6125-24-2Relevant academic research and scientific papers
Expanding the Biocatalytic Toolbox with a New Type of ene/yne-Reductase from Cyclocybe aegerita
Karrer, Dominik,Gand, Martin,Rühl, Martin
, p. 2191 - 2199 (2021/02/26)
This study introduces a new type of ene/yne-reductase from Cyclocybe aegerita with a broad substrate scope including aliphatic and aromatic alkenes/alkynes from which aliphatic C8-alkenones, C8-alkenals and aromatic nitroalkenes were the preferred substrates. By comparing alkenes and alkynes, a ～2-fold lower conversion towards alkynes was observed. Furthermore, it could be shown that the alkyne reduction proceeds via a slow reduction of the alkyne to the alkene followed by a rapid reduction to the corresponding alkane. An accumulation of the alkene was not observed. Moreover, a regioselective reduction of the double bond in α,β-position of α,β,γ,δ-unsaturated alkenals took place. This as well as the first biocatalytic reduction of different aliphatic and aromatic alkynes to alkanes underlines the novelty of this biocatalyst. Thus with this study on the new ene-reductase CaeEnR1, a promising substrate scope is disclosed that describes conceivably a broad occurrence of such reactions within the chemical landscape.
Iridium-catalyzed highly chemoselective and efficient reduction of nitroalkenes to nitroalkanes in water
Chen, Yang,Liu, Changmeng,Xu, Dong,Xu, Jiaxi,Yang, Zhanhui
supporting information, p. 6050 - 6058 (2021/08/23)
An iridium-catalyzed highly chemoselective and efficient transfer hydrogenation reduction of structurally diverse nitroalkenes was realized at very low catalyst loading (S/C = up to 10000 or 20?000), using formic acid or sodium formate as a traceless hydride donor in water. Excellent functionality tolerance is also observed. The turnover number and turnover frequency of the catalyst reach as high as 18?600 and 19?200 h-1, respectively. An inert atmosphere protection is not required. The reactivities of nitroalkenes are dependent on their substitution pattern, and the pH value is a key factor to accomplish the complete conversion and excellent chemoselectivity. Purification of products is achieved by simple extraction without column chromatography. The reduction procedure is facilely amplified to 10 g scale at 10?000 S/C ratio. The potential of this green reduction in enantioselective hydrogenation has been demonstrated.
Method for high-selectivity reduction of nitroolefin C=C double bonds
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Paragraph 0053-0056, (2021/06/21)
The invention provides a method for high-selectivity reduction of nitroolefin C=C double bonds. According to the method, a bidentate nitrogen ligand-[Cp* IrCl2] complex is used as the catalyst, nitroolefin can be conveniently converted into nitroalkane, the catalytic efficiency is extremely high, and the substrate conversion rate is 99% or above. The high-purity nitroalkane can be separated through simple extraction, liquid separation and solvent removal under reduced pressure. The selected solvent is water or a mixture of water and a hydrophilic solvent. The method is green, environment-friendly and high in reaction efficiency. The nitroalkane compound prepared by the invention is a very important organic intermediate, and has wide application in the fields of national defense, pesticide, biology, medicine, fine chemical engineering and the like.
Metal-Free Deoxygenation of Chiral Nitroalkanes: An Easy Entry to α-Substituted Enantiomerically Enriched Nitriles
Pirola, Margherita,Faverio, Chiara,Orlandi, Manuel,Benaglia, Maurizio
supporting information, p. 10247 - 10250 (2021/06/18)
A metal-free, mild and chemodivergent transformation involving nitroalkanes has been developed. Under optimized reaction conditions, in the presence of trichlorosilane and a tertiary amine, aliphatic nitroalkanes were selectively converted into amines or nitriles. Furthermore, when chiral β-substituted nitro compounds were reacted, the stereochemical integrity of the stereocenter was maintained and α-functionalized nitriles were obtained with no loss of enantiomeric excess. The methodology was successfully applied to the synthesis of chiral β-cyano esters, α-aryl alkylnitriles, and TBS-protected cyanohydrins, including direct precursors of four active pharmaceutical ingredients (ibuprofen, tembamide, aegeline and denopamine).
A stable well-defined copper hydride cluster consolidated with hemilabile phosphines
Yuan, Shang-Fu,Luyang, Heng-Wang,Lei, Zhen,Wan, Xian-Kai,Li, Jiao-Jiao,Wang, Quan-Ming
, p. 4315 - 4318 (2021/05/05)
Copper hydrides are very useful in hydrogenation reactions. We report a stable Stryker-type copper hydride reagent protected by hemilabile phosphines: [Cu8H6(dppy)6](OTf)2(Cu8-H, dppy = diphenylphosphino-2-pyridine). The metal core of this cluster has a bicapped octahedral configuration, and the copper-bound hydrides each triply bridges over a triangular face of the octahedron. This cluster is attractive due to its facile preparation and excellent stability under ambient conditions. The comparable activity and selectivity both in the stoichiometric and catalytic reactions makeCu8-Ha promising alternative to Stryker's reagent.
Nitroalkene reduction in deep eutectic solvents promoted by BH3NH3
Benaglia, Maurizio,Boselli, Monica Fiorenza,Faverio, Chiara,Gonzalez, Patricia Camarero,Puglisi, Alessandra
supporting information, p. 1041 - 1047 (2021/05/17)
Deep eutectic solvents (DESs) have gained attention as green and safe as well as economically and environmentally sustainable alternative to the traditional organic solvents. Here, we report the combination of an atom-economic, very convenient and inexpensive reagent, such as BH3NH3, with bio-based eutectic mixtures as biorenewable solvents in the synthesis of nitroalkanes, valuable precursors of amines. A variety of nitrostyrenes and alkyl-substituted nitroalkenes, including α- and β-substituted nitroolefins, were chemoselectively reduced to the nitroalkanes, with an atom economy-oriented, simple and convenient experimental procedure. A reliable and easily reproducible protocol to isolate the product without the use of any organic solvent was established, and the recyclability of the DES mixture was successfully investigated.
METTL3 INHIBITORY COMPOUNDS
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Paragraph 00290; 00573, (2020/10/20)
The present invention relates to compounds of formula (I) that function as inhibitors of METTL3 (N6-adenosine-methyltransferase 70 kDa subunit) enzyme activity: X-Y-Z5 (I) wherein X, Y and Z are each as defined herein. The present invention also relates to processes for the preparation of these compounds, to pharmaceutical compositions comprising them, and to their use in the treatment of proliferative disorders, such as cancer, and autoimmune diseases, as well as other diseases or conditions in which METTL3 activity 10 is implicated.
Reduction of Activated Alkenes by PIII/PV Redox Cycling Catalysis
Longwitz, Lars,Werner, Thomas
supporting information, p. 2760 - 2763 (2020/02/05)
The carbon–carbon double bond of unsaturated carbonyl compounds was readily reduced by using a phosphetane oxide catalyst in the presence of a simple organosilane as the terminal reductant and water as the hydrogen source. Quantitative hydrogenation was observed when 1.0 mol % of a methyl-substituted phosphetane oxide was employed as the catalyst. The procedure is highly selective towards activated double bonds, tolerating a variety of functional groups that are usually prone to reduction. In total, 25 alkenes and two alkynes were hydrogenated to the corresponding alkanes in excellent yields of up to 99 %. Notably, less active poly(methylhydrosiloxane) could also be utilized as the terminal reductant. Mechanistic investigations revealed the phosphane as the catalyst resting state and a protonation/deprotonation sequence as the crucial step in the catalytic cycle.
Reduction method of nitroolefin
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Paragraph 0041-0043, (2019/12/11)
Relating to the technical field of organic synthesis, the invention particularly discloses a reduction method of nitroolefin. The method includes: adding a compound 1 into a mixed solvent of alcohol/water in a certain ratio, adding a metal borohydride at 0-50DEG C, and carrying out stirring reaction; concentrating the obtained solution to a constant weight, and adding ethyl acetate and a saturatedammonium chloride solution into the concentrate; separating the liquid to obtain an upper ethyl acetate layer, and conducting drying and concentrating to obtain a reduction product compound 2. The synthesis method provided by the invention is suitable for aromatic rings and straight-chain alkanes, can control dimer impurities at 3.0% or below and the HPLC purity of aliphatic or aromatic nitro compounds at 95.0% or above. The synthesis method provided by the invention has the advantages of cheap raw materials, green and environment-friendly process, economical efficiency and practicability, and is suitable for industrial production.
Substituted Pyrrolidine Amides II
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Paragraph 0452; 0455; 0456, (2019/07/03)
The invention relates to compounds according to general formula (I), which act as modulators of the glucocorticoid receptor and can be used in the treatment and/or prophylaxis of disorders which are at least partially mediated by the glucocorticoid receptor.
