- A metal-metalloporphyrin framework based on an octatopic porphyrin ligand for chemical fixation of CO2 with aziridines
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A new porous metal-metalloporphyrin framework, MMPF-10, has been constructed from an octatopic porphyrin ligand, which links copper paddlewheel units to form a framework with fmj topology. In situ metallation of the porphyrin ligands provides MMPF-10 with two unique accessible Cu(ii) centers. This allows it to behave as an efficient Lewis acid catalyst in the first reported reaction of CO2 with aziridines to synthesize oxazolidinones catalyzed by an MMPF.
- Wang, Xun,Gao, Wen-Yang,Niu, Zheng,Wojtas, Lukasz,Perman, Jason A.,Chen, Yu-Sheng,Li, Zhong,Aguila, Briana,Ma, Shengqian
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- Activation of (salen)CoI complex by phosphorane for carbon dioxide transformation at ambient temperature and pressure
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We report the activation of (salen)CoI complex 3g by a phosphorane to form a bifunctional catalyst for the reaction of carbon dioxide with terminal epoxides or aziridines at ambient temperature and 1 bar carbon dioxide pressure. Only 1.0 mol% of both (salen)CoI 3g and phosphorane 4d are required for cyclic carbonate synthesis, and the catalyst loading could even be lowered down to 0.1 mol%. Under these conditions, no polycarbonate formation is detected by NMR analysis. It is proposed that the high efficiency originates from the activation of (salen)CoI by a phosphorane to form a phosphorane-salen Co(iii) complex with enhanced Lewis acidity for the electrophilic activation while generating an iodide anion as a Lewis base co-catalyst to facilitate the ring-opening of epoxides. Further investigation revealed that the phosphorane-(salen)CoI complex could also successfully catalyze the coupling of CO2 with aziridines under ambient conditions at a catalyst loading of 2.5 mol%.
- Zhou, Feng,Xie, Shi-Liang,Gao, Xiao-Tong,Zhang, Rong,Wang, Cui-Hong,Yin, Guang-Qiang,Zhou, Jian
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- The solvent-free and catalyst-free conversion of an aziridine to an oxazolidinone using only carbon dioxide
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It has been found for the first time at room temperature that the reaction of an unactivated 2-alkyl or 2-aryl aziridine with carbon dioxide to generate the corresponding oxazolidinone does not need any form of catalysis or solvent to proceed in high yiel
- Phung, Chau,Ulrich, Rani M.,Ibrahim, Mostafa,Tighe, Nathaniel T. G.,Lieberman, Deborah L.,Pinhas, Allan R.
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- Bifunctional aluminum catalyst for CO2 fixation: Regioselective ring opening of three-membered heterocyclic compounds
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Regioselective ring opening of three-membered heterocyclic compounds (epoxides or N-substituted aziridines) at various temperatures was observed in coupling reactions with CO2 by the use of an aluminum - salen catalyst in conjunction with intramolecular quaternary ammonium salts as cocatalysts, affording the corresponding five-membered cyclic products with complete configuration retention at the methine carbon. Notably, this bifunctional aluminum-based catalyst exhibited nearly 100% regioselectivity for the ring opening at the methylene C-O bond for various terminal epoxides. This was true for those bearing an electron-withdrawing group, such as styrene oxide or epichlorohydrin, thereby affording the synthesis of various enantiopure cyclic carbonates that have previously been obtained only rarely by other methods. An intramolecular cooperative catalysis is suggested to contribute to the high activity and excellent stereochemistry control observed. Surprisingly, the highly selective ring opening at the methine carbon of N-substituted aziridines was found in the coupling with CO2, predominantly giving 5-substituted oxazolininones with retention of configuration as a result of double inversion at the methine carbon. (Chemical Equation Presented).
- Ren, Wei-Min,Liu, Ye,Lu, Xiao-Bing
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- The use of NMR chemical shifts to predict reaction pathways: Methanol formation from oxazolidinones
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The reduction of various N-substituted oxazolidin-2-ones with LiAlH 4 was investigated to open a pathway for methanol formation. By 15N and 13C NMR analysis and correlation with Hammett σp parameters appropriate substituents can be found which direct the reduction into the desired pathway. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Froehlich, Joerg,Berger, Stefan
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- A Multicomponent Route to Functionalized Amides and Oxazolidinones
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An organobase-mediated multicomponent reaction of unactivated esters, epoxides, and amines is reported, furnishing functionalized amide derivatives. A wide range of substrates are tolerated under the reaction conditions, including chiral epoxides, which react with no erosion of enantiopurity. Facile modification of the method through replacing the ester derivative with dimethyl carbonate enables access to the corresponding oxazolidinone derivatives.
- McPherson, Christopher G.,Cooper, Alasdair K.,Bubliauskas, Andrius,Mulrainey, Paul,Jamieson, Craig,Watson, Allan J. B.
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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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- A Multicomponent Approach to Oxazolidinone Synthesis Catalyzed by Rare-Earth Metal Amides
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Three-component reaction of epoxides, amines, and dimethyl carbonate catalyzed by rare-earth metal amides has been developed to synthesize oxazolidinones. 47 examples of 3,5-disubstituted oxazolidinones were prepared in 13–97 % yields. This is a simple and most practical method which employs easily available substrates and catalysts, and is applicable to a wide range of aromatic and aliphatic amines, as well as mono-substituted epoxides. Scope of disubstituted epoxides is rather limited, which requires further study. Preliminary mechanistic study reveals two possible reaction pathways through intermediates of β-amino alcohols or amides.
- Zhou, Meixia,Zheng, Xizhou,Wang, Yaorong,Yuan, Dan,Yao, Yingming
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p. 5783 - 5787
(2019/04/14)
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- Synthesis of Oxazolidinones by using Carbon Dioxide as a C1 Building Block and an Aluminium-Based Catalyst
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Oxazolidinone synthesis through the coupling of carbon dioxide and aziridines was catalysed by an aluminium(salphen) complex at 50–100 °C and 1–10 bar pressure under solvent-free conditions. The process was applicable to a variety of substituted aziridines, giving products with high regioselectivity. It involved the use of a sustainable and reusable aluminium-based catalyst, used carbon dioxide as a C1 source and provided access to pharmaceutically important oxazolidinones as illustrated by a total synthesis of toloxatone. This protocol was scalable, and the catalyst could be recovered and reused. A catalytic cycle was proposed based on stereochemical, kinetic and Hammett studies.
- Sengoden, Mani,North, Michael,Whitwood, Adrian C.
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p. 3296 - 3303
(2019/07/05)
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- Ruthenium Porphyrin Catalyzed Synthesis of Oxazolidin-2-ones by Cycloaddition of CO2 to Aziridines
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The reaction between N-substituted-2-arylaziridines and CO2 is efficiently promoted by ruthenium(VI) imidoporphyrin complexes and yields a mixture of 5-aryl (A) and 4-aryl (B) substituted oxazolidin-2-ones with a regioisomeric A/B ratio up to 9
- Carminati, Daniela,Gallo, Emma,Damiano, Caterina,Caselli, Alessandro,Intrieri, Daniela
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p. 5258 - 5262
(2019/01/04)
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- Potassium phosphate-catalyzed one-pot synthesis of 3-aryl-2-oxazolidinones from epoxides, amines, and atmospheric carbon dioxide
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Potassium phosphate was found to be a highly active catalyst in the three-component cycloaddition of amines, epoxides, and carbon dioxide in DMF at ambient temperature to form 3-aryl-2-oxazolidinones. Atmospheric CO2 and a broad range of amines were employed in this transformation. Aryl isocyanate and 1,2-aminoalcohol were generated in situ as key intermediates. This one-pot reaction is applicable to a variety of terminal epoxides and amines. The key advantages are high yields, simple work-up, inexpensive catalysts, and a practical ten gram-scale synthesis.
- Seo, Ue Ryung,Chung, Young Keun
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p. 803 - 808
(2017/08/15)
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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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- Palladium-catalyzed double carbonylation using near stoichiometric carbon monoxide: Expedient access to substituted 13C2-labeled phenethylamines
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A novel and general approach for 13C2- and 2H-labeled phenethylamine derivatives has been developed, based on a highly convergent single-step assembly of the carbon skeleton. The efficient incorporation of two carbon-13 isotopes into phenethylamines was accomplished using a palladium-catalyzed double carbonylation of aryl iodides with near stoichiometric carbon monoxide.
- Nielsen, Dennis U.,Neumann, Karoline,Taaning, Rolf H.,Lindhardt, Anders T.,Modvig, Amalie,Skrydstrup, Troels
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p. 6155 - 6165
(2012/09/21)
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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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supporting information; experimental part
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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- 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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- 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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- 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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- 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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- 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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- 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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- Synthesis of oxazolidinones and 1,2-diamines from N-alkyl aziridines
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Reactions of N-alkyl-substituted aziridines with Lil followed by an electrophile are discussed. In the first series of reactions, the electrophile is carbon dioxide and the product is an oxazolidinone. In all cases, either no reaction occurred or a high y
- Hancock, Matthew T.,Pinhas, Allan R.
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p. 2347 - 2355
(2007/10/03)
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- A convenient and inexpensive conversion of an aziridine to an oxazolidinone
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The conversion of an aziridine to the corresponding oxazolidinone using only carbon dioxide and a catalytic amount of lithium iodide is discussed. In all cases, either no reaction occurred or a high yield of product was obtained. HMPA has been added to th
- Hancock, Matthew T.,Pinhas, Allan R.
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p. 5457 - 5460
(2007/10/03)
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- A GENERAL METHOD FOR STEREO- AND REGIO-SPECIFIC OXYAMINATION OF OLEFINS
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A new synthetic method for stereo and regioscpecific oxyamination of olefins is described.
- Das, Jagabandhu
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p. 907 - 916
(2007/10/02)
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