2320-30-1Relevant academic research and scientific papers
Selective oxidation of alcohols to aldehydes/ketones over copper oxide-supported gold catalysts
Wang, Hui,Fan, Weibin,He, Yue,Wang, Jianguo,Kondo, Junko N.,Tatsumi, Takashi
, p. 10 - 19 (2013)
Selective oxidation of alcohols to aldehydes/ketones with O2 over a series of supported gold catalysts was studied. The catalytic performance depends strongly on the support. It is also strongly influenced by the preparation method and the pH value and stirring rate during the co-precipitation process as a result of their effect on the structure of the support and the particle size and electronic state of gold. The Au/CuO co-precipitated at pH 10 and stirring rate 100 rpm showed high activity, selectivity, and stability. The reaction might occur via oxidative dehydroxylation of alcohols to aldehydes/ketones by direct β-CH elimination, as indicated by the IR result. The oxidation of different cycloalcohols showed that the activity increased with an increase in their methyl groups. Both conversion and ketone selectivity higher than 99% were achieved for cyclooctanol and cyclododecanol.
Total synthesis of (±)-arohynapene B
Sugimura, Hideyuki,Uchida, Yuki
, p. 352 - 353 (2005)
The total synthesis of (±)-arohynapene B, an anticoccidial agent isolated from the fermentation broth of a fungal strain, has been achieved. The tetrahydronaphthalene ring was constructed by the Diels-Alder reaction between dimethyl acetylenedicarboxylate
A robust and stereocomplementary panel of ene-reductase variants for gram-scale asymmetric hydrogenation
Nett, Nathalie,Duewel, Sabine,Schmermund, Luca,Benary, Gerrit E.,Ranaghan, Kara,Mulholland, Adrian,Opperman, Diederik J.,Hoebenreich, Sabrina
, (2021/01/25)
We report an engineered panel of ene-reductases (ERs) from Thermus scotoductus SA-01 (TsER) that combines control over facial selectivity in the reduction of electron deficient C[dbnd]C double bonds with thermostability (up to 70 °C), organic solvent tolerance (up to 40 % v/v) and a broad substrate scope (23 compounds, three new to literature). Substrate acceptance and facial selectivity of 3-methylcyclohexenone was rationalized by crystallisation of TsER C25D/I67T and in silico docking. The TsER variant panel shows excellent enantiomeric excess (ee) and yields during bi-phasic preparative scale synthesis, with isolated yield of up to 93 % for 2R,5S-dihydrocarvone (3.6 g). Turnover frequencies (TOF) of approximately 40 000 h?1 were achieved, which are comparable to rates in hetero- and homogeneous metal catalysed hydrogenations. Preliminary batch reactions also demonstrated the reusability of the reaction system by consecutively removing the organic phase (n-pentane) for product removal and replacing with fresh substrate. Four consecutive batches yielded ca. 27 g L?1 R-levodione from a 45 mL aqueous reaction, containing less than 17 mg (10 μM) enzyme and the reaction only stopping because of acidification. The TsER variant panel provides a robust, highly active and stereocomplementary base for further exploitation as a tool in preparative organic synthesis.
Preparation method of cis, cis-3, 5-dimethyl-1-cyclohexanol
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Paragraph 0084-0086; 0087-0090, (2020/08/18)
The invention belongs to the field of chemistry, and discloses a synthesis method of a cis, cis-3, 5-dimethyl-1-cyclohexanol compound shown as a formula (I). Acetaldehyde and ethyl acetoacetate are used as raw materials, and cis, cis-3, 5-dimethyl-1-cyclohexanol is synthesized by a series of reactions such as knoevenagel condensation, hydrolysis, decarboxylation, hydrogenation reduction, reduction, acylating chlorination, hydrolysis and the like. The raw materials and auxiliary materials of the route are simple and easily available, the reaction conditions are mild, the operation is simple andconvenient, the synthesis cost is low, and the obtained product has high chiral purity (the product/isomer ratio is 30: 1-100: 1) and is suitable for large-scale production.
Ductile Pd-Catalysed Hydrodearomatization of Phenol-Containing Bio-Oils Into Either Ketones or Alcohols using PMHS and H2O as Hydrogen Source
Di Francesco, Davide,Subbotina, Elena,Rautiainen, Sari,Samec, Joseph S. M.
supporting information, p. 3924 - 3929 (2018/09/14)
A series of phenolic bio-oil components were selectively hydrodearomatized by palladium on carbon into the corresponding ketones or alcohols in excellent yields using polymethylhydrosiloxane and water as reducing agent. The selectivity of the reaction was governed by the water concentration where selectivity to alcohol was favoured at higher water concentrations. As phenolic bio-oil examples cardanol and beech wood tar creosote were studied as substrate to the developed reaction conditions. Cardanol was hydrodearomatized into 3-pentadecylcyclohexanone in excellent yield. From beech wood tar creosote, a mixture of cyclohexanols was produced. No hydrodeoxygenation occurred, suggesting the applicability of the reported method for the production of ketone-alcohol oil from biomass. (Figure presented.).
Pinpointing a Mechanistic Switch Between Ketoreduction and “Ene” Reduction in Short-Chain Dehydrogenases/Reductases
Lygidakis, Antonios,Karuppiah, Vijaykumar,Hoeven, Robin,Ní Cheallaigh, Aisling,Leys, David,Gardiner, John M.,Toogood, Helen S.,Scrutton, Nigel S.
supporting information, p. 9596 - 9600 (2016/08/10)
Three enzymes of the Mentha essential oil biosynthetic pathway are highly homologous, namely the ketoreductases (?)-menthone:(?)-menthol reductase and (?)-menthone:(+)-neomenthol reductase, and the “ene” reductase isopiperitenone reductase. We identified a rare catalytic residue substitution in the last two, and performed comparative crystal structure analyses and residue-swapping mutagenesis to investigate whether this determines the reaction outcome. The result was a complete loss of native activity and a switch between ene reduction and ketoreduction. This suggests the importance of a catalytic glutamate vs. tyrosine residue in determining the outcome of the reduction of α,β-unsaturated alkenes, due to the substrate occupying different binding conformations, and possibly also to the relative acidities of the two residues. This simple switch in mechanism by a single amino acid substitution could potentially generate a large number of de novo ene reductases.
A Scalable Synthesis of (R,R)-2,6-Dimethyldihydro-2H-pyran-4(3H)-one
Young, Ian S.,Haley, Matthew W.,Tam, Annie,Tymonko, Steven A.,Xu, Zhongmin,Hanson, Ronald L.,Goswami, Animesh
, p. 1360 - 1368 (2015/11/02)
A scalable synthesis of (R,R)-2,6-dimethyldihydro-2H-pyran-4(3H)-one is reported. Key to this strategy is the Ti(OiPr)4-catalyzed Kulinkovich cyclopropanation of silyl protected (R)-ethyl 3-hydroxybutanoate, and subsequent oxidative fragmentati
Highly Selective Hydrogenation of Aromatic Ketones and Phenols Enabled by Cyclic (Amino)(alkyl)carbene Rhodium Complexes
Wei, Yu,Rao, Bin,Cong, Xuefeng,Zeng, Xiaoming
supporting information, p. 9250 - 9253 (2015/08/11)
Air-stable Rh complexes ligated by strongly σ-donating cyclic (amino)(alkyl)carbenes (CAACs) show unique catalytic activity for the selective hydrogenation of aromatic ketones and phenols by reducing the aryl groups. The use of CAAC ligands is essential for achieving high selectivity and conversion. This method is characterized by its good compatibility with unsaturated ketones, esters, carboxylic acids, amides, and amino acids and is scalable without detriment to its efficiency.
Copper nanoparticles from copper aluminum hydrotalcite: An efficient catalyst for acceptor- and oxidant-free dehydrogenation of amines and alcohols
Damodara, Dandu,Arundhathi, Racha,Likhar, Pravin R.
supporting information, p. 189 - 198 (2014/03/21)
An efficient and simple process for the preparation of stable nanocopper(0) on alumina [Cu(0)/Al2O3] from the inorganic composite precursor copper aluminum hydrotalcite (Cu-AlHT) by a chemical reduction method is described. Cu(0)/ Al2O3 was employed as an efficient catalyst in the acceptor- and oxidant-free dehydrogenation of various amines and alcohols to their corresponding dehydrogenated products in good to excellent yields. The stability of Cu(0)/Al2O3 was assessed by studying its recoverability and reusability in the dehydrogenation of amines and alcohols for up to five cycles.
Kinetic resolution of chiral cyclohex-2-enones by rhodium(I)/binap- catalyzed 1,2- and 1,4-additions
Kolb, Andreas,Hirner, Sebastian,Harms, Klaus,Zezschwitz, Paultheo Von
supporting information; experimental part, p. 1978 - 1981 (2012/06/18)
The feasibility of kinetic resolutions of racemic monosubstituted cyclohex-2-enones by Rh/binap-catalyzed reactions was investigated. 1,2-Addition of AlMe3 to the 5-substituted derivatives furnished allylic alcohols in the matched case, while t
