85536-83-0Relevant academic research and scientific papers
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.]
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.
One-Pot Enzyme Cascade Catalyzed Asymmetrization of Primary Alcohols: Synthesis of Enantiocomplementary Chiral β-Nitroalcohols
Chatterjee, Ayon,Kumar Padhi, Santosh,Rao, D. H. Sreenivasa
supporting information, p. 5310 - 5318 (2021/10/02)
Biocatalytic asymmetrization of inexpensive and stable primary alcohols to prepare enantioenriched β-nitroalcohols is an important development in green chemistry for the production of chiral pharmaceutical intermediates. Herein, we report a one-pot, two-step cascade reaction sequence in which first benzylic alcohols were oxidized to produce corresponding benzaldehydes using horse liver alcohol dehydrogenase (HLADH). The in situ generated aldehydes were then reacted in a biphasic medium with nitromethane by Arabidopsis thaliana hydroxynitrile lyase (AtHNL) or Baliospermum montanum HNL (BmHNL) catalyzed Henry reaction to produce stereoselective β-nitroalcohols with (R) or (S) configuration, respectively. Using HLADH-AtHNL, (R)-β-nitroalcohols were obtained in up to 64% conversion, and HLADH-BmHNL, (S)-β-nitroalcohols in up to 70% conversion, while in both cases excellent stereoselectivity (up to >99% ee) was achieved. The concept was proven by functionalization of sp3 C?H bond of ten simple achiral benzylic alcohols to enantiocomplementary chiral β-nitroalcohols. (Figure presented.).
Synthesis, Characterization and Catalytic Activity of Magnetic KI@Fe3O4 Nanoparticles for Henry Reaction Under Solvent Free Conditions
Rokhum, Lalthazuala,Pathak, Gunindra
, p. 2887 - 2898 (2019/05/28)
Abstract: In this paper, we, for the first time reported the synthesis of KI loaded Fe3O4 nanoparticles (KI@Fe3O4 NPs) and investigated its applications in the synthesis of β-nitroalcohol via Henry reaction at room temperature under solvent-free conditions. The synthesized KI@Fe3O4 nanoparticle was characterized by SEM, HRTEM, XRD, XPS, EDX, VSM and FT-IR spectroscopy techniques. The XRD peaks at 2θ = 21.9, 25.65, 33.54, 36.35, 40.97, 42.81, 44.79, 54.43, 57.37, 58.83 and 63.13° corresponds to the formation of crystalline KI@Fe3O4 NPs. The activity of the catalyst by varying the amount of KI loading on Fe3O4 NPs was also investigated. Mild reaction conditions, good yield, short reaction time, solvent-free conditions, easy recoverability and recyclability of the nanocatalysts are the major advantages of our method. Graphical Abstract: [Figure not available: see fulltext.].
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.
Ketoreductase catalyzed stereoselective bioreduction of α-nitro ketones
Wang, Zexu,Wu, Xiaofan,Li, Zhining,Huang, Zedu,Chen, Fener
supporting information, 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.
Base-catalyzed reactions enhanced by solid acids: Amine-catalyzed nitroaldol (Henry) reactions enhanced by silica gel or mesoporous silica SBA-15
Tanemura, Kiyoshi,Suzuki, Tsuneo
supporting information, p. 392 - 396 (2017/12/28)
The reactions of various aldehydes with CH3NO2 catalyzed by Et3N, n-C6H13NH2, and Me2N(CH2)2NH2 were accelerated by the addition of silica gel to give aromatic (aliphatic) β-nitroalcohols, aromatic nitroalkenes, and aromatic 1,3-dinitroalkanes, respectively. Mesoporous silica SBA-15 showed higher activity than silica gel for the synthesis of aromatic nitroalkenes by the reactions of the corresponding aldehydes with CH3NO2 catalyzed by n-C6H13NH2.
Biphenyl-Based Bis(thiourea) Organocatalyst for Asymmetric and syn -Selective Henry Reaction
Otevrel, Jan,Bobal, Pavel
supporting information, p. 593 - 603 (2017/01/25)
A scalable, efficient and chromatography-free synthesis of a new enantiopure C 2-symmetric bis(thiourea) catalyst was accomplished from a readily available starting material. The developed strategy could be conducted on a multi-gram scale. Both the prepared enantiomers of the bis(thiourea) organocatalyst have been tested in the asymmetric Henry reaction under thoroughly optimized conditions during which an unusual solvent effect on enantioselectivity was found. The corresponding adducts were obtained in excellent yields with good to excellent enantioselectivities. The achieved high reactivity and enantioselectivity in the nitroaldol reaction of nitroalkanes with aromatic aldehydes suggests promising potential for this catalyst. Moreover, a significant syn-diastereoselectivity was observed.
Salen-Based Covalent Organic Framework
Li, Li-Hua,Feng, Xiao-Lin,Cui, Xiao-Hui,Ma, Yun-Xiang,Ding, San-Yuan,Wang, Wei
supporting information, p. 6042 - 6045 (2017/05/09)
The Salen unit represents one of the most important ligands in coordination chemistry. We report herein the first example of a Salen-based covalent organic framework (COF), in which both the construction of the COF structure and the functionalization with Salen moieties have been realized in a single step. Due to its structural uniqueness, the obtained COF material, Salen-COF, possesses high crystallinity and excellent stability. Based on this, a series of metallo-Salen-based COFs were prepared via metalation for further applications.
Polymer supported DMAP: An easily recyclable organocatalyst for highly atom-economical Henry reaction under solvent-free conditions
Das, Diparjun,Pathak, Gunindra,Rokhum, Lalthazuala
, p. 104154 - 104163 (2016/11/17)
Polymer supported catalysts are regarded as a borderline class of catalysts, which retains the advantages of homogeneous catalysts while securing the ease of recovery by simple filtration and workup of heterogeneous systems. Additionally, such catalysts are less hygroscopic due to the long polymer backbone. Here we have demonstrated that a catalytic amount of polymer supported DMAP (10 mol%) can lead to excellent conversion of an equimolar mixture of aldehyde and nitroalkane exclusively into β-nitroalcohols via the Henry reaction. Unlike most of the commonly used catalysts, polymer supported DMAP can be recovered by simple filtration and reused several times, thereby reducing the operational cost. High synthetic efficiency, total atom economy, near quantitative yields, mild reaction conditions, operational simplicity, easy recovery and reusability of the catalyst, solvent-free reaction conditions and avoidance of traditional reaction workup make the protocol highly significant from Green and Sustainable Chemistry perspectives.
