38316-05-1Relevant articles and documents
A mixed dicarboxylate strut approach to enhancing catalytic activity of a de novo urea derivative of metal-organic framework UiO-67
Siu, Paul W.,Brown, Zachary J.,Farha, Omar K.,Hupp, Joseph T.,Scheidt, Karl A.
, p. 10920 - 10922 (2013)
A hydrogen-bond donating MOF catalyst based on the UiO-67 framework, containing both urea-functionalized dicarboxylate and biphenyl-4,4′- dicarboxylate struts, was synthesized by a de novo route. The mixed strut framework has larger pore sizes and improved catalytic activity for Henry reactions than the pure strut analogue, which contains only the urea-functionalized dicarboxylate linker. The Royal Society of Chemistry 2013.
Highly efficient nanosized mesoporous CuMgAl ternary oxide catalyst
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Page/Page column 17; 21; 22-23, (2021/07/01)
Highly efficient nanosized mesoporous CuMgAl ternary oxide catalysts are provided.
Synthesis of nitroaldols through the Henry reaction using a copper(II)–Schiff base complex anchored on magnetite nanoparticles as a heterogeneous nanocatalyst
Parandeh-Khoozani, Niloufar,Moradian, Mohsen
, p. 2035 - 2054 (2021/05/21)
A Cu(II)-Schiff base complex supported on functionalized Fe3O4 magnetic nanoparticles (MNPs@Salen-Cu(II)) was obtained as a new heterogeneous nanocatalyst. The nanocomposite materials were characterized by vibrating sample magnetometer (VSM), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), Fourier transform infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA). The catalyst was used in the Henry reaction in order to accomplish one-pot synthesis of nitroaldol derivatives in green conditions. This nanocatalyst can be easily separated from media of reaction using an external magnet and reused several times without loss of its catalytic activity. Furthermore, the non-toxicity of the catalysts and the high yield of the products are other advantages of this method.
Revisit to Henry reaction by non conventional heterogeneous and efficient catalyst for nitroalcohol synthesis
Jadhav, Swati D.,Jagdale, Ashutosh A.,Patil, Rupesh C.,Patil, Suresh S.
, (2021/11/03)
A sustainable, green and efficient process for the synthesis of 2-nitro alcohol derivatives from different substituted aromatic aldehydes with nitroalkane by stirring at ambient temperature with high product yield is reported. Adoption of very mild reaction conditions, use of Calcined Eggshell (CES) as natural catalyst and simple workup are expected to contribute to the development of environmentally benign synthetic method for Henry (nitroaldol) reaction. CES is ecologically safe, inexpensive, and attractive heterogeneous base catalyst obtained from renewable resources, thus opening a new perspective for this process. Graphical abstract: [Figure not available: see fulltext.]
(3S,4S)-N-substituted-3,4-dihydroxypyrrolidines as ligands for the enantioselective Henry reaction
Rénio, Márcia R.R.,Sousa, Francisco J.P.M.,Tavares, Nélia C.T.,Valente, Artur J.M.,da Silva Serra, M. Elisa,Murtinho, Dina
, (2021/02/03)
The enantioselective Henry reaction is a very important and useful carbon–carbon bond forming reaction. The execution of this reaction requires the use of efficient chiral catalysts. In this work, in situ formed complexes of N-substituted dihydroxypyrrolidines, chiral ligands derived from L-tartaric acid and amines, were evaluated as catalysts in the enantioselective Henry reaction. The results showed that the nature of the N-substituent on the ligand significantly influences the outcome of the reaction. Best results were obtained using a Cu (II) complex of (3S,4S)-N-benzyl-3,4-dihydroxypyrrolidine, in the presence of DIPEA, for the reaction of aromatic aldehydes with nitromethane, at room temperature, originating products with er up to 92:8 (R:S) and conversions up to 96%. The interaction between the pyrrolidine ligand and the copper ion, in isopropanol, was followed by UV-vis spectrophotometry, showing a 1:1 stoichiometry and a binding constant of 4.4. The results obtained will contribute to the design and development of more efficient chiral catalysts for this type of reaction.
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).
Efficient Synthesis of α-Ketothioamides From α-Nitroketones, Amines or DMF and Elemental Sulfur Under Oxidant-Free Conditions
Zhang, Zhenlei,Yang, Jiusi,Yu, Renjie,Wu, Kairui,Bu, Jiping,Li, Shaoke,Qian, Peng,Sheng, Liangquan
supporting information, p. 5209 - 5212 (2021/10/19)
We have developed a practical, general protocol for denitration of readily available α-nitroketones with sulfur and amines to access a broad range of α-ketothioamides under mild conditions. Such a reaction proceeds under metal-, oxidant-, and catalyst-free conditions to provide synthetically useful α-ketothioamides. Furthermore, the mild reaction conditions tolerate a wide range of substrates especially for the synthesis of aliphatic α-ketothioamides which are rarely reported.
Highly Mesoporous Metal-Organic Frameworks as Synergistic Multimodal Catalytic Platforms for Divergent Cascade Reactions
Cho, Seung Hwan,Dubbu, Sateesh,Dutta, Soumen,Jang, Sun Woo,Kawano, Masaki,Kim, Junghoon,Kumar, Amit,Kumari, Nitee,Lee, In Su,Ohtsu, Hiroyoshi
supporting information, p. 3416 - 3422 (2020/02/11)
Rational engineering and assimilation of diverse chemo- and biocatalytic functionalities in a single nanostructure is highly desired for efficient multistep chemical reactions but has so far remained elusive. Here, we design and synthesize multimodal catalytic nanoreactors (MCNRs) based on a mesoporous metal-organic framework (MOF). The MCNRs consist of customizable metal nanocrystals and stably anchored enzymes in the mesopores, as well as coordinatively unsaturated cationic metal MOF nodes, all within a single nanoreactor space. The highly intimate and diverse catalytic mesoporous microenvironments and facile accessibility to the active site in the MCNR enables the cooperative and synergistic participation from different chemo- and biocatalytic components. This was shown by one-pot multistep cascade reactions involving a heterogeneous catalytic nitroaldol reaction followed by a [Pd/lipase]-catalyzed chemoenzymatic dynamic kinetic resolution to yield optically pure (>99 % ee) nitroalcohol derivatives in quantitative yields.
Ketoreductase catalyzed stereoselective bioreduction of α-nitro ketones
Wang, Zexu,Wu, Xiaofan,Li, Zhining,Huang, Zedu,Chen, Fener
, p. 3575 - 3580 (2019/04/14)
We report here the stereoselective bioreduction of α-nitro ketones catalyzed by ketoreductases (KREDs) with publicly known sequences. YGL039w and RasADH/SyADH were able to reduce 23 class I substrates (1-aryl-2-nitro-1-ethanone (1)) and ten class II substrates (1-aryloxy-3-nitro-2-propanone (4)) to furnish both enantiomers of the corresponding β-nitro alcohols, with good-to-excellent conversions (up to >99%) and enantioselectivities (up to >99% ee) being achieved in most cases. To the best of our knowledge, KRED-mediated reduction of class II α-nitro ketones (1-aryloxy-3-nitro-2-propanone (4)) is unprecedented. Select β-nitro alcohols, including the synthetic intermediates of bioactive molecules (R)-tembamide, (S)-tembamide, (S)-moprolol, (S)-toliprolol and (S)-propanolol, were stereoselectively synthesized in preparative scale with 42% to 90% isolated yields, showcasing the practical potential of our developed system in organic synthesis. Finally, the advantage of using KREDs with known sequence was demonstrated by whole-cell catalysis, in which β-nitro alcohol (R)-2k, the key synthetic intermediate of hypoglycemic natural product (R)-tembamide, was produced in a space-time yield of 178 g L?1 d?1 as well as 95% ee by employing the whole cells of a recombinant E. coli strain coexpressing RasADH and glucose dehydrogenase as the biocatalyst.
Design and development of novel Co-MOF nanostructures as an excellent catalyst for alcohol oxidation and Henry reaction, with a potential antibacterial activity
Aryanejad, Sima,Bagherzade, Ghodsieh,Moudi, Maryam
, (2019/03/17)
The novel metal–organic framework Co2(bdda)1.5(OAc)1·5H2O (UoB-3) was synthesized via a simple method at room temperature. UoB-3 was characterized by the different methods, including X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), N2-adsorption/desorption and elemental analysis. The catalytic ability of UoB-3 was detected to be excellent for primary and secondary alcohols oxidation reaction with high yields under solvent-free conditions. Moreover, UoB-3 was highly active for Henry reaction of different aldehydes with nitromethane in water as a green solvent. The nanocatalyst can be recycled for five consecutive cycles without losing its activity and structural rigidity. The antibacterial activity of UoB-3 nanostructures towards Gram-negative bacteria, Escherichia coli and Gram-positive bacteria, Bacillus cereus was also evaluated by using an inhibition zone test. These nanostructures exhibited strong antibacterial effect against both of them. The purpose of this study was the developing metal–organic framework materials with the enhanced activity in various fields.
