39682-48-9Relevant academic research and scientific papers
Preparation of the diastereomerically pure 2S-hydroxy derivative of dihydrolevoglucosenone (cyrene)
Sharipov, Bulat T.,Davydova, Anna N.,Faizullina, Liliya Kh.,Valeev, Farid A.
, p. 200 - 202 (2019)
Diastereomerically pure levoglucosenone alcohol, synthesized from levoglucosenone, upon hydrogenation on Raney Ni or Pd/BaSO4 undergoes epimerization at C2 atom caused by formation of cyrene by-product and its subsequent non-specific
Catalytic hydrogenation of dihydrolevoglucosenone to levoglucosanol with a hydrotalcite/mixed oxide copper catalyst
De Bruyn, Mario,Sener, Canan,Petrolini, Davi D.,McClelland, Daniel J.,He, Jiayue,Ball, Madelyn R.,Liu, Yifei,Martins, Leandro,Dumesic, James A.,Huber, George W.,Weckhuysen, Bert M.
, p. 5000 - 5007 (2019)
Levoglucosanol (LGOL) is a critical intermediate for the bio-based production of hexane-1,2,5,6-tetrol, 1,2,6-hexanetriol, and 1,6-hexanediol. Here we report on the aqueous-phase hydrogenation of cellulose-derived dihydrolevoglucosenone (Cyrene) to LGOL using a calcined and reduced heterogeneous copper/hydrotalcite/mixed oxide catalyst, denoted as Cu8/MgAlOx-HP. The turnover frequency for LGOL conversion over this copper-containing catalyst is equal to 0.013 s-1 at 353 K as measured in a flow reactor which is half the one obtained using 0.4 wt% Pd/Al2O3. Moreover, while Cu8/MgAlOx-HP shows a stable activity, the activity of 0.4 wt% Pd/Al2O3 decreases with time-on-stream. Neither Cu-nor Al-leaching is observed (resp. 2O mixture (pH 3.5-4.5 range), which is due to the occurrence of the geminal diol moiety of Cyrene, an acidic species. In contrast, additional and consecutive oxidation and reduction of the catalyst leads to a gradual decrease in activity over time. Applying still further oxidation/reduction cycles to this catalyst tends to decrease its activity with some overall stabilization being observed from the fourth run onwards. Mg-leaching is shown to change the relative meso-to-macro pore content, but leaves the total pore volume unchanged between the fresh and the spent catalyst. In spite of the high copper loading (8 wt%), small Cu-nanoparticles (2-3 nm) are present over the hydrotalcite/mixed oxide surface of the Cu8/MgAlOx-HP material, and these particles do not aggregate during the hydrogenation reaction.
Reactivity, Selectivity, and Synthesis of 4-C-Silylated Glycosyl Donors and 4-Deoxy Analogues
J?ger Pedersen, Martin,Pedersen, Christian Marcus
supporting information, p. 2689 - 2693 (2020/12/01)
A method for introducing dimethylphenylsilyl at the 4-position in carbohydrates has been developed. Two C-silylated glycosyl donors were prepared via levoglucosenone, starting from cellulose. The glycosylation properties were studied using three glucoside
CNN pincer ruthenium complexes for efficient transfer hydrogenation of biomass-derived carbonyl compounds
Figliolia, Rosario,Cavigli, Paolo,Comuzzi, Clara,Del Zotto, Alessandro,Lovison, Denise,Strazzolini, Paolo,Susmel, Sabina,Zuccaccia, Daniele,Ballico, Maurizio,Baratta, Walter
supporting information, p. 453 - 465 (2020/01/21)
The ligand HCNNOMe (6-(4-methoxyphenyl)-2-aminomethylpyridine) is easily prepared from the commercially available 6-(4-methoxyphenyl)pyridine-2-carbaldehyde by the reaction of hydroxylamine and hydrogenation (H2, 1 atm) with Pd/C. The pincer complexes cis-[RuCl(CNNOMe)(PPh3)2] (1) and [RuCl(CNNOMe)(PP)] (PP = dppb, 2; and dppf, 3) are synthesized from [RuCl2(PPh3)3], HCNNOMe and PP (for 2 and 3) in 2-propanol with NEt3 at reflux and are isolated in 85-93% yield. Carbonylation of 1 (CO, 1 atm) gives [RuCl(CNNOMe)(CO)(PPh3)] (4) (79% yield) which cleanly reacts with Na[BArf4] and PCy3, affording the cationic trans-[Ru(CNNOMe)(CO)(PCy3)(PPh3)][BArf4] (5) (92% yield). These robust pincer complexes display remarkably high catalytic activity in the transfer hydrogenation (TH) of lignocellulosic biomass carbonyl compounds, using 2-propanol at reflux in a basic medium (NaOiPr or K2CO3). Thus, furfural, 5-(hydroxymethyl)furfural and Cyrene are reduced to the corresponding alcohols with 2 and 3, at S/C in the range of 10 000-100 000, within minutes or hours (TOF up to 1 500 000 h-1). The monocarbonyl complex 5 was found to be extremely active in the TH of cinnamaldehyde, vanillin derivatives and ethyl levulinate at S/C in the range of 10 000-50 000. Vanillyl alcohol is also obtained by the TH of vanillin with 5 (S/C = 500) in 2-propanol in the presence of K2CO3.
Hydrogenation of levoglucosenone to renewable chemicals
Krishna, Siddarth H.,McClelland, Daniel J.,Rashke, Quinn A.,Dumesic, James A.,Huber, George W.
, p. 1278 - 1285 (2017/08/15)
We have studied the hydrogenation of levoglucosenone (LGO) to dihydrolevoglucosenone (Cyrene), levoglucosanol (Lgol), and tetrahydrofurandimethanol (THFDM) and elucidated the reaction network over supported palladium catalysts. At low temperature (40 °C) over a Pd/Al2O3 catalyst, LGO is selectively hydrogenated to Cyrene. At intermediate temperatures (100 °C) over a Pd/Al2O3 catalyst, Cyrene is selectively hydrogenated to Lgol, with an excess of the exo-Lgol isomer produced over the endo-Lgol isomer. At higher temperatures (150 °C) over a bifunctional Pd/SiO2-Al2O3 catalyst, Lgol is converted to THFDM in 58% selectivity, with 78% overall selectivity to 1,6-hexanediol precursors. The ratio of cis-THFDM relative to trans-THFDM is approximately 2.5, and this ratio is independent of the Lgol feed stereoisomer ratio. Tetrahydropyran-2-methanol-5-ketone (THP2M5one) and tetrahydropyran-2-methanol-5-hydroxyl (THP2M5H) are side-products of Lgol hydrogenolysis, but neither of these species are precursors to THFDM.
