5077-67-8Relevant academic research and scientific papers
Oxidation of but-3-en-1,2-diol: Green access to hydroxymethionine intermediate
Grasset,Rey,Bellière-Baca,Araque,Paul,Dumeignil,Wojcieszak,Katryniok
, p. 164 - 167 (2017)
Supported metallic and bimetallic systems were used for the selective oxidation of but-3-en-1,2-ol (BDO) to hydroxybut-3-en-2-one (HBO), an intermediate in the hydroxymethionine synthesis. All catalysts were active in this reaction. However, bimetallic systems were found more active and selective to HBO in the liquid aqueous phase at 50 °C using molecular O2 as a benign oxidant. The best performance (87% BDO conversion and 88% HBO selectivity) was observed over a 2%PdPt/TiO2 catalyst. No metal leaching was observed under the conditions studied.
Oxidation of 3-butene-1,2-diol by alcohol dehydrogenase
Kemper, Raymond A.,Elfarra, Adnan A.
, p. 1127 - 1134 (1996)
3-Butene-1,2-diol(BDD)is a metabolite of the carcinogenic petrochemical 1,3-butadiene. BDD is produced by cytochrome P450-mediated oxidation of 1,3- butadiene to butadiene monoxide, followed by enzymatic hydrolysis by epoxide hydrolase. The metabolic disposition of BDD is unknown. The current work characterizes BDD oxidation by purified horse liver alcohol dehydrogenase (ADH) and by cytosolic ADH from mouse, rat, and human liver. BDD is oxidized by purified horse liver ADH in a stereoselective manner, with (S)-BDD oxidized at approximately 7 times the rate of (R)-BDD. Attempts to detect and identify metabolites of BDD using purified horse liver ADH demonstrated formation of a single stable metabolite, 1-hydroxy-2-butanone (HBO). A second possible metabolite, 1-hydroxy-3-butene-2-one (HBONE), was tentatively identified by GC/MS, but HBONE formation could not be clearly attributed to BDD oxidation, possibly due to its rapid decomposition in the incubation mixture. Formation of HBO by ADH was dependent upon reaction time, protein concentration, substrate concentration, and the presence of NAD. Inclusion of GSH or 4-methylpyrazole in the incubation mixture resulted in inhibition of HBO formation. Based on these results and other lines of evidence, a mechanism is proposed for HBO formation involving generation of several potentially reactive intermediates which could contribute to toxicity of 1,3- butadiene in exposed individuals. Comparison of kinetics of BDD oxidation in rat, mouse, and human liver cytosol did not reveal significant differences in catalytic efficiency (V(max)/K(m)) between species. These results may contribute to a better understanding of 1,3-butadiene metabolism and toxicity.
Palladium-Catalyzed (3+3) Annulation of Allenylethylene Carbonates with Nitrile Oxides
Pan, Ting,Gao, Xing,Yang, Sen,Wang, Lan,Hu, Yimin,Liu, Min,Wang, Wei,Wu, Yongjun,Zheng, Bing,Guo, Hongchao
supporting information, p. 5750 - 5754 (2021/08/16)
In this paper, we designed and synthesized a new type of cyclic carbonates, allenylethylene carbonates (AECs). With AECs as reactive precursors, we developed palladium-catalyzed (3+3) annulation of AECs with nitrile oxides. Various AECs worked well in this reaction under mild reaction conditions. A variety of 5,6-dihydro-1,4,2-dioxazine derivatives with allenyl quaternary stereocenters can be accessed in a facile manner in high yields (≤98%).
Enantioselective Cascade Biocatalysis for Deracemization of Racemic β-Amino Alcohols to Enantiopure (S)-β-Amino Alcohols by Employing Cyclohexylamine Oxidase and ω-Transaminase
Zhang, Jian-Dong,Chang, Ya-Wen,Dong, Rui,Yang, Xiao-Xiao,Gao, Li-Li,Li, Jing,Huang, Shuang-Ping,Guo, Xing-Mei,Zhang, Chao-Feng,Chang, Hong-Hong
, p. 124 - 128 (2020/09/21)
Optically active β-amino alcohols are very useful chiral intermediates frequently used in the preparation of pharmaceutically active substances. Here, a novel cyclohexylamine oxidase (ArCHAO) was identified from the genome sequence of Arthrobacter sp. TYUT010-15 with the R-stereoselective deamination activity of β-amino alcohol. ArCHAO was cloned and successfully expressed in E. coli BL21, purified and characterized. Substrate-specific analysis revealed that ArCHAO has high activity (4.15 to 6.34 U mg?1 protein) and excellent enantioselectivity toward the tested β-amino alcohols. By using purified ArCHAO, a wide range of racemic β-amino alcohols were resolved, (S)-β-amino alcohols were obtained in >99 % ee. Deracemization of racemic β-amino alcohols was conducted by ArCHAO-catalyzed enantioselective deamination and transaminase-catalyzed enantioselective amination to afford (S)-β-amino alcohols in excellent conversion (78–94 %) and enantiomeric excess (>99 %). Preparative-scale deracemization was carried out with 50 mM (6.859 g L?1) racemic 2-amino-2-phenylethanol, (S)-2-amino-2-phenylethanol was obtained in 75 % isolated yield and >99 % ee.
Preparation method of 1-hydroxyl-2-alkanone
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Paragraph 0033-0034; 0042; 0046-0047, (2020/07/12)
The invention discloses a preparation method of 1-hydroxyl-2-alkanone. According to the preparation method, dihydric alcohol is converted into 1-hydroxy-2-alkanone in the presence of a copper-based catalyst (a conversion step). The reaction conditions of the conversion step are as follows: the reaction temperature is 200-400 DEG C, the reaction pressure is 0.01-0.5 MPa, and the liquid hour space velocity is 0.1-10 h. The method has a high dihydric alcohol conversion rate and 1-hydroxyl-2-alkanone selectivity, and is easy for industrial implementation.
A mechanism study on the efficient conversion of cellulose to acetol over Sn-Co catalysts with low Sn content
Liu, Xiaodong,Liu, Xiaohao,Ma, Longlong,Wang, Haiyong,Xiao, Tianci,Zhang, Ying
, p. 6579 - 6587 (2020/11/16)
Efficient conversion of renewable cellulose to high value-added C3 chemicals is a great challenge in the field of biomass valorization. In this work, we found that the combination of Co and Sn could significantly improve the efficiency of cellulose conversion to acetol. 54.4% yield of acetol and 66.6% total yield of C3 products were obtained when using 2%Sn-10%Co/SiO2 (2 wt% Sn content) as a catalyst. However, using the same Sn content of 2%Sn-10%Ni/SiO2, no acetol and only 7.1% yield of C3 products were produced. By studying the effects of different Sn and Co concentrations on cellulose conversion, it was found that the Sn species play an important role in catalyzing glucose conversion to C3 intermediates, while Co mainly played a role in hydrogenation, the same as Ni. The study demonstrated that Sn-Co/SiO2 with low Sn content can convert glucose to C3 intermediates more efficiently than the Sn-Ni/SiO2 catalyst. Moreover, Sn-Co/SiO2 could effectively convert C3 intermediates to acetol at a high temperature which is essential for acetol production from cellulose; but under the same conditions, the Sn-Ni/SiO2 catalyst tended to catalyze the polymerization of C3 intermediates. A series of characterization methods including AAS, TEM, HRTEM, EDS, XRD, ex situ XPS, in situ XPS, and CO2-TPD found that the combination of Sn and Co could significantly increase the noninteger valent SnOx species in the catalyst. These species increased the basicity of the catalyst and were beneficial in catalyzing the isomerization of glucose and the retro-aldol condensation of fructose. This journal is
Reductive Electrochemical Activation of Molecular Oxygen Catalyzed by an Iron-Tungstate Oxide Capsule: Reactivity Studies Consistent with Compound i Type Oxidants
Bugnola, Marco,Shen, Kaiji,Haviv, Eynat,Neumann, Ronny
, p. 4227 - 4237 (2020/05/05)
The reductive activation of molecular oxygen catalyzed by iron-based enzymes toward its use as an oxygen donor is paradigmatic for oxygen transfer reactions in nature. Mechanistic studies on these enzymes and related biomimetic coordination compounds designed to form reactive intermediates, almost invariably using various "shunt" pathways, have shown that high-valent Fe(V)=O and the formally isoelectronic Fe(IV) =O porphyrin cation radical intermediates are often thought to be the active species in alkane and arene hydroxylation and alkene epoxidation reactions. Although this four decade long research effort has yielded a massive amount of spectroscopic data, reactivity studies, and a detailed, but still incomplete, mechanistic understanding, the actual reductive activation of molecular oxygen coupled with efficient catalytic transformations has rarely been experimentally studied. Recently, we found that a completely inorganic iron-tungsten oxide capsule with a keplerate structure, noted as {Fe30W72}, is an effective electrocatalyst for the cathodic activation of molecular oxygen in water leading to the oxidation of light alkanes and alkenes. The present report deals with extensive reactivity studies of these {Fe30W72} electrocatalytic reactions showing (1) arene hydroxylation including kinetic isotope effects and migration of the ipso substituent to the adjacent carbon atom ("NIH shift"); (2) a high kinetic isotope effect for alkyl C - H bond activation; (3) dealkylation of alkylamines and alkylsulfides; (4) desaturation reactions; (5) retention of stereochemistry in cis-alkene epoxidation; and (6) unusual regioselectivity in the oxidation of cyclic and acyclic ketones, alcohols, and carboxylic acids where reactivity is not correlated to the bond disassociation energy; the regioselectivity obtained is attributable to polar effects and/or entropic contributions. Collectively these results also support the conclusion that the active intermediate species formed in the catalytic cycle is consistent with a compound I type oxidant. The activity of {Fe30W72} in cathodic aerobic oxidation reactions shows it to be an inorganic functional analogue of iron-based monooxygenases.
Asymmetric ring opening of racemic epoxides for enantioselective synthesis of (S)-β-amino alcohols by a cofactor self-sufficient cascade biocatalysis system
Zhang, Jian-Dong,Yang, Xiao-Xiao,Jia, Qiao,Zhao, Jian-Wei,Gao, Li-Li,Gao, When-Chao,Chang, Hong-Hong,Wei, Wen-Long,Xu, Jian-He
, p. 70 - 74 (2019/01/10)
A novel one-pot epoxide hydrolase/alcohol dehydrogenase/transaminase cascade process for the asymmetric ring opening of racemic epoxides to enantiopure β-amino alcohols is reported. The product (S)-β-amino alcohols were obtained in 97-99% ee and 79-99% conversion from readily available racemic epoxides.
Well-dispersed nickel nanoparticles on the external and internal surfaces of SBA-15 for hydrocracking of pyrolyzed α-cellulose
Trisunaryanti, Wega,Suarsih, Endah,Triyono,Falah, Iip Izul
, p. 1230 - 1237 (2019/01/23)
Catalysts comprising nickel supported on SBA-15 were prepared by wet impregnation and co-impregnation methods. Wet impregnation was performed by directly dispersing an Ni(NO3)2·6H2O aqueous solution into SBA-15, whereas in co-impregnation, ethylene glycol (EG) was added to nickel nitrate aqueous solution prior to dispersion into SBA-15. After drying and calcination, NiO/SBA-15w and NiO/SBA-15c were produced. Later, after the reduction process, Ni/SBA-15w and Ni/SBA-15c were obtained. The prepared catalysts were evaluated for the hydrocracking of pyrolyzed α-cellulose. The TEM images revealed that the catalysts prepared by wet impregnation showed inhomogeneous distribution of nickel loading, whereas catalysts prepared by co-impregnation using EG exhibited homogeneous distribution and formed no nickel aggregates. During hydrocracking of pyrolyzed α-cellulose, Ni/SBA-15c with total acidity, nickel loading, particle size, and specific surface area of 7.27 m mol g?1, 5.20 wt%, 3.17 nm, and 310.0 m2 g?1, respectively, exhibited the best catalytic performance compared to other prepared catalysts with 67.35 wt% conversion of liquid product with maximum selectivity in producing 13.09 wt% of 3-methyl-pentane. Moreover, Ni/SBA-15w with total acidity, nickel loading, particle size, and specific surface area of 10.87 m mol g?1, 8.15 wt%, 7.01 nm, and 628.0 m2 g?1, respectively, produced 69.89 wt% liquid product without hydrocarbons. Study of selectivity towards the formation of liquid hydrocarbons was carried out via double step hydrocracking using Ni/SBA-15w, and 18.55 wt% of n-hexane was produced in the liquid product.
Selective Conversion of Cellulose to Hydroxyacetone and 1-Hydroxy-2-Butanone with Sn–Ni Bimetallic Catalysts
Wang, Haiyong,Zhu, Changhui,Liu, Qiying,Tan, Jin,Wang, Chenguang,Liang, Zheng,Ma, Longlong
, p. 2154 - 2160 (2019/03/21)
The high-value-added chemicals hydroxyacetone (HA) and 1-hydroxy-2-butanone (HB) were produced from agricultural waste over a Ni3Sn4-SnOx catalyst. The Sn–Ni intermetallic compound and SnOx acted as the active sites for HA and HB production by selectively cleaving the target C?C and C?O bonds. Approximately 70 % of the total HA and HB yield was obtained by selective hydrogenolysis of cellulose. This strategy expands the application of cellulose towards renewable production of high-value C3 and C4 keto-alcohols from cellulosic biomass.
