- (Salen)chromium(III)/DMAP: An efficient catalyst system for the selective synthesis of 5-substituted oxazolidinones from carbon dioxide and aziridines
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(Equation Presented) (Salen)chromium(III)/DMAP was found to be an active catalyst system for the coupling of CO2 and aziridines. The oxazolidinone products were produced in high yield and selectivity from the opening of the aziridine at the most substituted N-C bond. This catalyst system worked well for a wide variety of monosubstituted N-aryl and N-alkyl aziridines as well as a 2,3-disubstituted N-alkyl aziridine.
- Miller, Aaron W.,Nguyen, SonBinh T.
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- Valorization of CO2 into N-alkyl Oxazolidin-2-ones Promoted by Metal-Free Porphyrin/TBACl System: Experimental and Computational Studies
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The cycloaddition of CO2 to N-alkyl aziridines was efficiently promoted by the convenient TPPH2/TBACl binary catalytic system. The metal-free procedure was effective for the synthesis of differently substituted N-alkyl oxazolidin-2-o
- Damiano, Caterina,Gallo, Emma,Manca, Gabriele,Sonzini, Paolo
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p. 2807 - 2814
(2021/06/25)
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- State-of-the-art catechol porphyrin COF catalyst for chemical fixation of carbon dioxide: Via cyclic carbonates and oxazolidinones
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A highly porous, crystalline catechol porphyrin COF was synthesized and applied as an organocatalyst for the chemical fixation of carbon dioxide to synthesize value-added chemicals such as cyclic carbonates and oxazolidinones under solvent-free and transition-metal-free conditions. The high surface area and the functionalities of the COF catalyst act synergistically to activate the starting material. The 2,3-DhaTph shows excellent activity towards cyclic carbonates at the atmospheric pressure of carbon dioxide. Additionally, this catalytic system is recyclable in nature and provides a higher turnover number than previously reported organocatalysts.
- Saptal, Vitthal,Shinde, Digambar Balaji,Banerjee, Rahul,Bhanage, Bhalchandra M.
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p. 6152 - 6158
(2016/08/05)
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- N-heterocyclic olefins as robust organocatalyst for the chemical conversion of carbon dioxide to value-added chemicals
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In this report, the activity of N-heterocyclic olefins (NHOs) as a newly emerging class of organocatalyst is investigated for the chemical fixation of carbon dioxide through reactions with aziridines to form oxazolidinones and the N-formylation of amines with polymethylhydrosiloxane (PMHS) or 9-borabicy-clo[3.3.1]nonane (9-BBN) as the reducing agent under mild conditions. The exocyclic carbon atoms of NHOs are highly nucleophilic owing to the electron-donating ability of the two nitrogen atoms. This high nucleophilicity of the NHOs activates CO2 molecules to form zwitterionic NHO–carboxylate (NHO– CO2) adducts, which are active in formylation reactions as well as the carboxylation of aziridines to oxazolidinones.
- Saptal, Vitthal B.,Bhanage, Bhalchandra M.
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p. 1980 - 1985
(2017/07/13)
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- Amine functionalized MCM-41 as a green, efficient, and heterogeneous catalyst for the regioselective synthesis of 5-aryl-2-oxazolidinones, from CO2 and aziridines
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Covalently linked amine functionalized MCM-41 catalysts were investigated as an efficient, heterogeneous and recyclable catalyst for the coupling of carbon dioxide (CO2) and aziridines providing high conversion with excellent regioselectivity towards 5-aryl-2-oxazolidinones under mild and solvent free conditions. The effect of various reaction parameters, such as temperature, time, and CO2 pressure for the synthesis of 5-aryl-2-oxazolidinones using amine functionalized MCM-41 catalyst was investigated. The optimized protocol was applied to a wide variety of 1-alkyl-2-arylaziridines producing the corresponding 5-aryl-2-oxazolidinones with good yield and excellent regioselectivity. Amine functionalized MCM-41 catalysts were characterized by FT-IR, TG/DTA, high and low angle XRD, and solid state 29Si CPMAS NMR analysis. Furthermore, the catalyst was effectively recycled for five consecutive cycles without any significant loss in its catalytic activity and selectivity under the described reaction conditions. Readily available reagents, mild reaction conditions and effective catalyst recyclability make this protocol simple, convenient, practical and environmentally friendly.
- Nale, Deepak B.,Rana, Surjyakanta,Parida, Kulamani,Bhanage, Bhalchandra M.
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p. 340 - 349
(2013/11/19)
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- Acid-base bifunctional periodic mesoporous metal phosphonates for synergistically and heterogeneously catalyzing CO2 conversion
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Integrating multiple functions into one host for improved catalytic performance is challenging and promising for both catalysis and material science. Herein a new acid-base bifunctional periodic mesoporous titanium phosphonate hybrid material is synthesized by a facile one-pot hydrothermal method, using alendronate sodium trihydrate as a coupling molecule. The new material possesses highly periodic mesopores with a large specific surface area of 540 m2 g-1 and pore volume of 0.43 cm3 g-1, favoring the smooth mass transport of reactants and products during the catalytic reaction. It also has an organic-inorganic hybrid framework with homogeneously incorporated phosphonate groups, in which a large number of accessible acidic P-OH and basic -NH2 sites can, respectively, activate aziridine and CO2, synergistically leading to the high conversion (>99%), yield (98%), and regioselectivity (98:2) for the CO2 cycloaddition reaction. The catalytic activity is better than that of the scarcely reported heterogeneous catalysts for aziridine and CO2 cycloaddition and even comparable to that of the state-of-the-art homogeneous ones. Moreover, being superior to the other catalysts, the metal phosphonate materials can be easily separated and reused repeatedly without activity loss, and no hazardous halogen ions, organic solvents, or cocatalysts are needed for the catalytic process. In comparison with previously reported multifunctional catalysts synthesized by complicated multistep fabrications, the facile one-pot preparation of mesoporous metal phosphonates with dual active sites makes it more practical for high-performance heterogeneous catalysis.
- Ma, Tian Yi,Qiao, Shi Zhang
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p. 3847 - 3855
(2015/02/19)
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- Design of task-specific ionic liquids for catalytic conversion of CO 2 with aziridines under mild conditions
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A series of polyethylene glycol (PEG)-functionalized ionic liquids (ILs) were developed as recyclable and efficient catalysts for selective synthesis of 5-aryl-2-oxazolidinones from aziridines and CO2 without addition of any organic solvents or additives. In particular, high yields, chemo- and regio-selectivities of oxazolidinones were attained when BrDBNPEG 150DBNBr (DBN: 1,5-diazabicyclo[4.3.0]non-5-ene) was used as the catalyst, presumably due to activation of CO2 by the ether linkage in the PEG backbone, and stabilization of the ring-opened species of aziridine by the delocalized cation BrDBNPEG150DBN+. Furthermore, the catalyst could be reused for over four consecutive cycles without appreciable loss of catalytic activity and selectivity. The effects of catalyst structure and various reaction parameters on the catalytic performance were also investigated in detail. It was demonstrated that the catalyst worked well for a variety of aziridines producing the corresponding oxazolidinones in good yields and excellent regio-selectivities. Therefore, this solvent-free process could thus represent an environmentally friendly approach for ILs-catalyzed conversion of CO2 into value-added chemicals.
- Zhao, Ya-Nan,Yang, Zhen-Zhen,Luo, Si-Hang,He, Liang-Nian
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- Regioselective synthesis of 5-aryl-2-oxazolidinones from carbon dioxide and aziridines using Br- Ph3+PPEG 600P+Ph3Br- as an efficient, homogenous recyclable catalyst at ambient conditions
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Polyethylene glycol functionalized phosphonium salt (Br- Ph 3+PPEG600P+Ph3Br -) was found to be an efficient, homogenous, recyclable catalyst for coupling of CO2 with a variety of aziridines producing corresponding 5-aryl-2-oxazolidinones with good yields and excellent regioselectivity under relatively mild and solvent free conditions. Furthermore, the catalyst was effectively recycled for four consecutive cycles without any significant loss in its catalytic activity and selectivity.
- Watile, Rahul A.,Bagal, Dattatraya B.,Patil, Yogesh P.,Bhanage, Bhalchandra M.
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p. 6383 - 6387
(2011/12/22)
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- Protic onium salts-catalyzed synthesis of 5-aryl-2-oxazolidinones from aziridines and CO2 under mild conditions
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Protic onium salts, e.g. pyridium iodide, proved to be highly efficient and recyclable catalysts for the selective synthesis of 5-aryl-2-oxazolidinones under a CO2 atmosphere at room temperature, presumably due to aziridine activation assisted by hydrogen bonding on the basis of 1H NMR and in situ FT IR under CO2 pressure study.
- Yang, Zhen-Zhen,Li, Yu-Nong,Wei, Yang-Yang,He, Liang-Nian
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p. 2351 - 2353
(2011/10/31)
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- N-Heterocyclic carbene functionalized MCM-41 as an efficient catalyst for chemical fixation of carbon dioxide
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N-Heterocyclic carbene (NHC) functionalized MCM-41 was synthesized by reacting 1,3-bis-(4-allyl-2,6-diisopropylphenyl) imidazolium chloride with MCM-41 using 3-mercaptopropyltrimethoxysilane as silane coupling agent, and its CO2 adduct (designated as MCM-41-IPr-CO2) was further synthesized by the reaction with CO2. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to investigate the reversible CO2 capture-release ability of MCM-41-NHC. MCM-41-IPr-CO2 adduct proved to be an efficient heterogeneous catalyst for the cycloaddition of CO2 to epoxides or aziridines with excellent regioselectivity under mild conditions. Moreover, the catalyst could be recovered easily through a simple filtration process and reused multiple times without obvious loss in activity, owing to CO2 as protective group for effectively stabilizing the NHC anchored on MCM-41. The Royal Society of Chemistry.
- Zhou, Hui,Wang, Yi-Ming,Zhang, Wen-Zhen,Qu, Jing-Ping,Lu, Xiao-Bing
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experimental part
p. 644 - 650
(2011/05/02)
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- Polymer supported diol functionalized ionic liquids: An efficient, heterogeneous and recyclable catalyst for 5-aryl-2-oxazolidinones synthesis from CO2 and aziridines under mild and solvent free condition
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Polymer supported diol functionalized ionic liquids (PS-DFILXs) were investigated as an efficient, heterogeneous and recyclable catalyst for coupling of carbon dioxide (CO2) to aziridines providing high conversion with excellent regioselectivit
- Watile, Rahul A.,Bagal, Dattatraya B.,Deshmukh, Krishna M.,Dhake, Kishor P.,Bhanage, Bhalchandra M.
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experimental part
p. 196 - 203
(2012/02/03)
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- Naturally occurring α-amino acid: a simple and inexpensive catalyst for the selective synthesis of 5-aryl-2-oxazolidinones from CO2 and aziridines under solvent-free conditions
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Naturally occurring α-amino acid successfully catalyzed cycloaddition of aziridine with carbon dioxide to afford 5-aryl-2-oxazolisinones under mild conditions without the need of any additives. The scope of this reaction is very general, providing the corresponding products in good yields and excellent regioselectivity (87:13-100:0) regardless of the α-amino acid examined and a wide variety of N-substituted aziridines employed. Two possible reaction pathways for the reaction were also discussed.
- Jiang, Huan-Feng,Ye, Jin-Wu,Qi, Chao-Rong,Huang, Liang-Bin
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experimental part
p. 928 - 932
(2010/05/18)
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- Polystyrene-supported amino acids as efficient catalyst for chemical fixation of carbon dioxide
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Four new polystyrene-supported amino acids have been synthesized and applied to the chemical fixation of carbon dioxide for the first time. Two series of experiments with polystyrene-supported threonine (PS-Thr) and polystyrene-supported tyrosine (PS-Tyr) as catalyst, respectively, were conducted to study the effect of the reaction conditions on the carboxylation of propylene oxide/carbon dioxide. There was no considerable decrease in the yield of propylene carbonate after the polystyrene-supported amino acids were used five times, indicating that these catalysts are very stable. It was demonstrated that these catalysts were very efficient in the carboxylation of various epoxides and aziridines with carbon dioxide under mild conditions without any solvents. The mechanism for this carboxylation is also discussed.
- Qi, Chaorong,Ye, Jinwu,Zeng, Wei,Jiang, Huanfeng
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supporting information; experimental part
p. 1925 - 1933
(2010/11/04)
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- Environmentally benign chemical fixation of CO2 catalyzed by the functionalized ion-exchange resins
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Basic ion-exchange resins, one kind of polystyryl-supported tertiary amine, were demonstrated to be highly efficient and recyclable catalysts for the fixation of carbon dioxide with aziridines under mild conditions, leading to the formation of 5-aryl-2-oxazolidinone with excellent regio-selectivities. Notably, neither solvents nor any additives were required, and the catalyst could be recovered by simple filtration and directly reused at least five times without significant loss of catalytic activity and selectivity. The present protocol has been applied to reactions of epoxides/propargyl amines with CO 2/CS2. This solvent-free process thus represents environmentally friendly catalytic conversion of CO2 into value-added chemicals and may have potential in various continuous flow reactors in industry.
- Liu, Anhua,He, Liangnian,Peng, Shiyong,Pan, Zhongda,Wang, Jinglun,Gao, Jian
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experimental part
p. 1578 - 1585
(2010/11/04)
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- Lewis basic ionic liquids-catalyzed synthesis of 5-aryl-2-oxazolidinones from aziridines and CO2 under solvent-free conditions
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A series of easily prepared Lewis basic ionic liquids were developed as recyclable and efficient catalysts for selective synthesis of 5-aryl-2-oxazolidinones from aziridines and CO2 without utilization of any organic solvent or additive. Notably, high conversion, chemo- and regio-selectivity were attained when 1-butyl-4-aza-1-azaniabicyclo[2.2.2]octane bromide ([C4DABCO]Br) was used as the catalyst. Furthermore, the catalyst could be recycled over four times without appreciable loss of catalytic activity. The effects of the catalyst structure and various reaction parameters on the catalytic performance were investigated in detail. This protocol was found to be applicable to a variety of aziridines producing the corresponding 5-aryl-2-oxazolidinones in good yields and excellent regioselectivities. Therefore, this solvent-free process thus represents an environmentally friendly process for ionic liquid-catalyzed conversion of CO2 into value-added chemicals. A possible catalytic cycle for CO2 activation induced by nucleophilic tertiary nitrogen of the ionic liquid was proposed, based on studies using in situ FT-IR spectroscopy under CO2 pressure.
- Yang, Zhen-Zhen,He, Liang-Nian,Peng, Shi-Yong,Liu, An-Hua
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supporting information; experimental part
p. 1850 - 1854
(2011/02/23)
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- Catalyst-free process for the synthesis of 5-aryl-2-oxazolidinones via cycloaddition reaction of aziridines and carbon dioxide
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A simple approach for facile synthesis of 5-aryl-2-oxazolidinones in excellent regioselectivity from aziridines under compressed CO2 conditions was developed in the absence of any catalyst and organic solvent. The reaction outcome was found to be tuned by subtly adjusting CO2 pressure. The adduct formed in situ of aziridine and CO2 is assumed to act as a catalyst in this reaction, which was also studied by means of in situ FT-IR technique.
- Dou, Xiao-Yong,He, Liang-Nian,Yang, Zhen-Zhen,Wang, Jing-Lun
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supporting information; experimental part
p. 2159 - 2163
(2010/10/21)
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- Zirconyl chloride: an efficient recyclable catalyst for synthesis of 5-aryl-2-oxazolidinones from aziridines and CO2 under solvent-free conditions
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Zirconyl chloride was found to be an efficient catalyst for the cycloaddition reaction of aziridines with CO2, thus leading to the preferential formation of 5-aryl-2-oxazolidinones under solvent-free conditions. The methodology could be extended to various substituted aziridines with high conversion and chemo-, regio-, and stereoselectivity. Furthermore, the catalyst could be reused over five times without significant loss in activity. Interestingly, the recovered catalyst showed higher activity in comparison with the fresh catalyst, presumably due to its morphological variation. The use of this cheap and moisture stable catalyst make this protocol practical, environmentally benign, and economically attractive.
- Wu, Ying,He, Liang-Nian,Du, Ya,Wang, Jin-Quan,Miao, Cheng-Xia,Li, Wei
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experimental part
p. 6204 - 6210
(2011/03/21)
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- Quaternary ammonium bromide functionalized polyethylene glycol: A highly efficient and recyclable catalyst for selective synthesis of 5-aryl-2-oxazolidinones from carbon dioxide and aziridines under solvent-free conditions
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(Chemical Equation Presented) A quaternary ammonium bromide covalently bound to polyethylene glycol (PEG, MW = 6000), i.e., PEG6000- (NBu3Br)2, was found to be an efficient and recyclable catalyst for the cycloaddition reaction of aziridines to CO2 under mild conditions without utilization of additional organic solvents or cocatalysts. As a result, 5-aryl-2-oxazolidinone was obtained in high yield with excellent regioselectivity. The catalyst worked well for a wide variety of 1-alkyl-2-arylaziridines. Besides, the catalyst could be recovered by centrifugation and reused without significant loss of catalytic activity and selectivity.
- Du, Ya,Wu, Ying,Liu, An-Hua,He, Liang-Nian
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p. 4709 - 4712
(2008/09/21)
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- N-substituted 5-aryl-1,3-oxazolidin-2-ones from arylethylene oxides
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Substituted 5-aryl-1,3-oxazolidin-2-ones can be efficiently prepared from arylethylene oxides and tert-butyl alkylcarbamates in the presence of catalytic amount of potassium tert-butoxide as a base. Their further hydrolysis under basic conditions provides aryl substituted aminoethanols in high yields.
- Wrobel,Bobin,Karczewski
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p. 907 - 912
(2007/10/03)
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