14697-46-2Relevant academic research and scientific papers
Achmatowicz rearrangement enables hydrogenolysis-free gas-phase synthesis of pentane-1,2,5-triol from furfuryl alcohol
Simeonov, Svilen P.,Lazarova, Hristina I.,Marinova, Maya K.,Popova, Margarita D.
, p. 5657 - 5664 (2019)
Highly efficient synthesis of pentane-1,2,5 triol, a promising member of biorenewable C5 alcohols, has been achieved by gas-phase hydrogenation of the Achmatowicz intermediate derived from furfuryl alcohol. The hydrogenation was carried out on monocomponent or bicomponent Ni and/or Pt modified mesoporous silica catalysts. The process features the absence of hydrogenolysis of the furan ring and rendered 100% selectivity together with additional green chemistry benefits, such as mild and simpler solvent free technology that operates at atmospheric pressure. The bicomponent Ni/Pt modified mesoporous silica catalysts exhibited the highest catalytic activity, with 10Ni1Pt/KIT-6 being the most active, providing up to 100% conversion.
Biocatalytic approaches to both enantiomers of (2R*,3S*)-2-allyloxy-3,4,5,6-tetrahydro-2H-pyran-3-ol
Sugai, Takeshi,Ikeda, Hajime,Ohta, Hiromichi
, p. 8123 - 8134 (1996)
Both enantiomers of (2R*,3S*)-2-allyloxy-3,4,5,6-tetrahydro-2H-pyran-3-ol, a precursor of chiral auxiliary for asymmetric addition of organometallics, and its analog, (2S,3S)-2-ethoxy-3,4,5,6-tetrahydro-2H-pyran-3-ol were prepared by biocatalytic optical resolutions. Lipase-catalyzed enantioselective acetylation of the racemate in organic solvent worked well with a high enantioseleclivity. Pseudomonas cepacia lipase was most effective (E = 11-17) for the kinetic resolution. Under the optimized condition, the products, (2R,3S)-2-allyloxy-3,4,5,6-tetrahydro-2H-pyran-3-ol and (2S,3S)-2-ethoxy analog with more than 97% e.e. were obtained in 31-45% yield with 52-62% conversion. The enantiomer, (2S,3R)-2-allyloxy compound was secured by two ways. The repetition of the lipase-catalyzed acetylation on partially enantiomerically enriched substrate afforded the acetate with a high e.e. (97%). A newly developed double resolution procedure in one-pot reaction was also successful. In this case, the apparent E value via two steps became as high as 71.Copyright
Selective hydrogenolysis of benzyl ethers in the presence of benzylidene acetals with Raney nickel
Vincent, Aurélie,Prunet, Jo?lle
, p. 4075 - 4077 (2006)
A simple method to remove selectively a benzyl group protecting a hydroxyl function in the presence of a benzylidene acetal by catalytic hydrogenolysis with Raney nickel is reported. This method was successfully applied to the synthesis of the C1-C14 fragment of dolabelides.
Biorefinery via Achmatowicz Rearrangement: Synthesis of Pentane-1,2,5-triol from Furfuryl Alcohol
Simeonov, Svilen P.,Ravutsov, Martin A.,Mihovilovic, Marko D.
, p. 2748 - 2754 (2019)
A new scalable synthesis of pentane-1,2,5-triol from the furanics platform has been developed. Excellent yields of up to 92 % are obtained under flow conditions by using readily available catalysts from the existing pool. The strategy exploits the highly functionalized Achmatowicz product as a key intermediate, thus circumventing problems related to the low reactivity of the parent furfural and furfuryl alcohol. Besides expanding the portfolio of biomass-derived C5 alcohols, this strategy may also be further applied for the establishment of a versatile bio-based chemical platform.
Adsorption Configuration-Determined Selective Hydrogenative Ring Opening and Ring Rearrangement of Furfural over Metal Phosphate
Tong, Zhikun,Li, Xiang,Dong, Jingyu,Gao, Rui,Deng, Qiang,Wang, Jun,Zeng, Zheling,Zou, Ji-Jun,Deng, Shuguang
, (2021)
Developing an economic catalyst to upgrade furfural to alcohols (such as linear alcohol and cyclopentanol) is highly significant for fine chemical synthesis and biomass utilization. Here, a class of metal phosphate nanoparticles (such as CoP, Co2P, and Ni2P) with different metal compositions and topological structures is synthesized. The acidity and hydrogen activation ability were well adjusted according to the types. An 80.2% yield of 1,2,5-pentanetriol was reported for the first time via a hydrogenative ring-opening route over CoP, whereas Ni2P shows a high catalytic efficiency for cyclopentanol with a 62.8% yield via a hydrogenative ring-rearrangement route. Based on the catalytic performance of Pd/C and the result of attenuated total reflectance-infrared spectroscopy, the route difference is derived from the adsorption configuration of furfural on the catalyst. After loading on the insert support, the metal phosphate/support catalysts show high activity and stability during the recycling experiments. This work provides an effective strategy to regulate the reaction path through an adsorption mechanism and shows the precise synergistic effect of hydrogenation and acid catalysis.
Hydrodeoxygenation of C4-C6 sugar alcohols to diols or mono-alcohols with the retention of the carbon chain over a silica-supported tungsten oxide-modified platinum catalyst
Betchaku, Mii,Cao, Ji,Liu, Lujie,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi,Yabushita, Mizuho
supporting information, p. 5665 - 5679 (2021/08/16)
The hydrodeoxygenation of erythritol, xylitol, and sorbitol was investigated over a Pt-WOx/SiO2 (4 wt% Pt, W/Pt = 0.25, molar ratio) catalyst. 1,4-Butanediol can be selectively produced with 51% yield (carbon based) by erythritol hydrodeoxygenation at 413 K, based on the selectivity over this catalyst toward the regioselective removal of the C-O bond in the -O-C-CH2OH structure. Because the catalyst is also active in the hydrodeoxygenation of other polyols to some extent but much less active in that of mono-alcohols, at higher temperature (453 K), mono-alcohols can be produced from sugar alcohols. A good total yield (59%) of pentanols can be obtained from xylitol, which is mainly converted to C2 + C3 products in the literature hydrogenolysis systems. It can be applied to the hydrodeoxygenation of other sugar alcohols to mono-alcohols with high yields as well, such as erythritol to butanols (74%) and sorbitol to hexanols (59%) with very small amounts of C-C bond cleavage products. The active site is suggested to be the Pt-WOx interfacial site, which is supported by the reaction and characterization results (TEM and XAFS). WOx/SiO2 selectively catalyzed the dehydration of xylitol to 1,4-anhydroxylitol, whereas Pt-WOx/SiO2 promoted the transformation of xylitol to pentanols with 1,3,5-pentanetriol as the main intermediate. Pre-calcination of the reused catalyst at 573 K is important to prevent coke formation and to improve the reusability.
Method for converting furfural into 1, 2, 5-pentanetriol through hydrogenation hydrolysis
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Paragraph 0020-0043, (2021/01/04)
The invention discloses a method for converting furfural into 1, 2, 5-pentanetriol through hydrogenation hydrolysis, and belongs to the field of fine organic chemicals. The method comprises the following steps: adding different metal phosphides or metal phosphides loaded with different carriers into a mixture of furfural and water as a catalyst, and performing reacting in a hydrogen atmosphere toobtain 1, 2, 5-pentanetriol. The invention discloses a novel method for preparing 1, 2, 5-pentanetriol by taking a biomass platform compound furfural as a raw material, which is simple in technological process, convenient to operate and mild in reaction condition, a catalyst can be separated and recycled, the production cost is reduced, and the method has a good application prospect.
C?O Hydrogenolysis of Tetrahydrofurfuryl Alcohol to 1,5-Pentanediol Over Bi-functional Nickel-Tungsten Catalysts
Soghrati, Elmira,Kok Poh, Chee,Du, Yonghua,Gao, Feng,Kawi, Sibudjing,Borgna, Armando
, p. 4652 - 4664 (2018/10/02)
In this study, we report a series of bimetallic Ni?WOx catalyst for the ring-opening of THFA into 15PDO. The structure-performance relationship of the catalysts was discussed based on extensive characterization using techniques such as BET, H2-TPR, NH3-TPD, Pyr-IR, IPA-TPD-MS, XRD, XPS and EXAFS/XANES. The acidity measurements show that higher W density leads to the higher amount of acid density, which could be assigned to the creation of Lewis acid sites mainly on the surface of the calcined catalysts. H2-TPR profiles of Ni?WOx catalysts show that there is a strong interaction between Ni and W species, enhancing the reducibility of WOx. XRD measurements of calcined Ni?WOx catalysts reveal that the dispersion of Ni particles is enhanced after addition of WOx species. After reduction, different peaks corresponding to metallic Ni and WO3?x are identified for 10Ni?WOx catalysts, as well as new peak assigned to Ni?W intermetallic phase on 10Ni?30WOx catalyst. The formation of Ni?W intermetallic phase was further proved using XPS and EXAFS studies. THFA hydrogenolysis was also conducted under aqueous-phase conditions over Ni?WOx catalysts, yielding up to 47 % selectivity to 15PDO, along with a highest combined C5 polyols (i. e., 15PDO and 125PTO) selectivity of approximately 64 %. However, the Ni?WOx catalytic system suffers from deactivation process due to the hydrothermal dissolution of the active phase. Further investigation reveals the better stability of metallic tungsten and Ni?W intermetallic phase (Ni4W) against leaching since their corresponding peaks in the XRD patterns of spent catalysts remains nearly unchanged. Finally, 1,4-dioxane as an organic solvent was employed in THFA hydrogenolysis reaction, resulting in different product distribution, with a THP yield of around 54 %. The catalyst crystalline structure is preserved because of very low Ni and W leaching when 1,4-dioxane is used as solvent.
Mechanistic study on -C-O- and -C-C- hydrogenolysis over Cu catalysts: Identification of reaction pathways and key intermediates
Kühne, Benjamin,Vogel, Herbert,Meusinger, Reinhard,Kunz, Sebastian,Kunz, Markwart
, p. 755 - 767 (2018/02/14)
Important petro-based polyol compounds with a longer carbon chain, such as oligohydroxy hexanes (e.g. 1,2- and 1,6-hexanediol or 1,2,6-hexanetriol), require at least three to four synthesis steps. Replacing this complex chemistry by a one-pot reaction via -C-O- bond cleavage from sugars would be a significant breakthrough for the use of renewable feedstocks. Cu is known for its dehydroxylation (deoxygenation) properties, yielding the desired products from sugars. In this joint research between academic and industrial chemistry, we have identified so far unknown intermediate products and present the first mechanism that explains the selective cleavage of OH-groups over copper. Strong interactions between polyols, unsaturated species and the copper surface are observed. Stable five-membered rings are formed with Cu via two vicinal OH-groups of the polyol reactant that makes these OH-groups inert to -C-O- bond cleavage. Adjacent free OH-groups in close proximity to the catalyst are dehydroxylated (deoxygenated). We further show that degradation of polyols not only occurs via commonly cited retro-aldol reactions. The formation of acid intermediates with subsequent decarboxylation is validated as a new pathway for -C-C- bond cleavage to short-chain polyols and CO2. The proposed mechanisms for -C-O- and -C-C- bond cleavage elucidate why hydrogenolysis reactions require high hydrogen pressure (up to 200 bar) to suppress the degradation of sugars and obtain high yields of deoxy C6 products. With this knowledge, the improvement of a standard commercial Cu-RANEY catalyst under optimized reaction conditions was shown. In contrast to alumina-supported Cu, the Cu-Al alloy in a RANEY-type catalyst shows selective -C-O- bond cleavage properties while maintaining the C6 carbon chain. These new insights into the transformation of sugars to value added commodities show the potential for new approaches in future biorefinery concepts.
Identification of a Water-Soluble Indirubin Derivative as Potent Inhibitor of Insulin-like Growth Factor 1 Receptor through Structural Modification of the Parent Natural Molecule
Cheng, Xinlai,Merz, Karl-Heinz,Vatter, Sandra,Zeller, Jochen,Muehlbeyer, Stephan,Thommet, Andrea,Christ, Jochen,W?lfl, Stefan,Eisenbrand, Gerhard
, p. 4949 - 4962 (2017/06/28)
Indirubins have been identified as potent ATP-competitive protein kinase inhibitors. Structural modifications in the 5-and 3′-position have been extensively investigated, but the impact of substituents in 5′-position is not equally well-studied. Here, we report the synthesis of new indirubin 3′-and 5′-derivatives in the search of water-soluble indirubins by introducing basic centers. Antiproliferative activity of all compounds in tumor cells was evaluated along with kinase inhibition of selected compounds. The results show the 3′-position to tolerate large substituents without compromising activity, whereas bulk and rigid substituents in 5′-position appear unfavorable. Screening molecular targets of water-soluble 3′-oxime ethers revealed 6ha as preferential inhibitor of insulin-like growth factor 1 receptor (IGF-1R) in a panel of 22 protein kinases and in cells. Consistently, 6ha inhibited tumor cell growth in the NCI 60 cell line panel and induced apoptosis. The results indicate that the 5′-position provides limited space for chemical modifications and identify 6ha as a potent water-soluble indirubin-based IGF-1R inhibitor.
