreaktor angewendet. Der Einflus verschiedener Reaktionsparameter wurde untersucht, was zu der Schlusfolgerung fuhrte, das der geschwindigkeitsbestimmende Schritt die Dehydrierungsreaktion der Glucose zu Gluconsaure und chemisorbiertem Wasserstoff ist. Anschliesend wird letzterer durch mitadsorbierte Fructose unter Bildung von Mannitol und Sorbitol (Verhaltnis 1, 5 bis 1, 9 zu 1) rasch verbraucht. Die alkalischen Abbauprodukte waren bei Temperaturen ≦ 25°C nur von geringer Bedeutung.
19 citations