- Studies of the Henry reaction catalyzed by Cu-O and Zn-O complexes with dimethoxysilane-bridged derivatives
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Dimethyldimethoxysilane, methylphenyldimethoxysilane, and diphenyldimethoxysilane have been synthesized by a one-step, simple method and used as catalysts in the Henry reaction with Cu(OAc)2.H2O and Zn(OAc)2.2H2O, affording 60-96% conversion under the optimum catalytic conditions. Springer Science+Business Media B.V. 2010.
- Mei, Luo,Yang, Han Bing,Song, Shu
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- Revisit to Henry reaction by non conventional heterogeneous and efficient catalyst for nitroalcohol synthesis
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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.]
- Jadhav, Swati D.,Patil, Rupesh C.,Jagdale, Ashutosh A.,Patil, Suresh S.
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p. 593 - 606
(2021/11/03)
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- Synthesis of DPA-triazole structures and their application as ligand for metal catalyzed organic reactions
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In this work, the use of DPA-triazole (DPA = dipicolylamine) molecules as ligands for metal catalyzed organic reactions has been investigated. A small library of ligands has been prepared by a CuAAC (click reaction) between propargyl-DPA and different azi
- Colombo Dugoni, Greta,Sacchetti, Alessandro,Urra Mancilla, Carolina
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- Synthesis of nitroaldols through the Henry reaction using a copper(II)–Schiff base complex anchored on magnetite nanoparticles as a heterogeneous nanocatalyst
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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.
- Parandeh-Khoozani, Niloufar,Moradian, Mohsen
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p. 2035 - 2054
(2021/05/21)
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- Metal-Free Deoxygenation of Chiral Nitroalkanes: An Easy Entry to α-Substituted Enantiomerically Enriched Nitriles
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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).
- Pirola, Margherita,Faverio, Chiara,Orlandi, Manuel,Benaglia, Maurizio
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supporting information
p. 10247 - 10250
(2021/06/18)
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- Efficient Synthesis of α-Ketothioamides From α-Nitroketones, Amines or DMF and Elemental Sulfur Under Oxidant-Free Conditions
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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.
- Zhang, Zhenlei,Yang, Jiusi,Yu, Renjie,Wu, Kairui,Bu, Jiping,Li, Shaoke,Qian, Peng,Sheng, Liangquan
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supporting information
p. 5209 - 5212
(2021/10/19)
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- Copper complexes of 1,4-diazabutadiene ligands: Tuning of metal oxidation state and, application in catalytic C-C and C-N bond formation
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Reaction of 1,4-diazabutadiene (p-RC6H4N = C(H)(H)C = NC6H4R-p; R = OCH3, CH3, H and Cl; abbreviated as L-R) with CuCl2·2H2O in methanol at ambient temperature (25 °C) affords a group of doubly chloro-bridged dicopper complexes of type [{CuI(L-R)Cl}2], designated as 1-R. Similar reaction carried out in acetonitrile furnishes a family of doubly chloro-bridged dicopper complexes of type [{CuII(L-R)Cl2}2], designated as 2-R. Molecular structures of 1-OCH3 and 2-OCH3 have been determined by X-ray crystallography. While copper(I) is having a nearly tetrahedral N2Cl2 coordination sphere in 1-OCH3, the N2Cl3 coordination sphere around copper(II) is distorted square pyramidal in nature in 2-OCH3. Isolated 2-R complexes, on dissolution in methanol, are found to undergo facile reduction of the metal center to generate the corresponding 1-R complexes. The 1-R and 2-R complexes show intense absorptions in the visible and ultraviolet regions. Cyclic voltammetry on the 1-R and 2-R complexes shows both metal-centered and ligand centered redox responses. The 1-R complexes are found to efficiently catalyze C-N cross-coupling reactions between arylboronic acids and aryl amines; while the 2-R complexes display notable catalytic efficiency for nitroaldol reactions.
- Mukherjee, Aparajita,Basu, Semanti,Bhattacharya, Samaresh
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- Waste-to-useful: A biowaste-derived heterogeneous catalyst for a green and sustainable Henry reaction
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Owing to the depletion of resources coupled with increasing waste generation, the conversion of waste biomass to value-added materials has gained interest. Here, we report for the first time the application of Musa acuminata (banana) peel ash (MAPA) as a heterogeneous catalyst for C-C bond formation via a Henry reaction under solvent-free conditions at ambient temperature. The catalyst was well characterized using different analytical techniques like FT-IR, SEM, TEM-EDS, XRD, XRF, XPS, BET and TGA, along with basicity determination by a Hammett indicator test and titration method. An excellent yield of nitroalcohol was obtained within 15-30 minutes. No dehydrated product was observed. The catalyst used in these studies has the advantage of being a waste material and is hence low-cost, easily prepared, recyclable and environmentally friendly. In addition, the use of a biogenic renewable catalyst, its atom economy, and room temperature and solvent-free reaction conditions and the avoidance of column chromatography make the protocol highly significant from green and sustainable chemistry perspectives.
- Rajkumari, Kalyani,Das, Diparjun,Pathak, Gunindra,Rokhum, Lalthazuala
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p. 2134 - 2140
(2019/02/05)
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- Microwave-assisted synthesis of urea-containing zirconium metal-organic frameworks for heterogeneous catalysis of Henry reactions
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Here we report the facile preparation of a urea-containing UiO-68 isoreticular zirconium metal-organic framework (MOF) with mixed dicarboxylate struts by utilizing a microwave-assisted heating method. It can work as an efficient hydrogen-bond-donating heterogeneous catalyst for Henry reactions of benzaldehydes and nitroalkanes. This mixed strut MOF exhibits improved catalytic activity compared to the pure urea-functionalized linker based analogue.
- Zhang, He,Gao, Xue-Wang,Wang, Li,Zhao, Xinsheng,Li, Qiu-Yan,Wang, Xiao-Jun
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p. 1358 - 1362
(2019/03/04)
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- Design and development of novel Co-MOF nanostructures as an excellent catalyst for alcohol oxidation and Henry reaction, with a potential antibacterial activity
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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.
- Aryanejad, Sima,Bagherzade, Ghodsieh,Moudi, Maryam
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- Synthesis, Characterization and Catalytic Activity of Magnetic KI@Fe3O4 Nanoparticles for Henry Reaction Under Solvent Free Conditions
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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.].
- Rokhum, Lalthazuala,Pathak, Gunindra
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p. 2887 - 2898
(2019/05/28)
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- Production of (S)-β-Nitro Alcohols by Enantioselective C?C Bond Cleavage with an R-Selective Hydroxynitrile Lyase
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Hydroxynitrile lyase (HNL)-catalysed stereoselective synthesis of β-nitro alcohols from aldehydes and nitroalkanes is considered an efficient biocatalytic approach. However, only one S-selective HNL—Hevea brasiliensis (HbHNL)—exists that is appropriate for the synthesis of (S)-β-nitro alcohols from the corresponding aldehydes. Further, synthesis catalysed by HbHNL is limited by low specific activity and moderate yields. We have prepared a number of (S)-β-nitro alcohols, by kinetic resolution with the aid of an R-selective HNL from Arabidopsis thaliana (AtHNL). Optimization of the reaction conditions for AtHNL-catalysed stereoselective C?C bond cleavage of racemic 2-nitro-1-phenylethanol (NPE) produced (S)-NPE (together with benzaldehyde and nitromethane, largely from the R enantiomer) in up to 99 % ee and with 47 % conversion. This is the fastest HNL-catalysed route known so far for the synthesis of a series of (S)-β-nitro alcohols. This approach widens the application of AtHNL for the synthesis not only of (R)- but also of (S)-β-nitro alcohols from the appropriate substrates. Without the need for the discovery of a new enzyme, but rather by use of a retro-Henry approach, it was used to generate a number of (S)-β-nitro alcohols by taking advantage of the substrate selectivity of AtHNL.
- Rao, D. H. Sreenivasa,Padhi, Santosh Kumar
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p. 371 - 378
(2019/01/08)
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- Ketoreductase catalyzed stereoselective bioreduction of α-nitro ketones
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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.
- Wang, Zexu,Wu, Xiaofan,Li, Zhining,Huang, Zedu,Chen, Fener
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supporting information
p. 3575 - 3580
(2019/04/14)
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- High-nitrogen containing covalent triazine frameworks as basic catalytic support for the Cu-catalyzed Henry reaction
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Functionalization of porous organic frameworks by a rational design of the monomer allows to prepare tailor-made materials. The use of nitrogen-based polydentate building blocks provides specific and versatile functional groups to allow a robust binding site and/or ligand for metal complexes. In this regard, a rigid and planar tris-bidentate ligand-based 5,6,11,12,17,18-hexaazatrinaphthylene (HATN) ligand was employed for the preparation of highly porous and stable Covalent Triazine Frameworks (CTFs). The resulting HATN-based CTF exhibits a remarkably high BET surface area of 1684 m2/g and a total pore volume of 0.79 cm3/g. After post-synthetic metalation with a Cu(OAc)2 complex, it can be utilized as an efficient heterogeneous catalyst for the Henry reaction of aromatic aldehydes and nitromethane under mild reaction conditions. The Cu@HATN-CTF catalyst exhibit an excellent catalytic performance and a higher TON than the conventional Cu-based porous materials. This is probably due to the geometry and the electronic configuration effect, as the paddlewheel structure of the complex is broken upon grafting onto the HATN-CTF.
- Tahir, Norini,Wang, Guangbo,Onyshchenko, Iuliia,De Geyter, Nathalie,Leus, Karen,Morent, Rino,Van Der Voort, Pascal
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p. 242 - 248
(2019/06/24)
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- Chiral-Organotin-Catalyzed Kinetic Resolution of Vicinal Amino Alcohols
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A highly efficient kinetic resolution of racemic amino alcohols has been achieved for the first time with a chiral tin catalyst. A chiral organotin compound with 3,4,5-trifluorophenyl groups at the 3,3′-positions of the binaphthyl framework enabled this transformation with excellent yield and high enantioselectivity. The process tolerates aryl- and alkyl-substituted amino alcohols and a variety of other substrates, affording the corresponding products in high enantioselectivity and with s factors up to >500.
- Yang, Hui,Zheng, Wen-Hua
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supporting information
p. 16177 - 16180
(2019/11/03)
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- Base-catalyzed reactions enhanced by solid acids: Amine-catalyzed nitroaldol (Henry) reactions enhanced by silica gel or mesoporous silica SBA-15
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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.
- Tanemura, Kiyoshi,Suzuki, Tsuneo
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supporting information
p. 392 - 396
(2017/12/28)
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- An ionic liquid gel: A heterogeneous catalyst for Erlenmeyer-Plochl and Henry reactions
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An ionic liquid gel has been prepared by entrapping 1-butyl-3-methylimidazolium hydroxide ([Bmim]OH) in an aqueous agar gel. The ionic liquid gel has been characterized by Fourier transform infrared (FT-IR), Fourier transform Raman (FT-Raman) spectroscopy, scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and energy dispersive X-ray analysis (EDX). The ionic liquid gel has been successfully employed as a heterogeneous catalyst in the Erlenmeyer-Plochl reaction involving aldehydes, hippuric acid and acetic anhydride as well as in the Henry reaction between aldehydes and nitromethane in ethanol at room temperature. The heterogeneity of the ionic liquid gel has been confirmed by conducting hot filtration tests and leaching studies. Additionally, the ionic liquid gel could be easily recovered by simple filtration and reused five times without significant loss in catalytic activity.
- Jagadale, Megha,Naikwade, Altafhusen,Salunkhe, Rajashri,Rajmane, Mohan,Rashinkar, Gajanan
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p. 10993 - 11005
(2018/07/06)
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- Organocatalytic asymmetric Michael/hemiacetalization/acyl transfer reaction of α-nitroketones with o-hydroxycinnamaldehydes: Synthesis of 2,4-disubstituted chromans
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An organocatalytic asymmetric cascade Michael/hemiketalization/acyl transfer reaction between o-hydroxycinnamaldehydes and α-nitroketones is developed. Prolinol TMS ether catalyst in combination with benzoic acid was found to be the most effective for this reaction which proceeds through an equilibrium of lactols to provide a single diastereomer of enantiopure 2,4-disubstituted chromans.
- Maity, Rajendra,Pan, Subhas Chandra
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supporting information
p. 1598 - 1608
(2018/03/08)
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- A three-dimensional (3D) manganese (II) coordination polymer: Synthesis, structure and catalytic activities
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A new Mn (II)-containing coordination polymer, [Mn6(Ipa)6(ad)?6H2O] (1; Ipa?=?isophthalate ligand; ad?=?adenine), was synthesized by reacting hydrated manganese nitrate with isophthalic acid and adenine under solvothermal
- Pal, Souvik,Maiti, Sudip,Nayek, Hari Pada
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- Copper(II) and Sodium(I) Complexes based on 3,7-Diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane-5-oxide: Synthesis, Characterization, and Catalytic Activity
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The reaction of 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) with metal salts of CuII or NaI/NiII under mild conditions led to the oxidized phosphane derivative 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane-5-oxide (DAPTA=O) and to the first examples of metal complexes based on the DAPTA=O ligand, that is, [CuII(μ-CH3COO)2(κO-DAPTA=O)]2 (1) and [Na(1κOO′;2κO-DAPTA=O)(MeOH)]2(BPh4)2 (2). The catalytic activity of 1 was tested in the Henry reaction and for the aerobic 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO)-mediated oxidation of benzyl alcohol. Compound 1 was also evaluated as a model system for the catechol oxidase enzyme by using 3,5-di-tert-butylcatechol as the substrate. The kinetic data fitted the Michaelis–Menten equation and enabled the obtainment of a rate constant for the catalytic reaction; this rate constant is among the highest obtained for this substrate with the use of dinuclear CuII complexes. DFT calculations discarded a bridging mode binding type of the substrate and suggested a mixed-valence CuII/CuI complex intermediate, in which the spin electron density is mostly concentrated at one of the Cu atoms and at the organic ligand.
- Mahmoud, Abdallah G.,Guedes da Silva, M. Fátima C.,?liwa, Ewelina I.,Smoleński, Piotr,Kuznetsov, Maxim L.,Pombeiro, Armando J. L.
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p. 2868 - 2880
(2018/09/20)
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- Organocatalytic Asymmetric Domino Michael/Acyl Transfer Reaction Between α-Nitroketones and in situ-Generated ortho-Quinone Methides: Route to 2-(1-Arylethyl)phenols
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An organocatalytic asymmetric domino Michael/acyl transfer reaction between α-nitroketones and o-quinone methides is disclosed. o-Quinone methides are generated in situ from 2-sulfonylmethylphenols in basic medium. With 10 mol% of bifunctional squaramide catalyst, high yields and excellent enantioselectivities are achieved for a variety of O-acyl 2-(1-arylethyl)phenols under mild reaction condition. (Figure presented.).
- Gharui, Chandan,Behera, Debasmita,Pan, Subhas Chandra
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supporting information
p. 4502 - 4508
(2018/11/10)
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- A amide preparation method of the compound
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The invention discloses a preparation method for an amide compound. The method comprises the steps of: a. taking R1CHO and R2CH2NO2, adding a catalyst and R3CN, carrying out stirring reaction for 24h-48h at 0DEG C-40DEG C to obtain a reaction liquid; and
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Paragraph 0110; 0111; 0112; 0113
(2017/06/02)
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- A nitroaryloxy aromatic preparation method (by machine translation)
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The invention discloses a nitroaryloxy aromatic preparation method, comprises the following steps: a, will R1 CHO, R2 CH2 NO2 , Catalyst and a polar organic solvent evenly, 0 °C -40 °C stirring for 6 hours -48 h
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Paragraph 0104; 0105; 0106; 0107; 0108
(2017/05/23)
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- A NbO type Cu(II) metal-organic framework showing efficient catalytic activity in the Friedl?nder and Henry reactions
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A three-dimensional NbO type porous metal-organic framework 1 containing both tertiary amine groups and paddle wheel dinuclear Cu2(COO)4 secondary building units as the active centre was synthesized at room temperature. The activated
- Gupta, Anoop K.,De, Dinesh,Bharadwaj, Parimal K.
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p. 7782 - 7790
(2017/07/11)
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- A porous two-dimensional Zn(II)-coordination polymer exhibiting SC-SC transmetalation with Cu(II): Efficient heterogeneous catalysis for the Henry reaction and detection of nitro explosives
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The linker 5-(benzylamino)isophthalic acid (H2L) forms a robust 2D Zn(ii)-coordination polymer, {[Zn8(L)6(μ3-OH)4(H2O)6]·(DMF)·(H2O)2.5}n(1Z
- Gupta, Mayank,De, Dinesh,Pal, Sanchari,Pal, Tapan K.,Tomar, Kapil
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supporting information
p. 7619 - 7627
(2017/07/10)
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- Organocatalytic Asymmetric Michael/Hemiketalization/Retro-aldol Reaction of α-Nitroketones with Unsaturated Pyrazolones: Synthesis of 3-Acyloxy Pyrazoles
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An organocatalytic asymmetric cascade Michael/hemiketalization/retro-aldol reaction between unsaturated pyrazolones and α-nitroketones is described. A bifunctional thiourea catalyst was found to be efficient for this reaction. With 10 mol % of catalyst, high yields as well as excellent enantioselectivities are attained for a variety of 3-acyloxy pyrazoles under mild reaction conditions.
- Maity, Rajendra,Gharui, Chandan,Sil, Arun K.,Pan, Subhas Chandra
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supporting information
p. 662 - 665
(2017/02/10)
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- Copper-Catalyzed N-Arylation of Nitroenamines with Diaryliodonium Salts
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A novel synthetic methodology was developed for the N-arylation of nitroenamine derivatives utilizing diaryliodonium triflates and copper(I) chloride as a catalyst. The procedure enables the easy aryl transfer from the hypervalent species under mild catalytic conditions with unusual heteroatom preference and high efficiency.
- Aradi, Klára,Mészáros, ádám,Tóth, Balázs L.,Vincze, Zoltán,Novák, Zoltán
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p. 11752 - 11764
(2017/11/24)
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- Synthesis, characterization and heterogeneous base catalysis of amino functionalized lanthanide metal-organic frameworks
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Lanthanide metal-organic frameworks (Ln-MOFs) are featured by their tolerance to water and dense structure. In this work, an amine-functionalized Ln-MOF was facilely synthesized by coordination of terbium with 2-aminoterephthalic acid under the condition of microwave irradiation. The crystal structure was characterized by single crystal X-ray diffraction, FT-IR, Raman, TG-DTA and XPS analysis. The basic catalytic activity of the NH2-Tb-MOF was evaluated for Knoevenagel condensation and Henry reactions. Apart from the high activity and 100% selectivity to the condensation product, the NH2-Tb-MOF catalyst could be easily recycled and reused owing to the high stability of the MOF framework formed by coordination of Tb3+ with carboxylic groups. Remarkably, the NH2-Tb-MOF exhibited size-selective catalysis to substrates. For the small-sized reactants, it displayed comparable activity to the homogeneous catalyst of aniline owing to the high dispersion of NH2? active sites and the low diffusion limits. However, in the same reaction system, extremely poor activity in Knoevenagel condensation and Henry reaction for the bulky substrate 4-(tert-butyl) benzaldehyde was observed due to the both effects of substitute and inhibition of diffusion into the micropores. Crystal structure analysis provided a mechanistic evidence that the heterogeneous base catalysis arose from the amino groups densely distributed inside the micropores.
- Huang, Jinping,Li, Chunmei,Tao, Lingling,Zhu, Huilin,Hu, Gang
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p. 853 - 860
(2017/06/27)
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- Polymer supported DMAP: An easily recyclable organocatalyst for highly atom-economical Henry reaction under solvent-free conditions
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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.
- Das, Diparjun,Pathak, Gunindra,Rokhum, Lalthazuala
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p. 104154 - 104163
(2016/11/17)
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- Application of natural feedstock extract: The Henry reaction
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For the first time, we have successfully performed the Henry reaction in neat 'Natural Feedstock Extract' at room temperature. Herein, we used two most abundant natural feedstock extracts such as 'Water Extract of Banana' (WEB) and 'Water Extract of Rice Straw Ash' (WERSA). This protocol is highly advantageous owing to the employment of natural feedstock as green reaction media resulting in significant novelty and advancement with respect to green and sustainable chemistry.
- Surneni, Naresh,Barua, Nabin C.,Saikia, Bishwajit
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supporting information
p. 2814 - 2817
(2016/06/09)
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- Vasicine from Adhatoda vasica as an organocatalyst for metal-free Henry reaction and reductive heterocyclization of o-nitroacylbenzenes
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Vasicine, a quinazoline alkaloid, from the leaves of Adhatoda vasica, has been utilized as an efficient catalyst for metal and base free Henry reaction of various aldehydes with nitro alkanes. The method can be used in the synthesis of various β-nitro alcohols under mild reaction conditions without use of hazardous organic solvents and expensive catalysts. Vasicine is also applied successfully for one pot synthesis of 2,1-benzisoxazoles from o-nitroacylbenzenes in good yields under mild conditions.
- Sharma, Sushila,Kumar, Manoranjan,Bhatt, Vinod,Nayal, Onkar S.,Thakur, Maheshwar S.,Kumar, Neeraj,Singh, Bikram,Sharma, Upendra
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supporting information
p. 5003 - 5008
(2016/10/25)
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- Dendronized piperidine: Highly effective and recyclable catalysts for Henry reaction
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Two types of dendronized tertiary amines were synthesized by attaching piperidine to the core of a Fréchet-type dendrimer or to the end of an alkyl chain that is linked to the dendritic core. The relationship between structure and property of the catalysts in the Henry reaction of 2-nitrobenzaldehyde and nitromethane was established. It was observed that the attachment of piperidine to the dendritic sector by using a hexamethylene chain effectively avoids the scenario of dendritic shell encapsulation. And the 4-G3′ catalyst of third-generation with dendritic link exhibits excellent catalytic performance, and can be recycled ten times without a significant loss of activity.
- Yi, Bing,Yin, Yanyan,Yi, Ziqi,Zhou, Wei,Liu, Haitao,Tan, Nianyuan,Yang, Hai
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supporting information
p. 2320 - 2323
(2016/05/10)
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- Microporous polyurethane material for size selective heterogeneous catalysis of the Knoevenagel reaction
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The first polyurethane material which is microporous (BET surface area of 312 m2 g-1) is prepared by solvothermal synthesis and acts as highly efficient and recyclable heterogeneous catalyst in the Knoevenagel condensation showing si
- Dey, Sandeep Kumar,De Sousa Amadeu, Nader,Janiak, Christoph
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supporting information
p. 7834 - 7837
(2016/07/06)
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- Keratin protein-catalyzed nitroaldol (henry) reaction and comparison with other biopolymers
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Here we describe a preliminary investigation on the ability of natural keratin to catalyze the nitroaldol (Henry) reaction between aldehydes and nitroalkanes. Both aromatic and heteroaromatic aldehydes bearing strong or moderate electron-withdrawing group
- H?ring, Marleen,Pettignano, Asja,Quignard, Fran?oise,Tanchoux, Nathalie,Díaz, David Díaz
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- Silver comes into play: Henry reaction and domino cycloisomerisation sequence catalysed by [Ag(i)(Pc-L)] complexes
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We report herein the synthesis of new pyridine-containing macrocyclic ligands (Pc-L) bearing a non-innocent pendant arm, by exploiting both chiral and functional properties of natural amino acids. The obtained macrocyclic ligands were employed to synthesize well-defined cationic silver(i) complexes that were shown to be competent catalysts for the Henry (nitroaldol) reaction. Good to excellent yields and full selectivity in the β-nitroalcohol product were obtained starting from electron-poor aromatic aldehydes or other activated aldehydes such as furfural under mild reaction conditions. The straightforward synthesis of the macrocyclic ligands starting from cheap commercially available starting materials allowed the introduction of a suitable basic functionality into the ligand pendant arm, thus providing a bifunctional catalyst. Based on our previous experience in the [Ag(i)(Pc-L)] catalysed domino addition/cycloisomerisation reaction of o-alkynylbenzaldehydes and nucleophiles, the synthesis of isochromenes coupling the Henry reaction and the cycloisomerisation in a single step was subsequently explored. Although with low selectivity, [Ag(i)(Pc-L)] cationic complexes were able to promote such a cascade reaction and a possible mechanism based on experimental evidence has been proposed.
- Tseberlidis, Giorgio,Dell'Acqua, Monica,Valcarenghi, Daniele,Gallo, Emma,Rossi, Elisabetta,Abbiati, Giorgio,Caselli, Alessandro
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p. 97404 - 97419
(2016/10/25)
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- Stereoselective reaction of 2-carboxythioesters-1,3-dithiane with nitroalkenes: An organocatalytic strategy for the asymmetric addition of a glyoxylate anion equivalent
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An efficient organocatalytic methodology has been developed to perform the stereoselective addition of 2-carboxythioesters-1,3-dithiane to nitroalkenes. Under mild reaction conditions γ-nitro-β-aryl-α-keto esters with up to 92% ee were obtained, realizing a formal catalytic stereoselective conjugate addition of the glyoxylate anion synthon. The reaction products are versatile starting materials for further synthetic transformations; for example, the simultaneous reduction of the nitro group and removal of the dithiane ring was accomplished, allowing the preparation of a GABAB receptor agonist baclofen.
- Massolo, Elisabetta,Benaglia, Maurizio,Genoni, Andrea,Annunziata, Rita,Celentano, Giuseppe,Gaggero, Nicoletta
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supporting information
p. 5591 - 5596
(2015/05/27)
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- Selective synthesis of nitroalcohols in the presence of Ambersep 900 OH as heterogeneous catalyst
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Abstract A green protocol has been developed for the selective synthesis of β-nitroalcohols using commercially available Ambersep 900 OH as reusable heterogeneous catalyst. The reaction between aldehyde and nitromethane was performed under solvent-free condition at room temperature within a short time (70-150 min) in the presence of 10 wt % of Ambersep 900 OH to produce corresponding nitroalcohols in high yield (72-91 %). After the reaction is over, the catalyst can be separated and reused (3 cycles) without appreciable loss in its activity.
- Lodh, Rajsekhar,Sarma, Manas Jyoti,Borah, Arun Jyoti,Phukan, Prodeep
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p. 969 - 972
(2015/02/19)
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- Synthesis of high surface area mixed metal oxide from the NiMgAl LDH precursor for nitro-aldol condensation reaction
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We have investigated the effect of divalent metal cations on the structural and catalytic activity of MgAl-layered double hydroxide (LDH), by partially substituting Mg2+ with M2+ (M2+ = Ni2+ or Co2+)
- Bharali, Dipshikha,Devi, Rasna,Bharali, Pankaj,Deka, Ramesh C.
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p. 172 - 178
(2015/02/19)
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- One-pot protocol to synthesize N-(β-nitro)amides by tandem Henry/Ritter reaction
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A novel, efficient and atom economical one pot protocol for the synthesis of N-(β-nitro)amides has been described by combining the Henry reaction with the Ritter reaction. The designed products could be obtained from easily available aldehydes, nitroalkan
- Ai, Wensi,Shi, Ronghua,Zhu, Liyan,Jiang, Dehong,Ma, Xiaobo,Yuan, Jilan,Wang, Zhouyu
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p. 24044 - 24048
(2015/03/30)
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- Merging Asymmetric Henry Reaction with Organocatalytic Cascade Reaction for the Construction of a Chiral Indolizidine Alkaloid Skeleton
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A sequential reaction combining the copper-catalyzed asymmetric Henry reaction with the organocatalytic Michael addition-hemiacetalization cascade reaction was developed. The C1-symmetric chiral diamine L1-copper complex was responsible for the first highly enantioselective Henry reaction, while diphenylprolinol silyl ether A acted as effective organocatalyst for the second cascade reaction between chiral β-nitro alcohol and α,β-unsaturated aldehydes. Via rational design and combination of the two independent catalytic systems, good yields and excellent enantioselectivities and diastereoselectivities were achieved for a broad substrate scope under mild reaction conditions. The synthetic utility of this sequential catalytic asymmetric cascade reaction was demonstrated as an alternative and straightforward stereoselective synthesis strategy for chiral indolizidine alkaloid and its analogues.
- Zhou, Yirong,Yang, Qin,Shen, Jian,Chen, Xin,Peng, Yiyuan,Gong, Yuefa
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p. 1446 - 1456
(2015/02/19)
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- Evaluation of the nitroaldol reaction in the presence of metal ion-crosslinked alginates
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Understanding the ability of biopolymers to promote selective C-C bond formation could provide important insights into the molecular mechanisms underlying evolution, and could help in the design of safer and "greener" catalysts in the future. This work de
- Kühbeck, Dennis,Mayr, Judith,H?ring, Marleen,Hofmann, Martin,Quignard, Fran?oise,Díaz Díaz, David
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p. 2306 - 2315
(2015/03/18)
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- Probing the evolution of an Ar-BINMOL-derived salen-Co(iii) complex for asymmetric Henry reactions of aromatic aldehydes: Salan-Cu(ii) versus salen-Co(iii) catalysis
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A new type of chiral salen-Co catalyst that features aromatic π-walls and an active Co(iii) center has been developed for enantioselective Henry/nitroaldol reactions on the basis of salen-Cu catalysis. The asymmetric Henry reaction of aromatic aldehydes a
- Wei, Yun-Long,Yang, Ke-Fang,Li, Fei,Zheng, Zhan-Jiang,Xu, Zheng,Xu, Li-Wen
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p. 37859 - 37867
(2014/11/07)
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- Probing the evolution of an Ar-BINMOL-derived salen-Co(iii) complex for asymmetric Henry reactions of aromatic aldehydes: Salan-Cu(ii) versus salen-Co(iii) catalysis
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A new type of chiral salen-Co catalyst that features aromatic π-walls and an active Co(iii) center has been developed for enantioselective Henry/nitroaldol reactions on the basis of salen-Cu catalysis. The asymmetric Henry reaction of aromatic aldehydes a
- Wei, Yun-Long,Yang, Ke-Fang,Li, Fei,Zheng, Zhan-Jiang,Xu, Zheng,Xu, Li-Wen
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p. 37859 - 37867
(2014/12/11)
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- Synthesis, spectral characterization and crystal structure of Ni(II) pyridoxal thiosemicarbazone complexes and their recyclable catalytic application in the nitroaldol (Henry) reaction in ionic liquid media
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The new square planar nickel(II) complexes 1, 2 and 3 have been synthesized from the reaction of [NiCl2(PPh3)2] with the tridentate Schiff base ligand, pyridoxal thiosemicarbazone (L1), pyridoxal N-methyl thiosemicarbazone (L2) and pyridoxal N-phenyl thiosemicarbazone (L3) respectively in ethanol. These complexes have been characterized by elemental analyses, IR, UV-Vis, 1H NMR, 31P NMR and ESI-MS spectroscopy. The molecular structure of the complex [Ni(L2)PPh3] (2) was determined by single-crystal X-ray diffraction, which reveals a distorted square planar geometry around the nickel(II) ion. The nitroaldol reaction was studied in detail using the nickel(II) complexes as catalysts in a homogeneous solution formed by an ionic liquid and methanol. The effect of solvent, ionic liquid, time, temperature, catalyst loading and substituent of the ligand moiety on the reaction was also studied. The β-nitroalcohol products were obtained in good yields of up to 97%. A two step substrate addition mechanism was tentatively proposed based on ESI-MS spectral monitoring of the reaction mass.
- Manikandan, Rajendran,Anitha, Panneerselvam,Prakash, Govindan,Vijayan, Paranthaman,Viswanathamurthi, Periasamy
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p. 619 - 627
(2014/11/07)
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- Investigation of structural change and basicity of NaY zeolite upon loading KF and their application in Henry nitroaldol reaction under microwave irradiation condition
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Potassium salt modified NaY zeolite along with methanol-water mixture as solvent under microwave irradiation offers an environmentally benign way to synthesize b-nitroalcohols rapidly with excellent yield and selectivities. Here, NaY zeolite was modified
- Devi, Rasna,Borah, Ruli,Deka, Ramesh C.
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p. 1751 - 1758
(2015/02/19)
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- (2S,5R)-2-Methylaminomethyl-1-methyl-5-phenylpyrrolidine, a chiral diamine ligand for copper(ii)-catalysed Henry reactions with superb enantiocontrol
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A cis-2-aminomethyl-5-phenylpyrrolidine, which is easily available from methyl Boc-l-pyroglutamate, was found to be a highly efficient chiral ligand for Cu(ii)-catalysed Henry reactions. Excellent yields (>90%) and superb levels of enantiocontrol (98.5-99.6% ee) were reached with aromatic, heteroaromatic, vinylic, and aliphatic aldehydes (36 examples). This journal is the Partner Organisations 2014.
- Scharnagel, Dagmar,Prause, Felix,Kaldun, Johannes,Haase, Robert G.,Breuning, Matthias
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supporting information
p. 6623 - 6625
(2014/06/10)
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- Ethyl acrylate conjugated polystyryl-diphenylphosphine - An extremely efficient catalyst for Henry reaction under solvent-free conditions (SolFC)
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Over the last few decades, the fast-growing development of polymer supported reagents has led to the synthesis of a variety of reagents on solid support. Some of the major advantages of using such reagents are that they are less hygroscopic, easy to recover, and can be recycled. Here, we have demonstrated that in situ generated ethyl acrylate conjugated polystyryl-diphenylphosphine (PDPP-EA) derived from the reaction of a mixture of polystyryl-diphenylphosphine and ethyl acrylate in a stoichiometric ratio can efficiently catalyze the synthesis of β-nitroalcohols from the reaction of aldehydes and nitroalkanes under solvent-free conditions (SolFC).
- Rokhum, Lalthazuala,Bez, Ghanashyam
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p. 300 - 306
(2013/06/05)
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- Chemoselective Henry reaction catalyzed by electro-generated base
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Chemoselective synthesis of 2-nitroalkanols catalyzed by electro-generated base (EGBs) in the presence of acetonitrile and lithium perchlorate has been studied by cyclic voltammetry and controlled potential electrolysis techniques. Cathodic reduction of nitromethane at platinum cathode produces organic anion which acts as EGBs and undergoes condensation with carbonyl group of substituted aldehydic substrate to produce 2-nitroalkanols in 75-85 % yields. The controlled nucleophilicity of EGBs in organic solvent during electrochemical reaction makes it chemoselective which is a unique feature of this work.
- Saraswat,Sharma,Singh,Siddiqui,Singh
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p. 1393 - 1399
(2013/06/05)
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- Dolomite (CaMg(CO3)2) as a recyclable natural catalyst in Henry, Knoevenagel, and Michael reactions
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Iranian dolomite (CaMg(CO3)2) which consists of double-layered carbonates with Ca2+ and Mg2+ ions was utilized as a heterogeneous base catalyst in the CC, CN, and CS bond forming reactions via the Henry, Knoevenagel, aza-Michael, and thia-Michael transformations under mild conditions in water. Iranian dolomite has been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Brunauer Emmett Teller (BET) and XRF chemical analysis, while its basic strength was evaluated by following the Hammett indicators procedure. This water-insoluble natural catalyst demonstrated high activity and was reusable.
- Tamaddon, Fatemeh,Tayefi, Mohammad,Hosseini, Elaheh,Zare, Elham
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- Enantioselective henry reaction catalyzed by "ship in a bottle" complexes
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Two chiral Schiff-base complexes of copper(II) have been successfully encapsulated inside the cavity of zeolite-NaY via a "ship in a bottle" synthesis method. The presence of the two complexes inside the cages of zeolite-Y has been confirmed based on vari
- Bania, Kusum K.,Karunakar, Galla V.,Goutham, Kommuru,Deka, Ramesh C.
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p. 8017 - 8029
(2013/08/23)
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- The henry reaction in [Bmim][PF6]-based microemulsions promoted by acylase
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An environmentally-friendly, enzyme-promoted procedure for the Henry reaction was first studied using water-in-[Bmim][PF6] microemulsions as reaction medium. The Amano acylase from Aspergillus oryzae showed better catalytic activity for the addition reactions of nitromethane with a series of aromatic aldehydes, and a highest yield of 90% was obtained.
- Xia, Wen-Jian,Xie, Zong-Bo,Jiang, Guo-Fang,Le, Zhang-Gao
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p. 13910 - 13919
(2014/01/06)
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