- The Synthesis of 3-Aryl-2-oxazolidinones from CO2, Ethylene Oxide, and Anilines Under Mild Conditions Using PVA-DFNT/Ni
-
Abstract: A novel nanocatalyst design using nanomaterials through active-zone crystallisation was proposed. The hydrothermal crystallisation of amorphous dendritic fibrous nano-titanium dioxide with Ni (DFNT/Ni) sites was determined to be the main step in producing extremely active dendritic DFNT/Ni zones, which in turn dramatically enhanced their catalytic activities. DFNT/Ni was then combined with polyvinyl alcohol (PVA) by using a traditional individual-nozzle electrospinning method, and the resulting material was named PVA-DFNT/Ni. This method was utilised to produce 3-aryl-2-oxazolidinones from ethylene oxide, CO2, and anilines. The prepared catalytic apparatus was eco-friendly and had the advantages of high catalytic activity, ability to improve the reaction mixture, and reusability without a considerable decrease in efficiency. It is extracted in the straight and adoptive chemical fixation of flue-gas CO2 obtained from industrial emissions, thereby achieving high degrees of CO2 absorption and conversion. Graphic Abstract: [Figure not available: see fulltext.].
- Lu, Jingjing,Liu, Haitao,Xu, Tiejun,Shamsa, Farzaneh
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p. 281 - 292
(2020/07/08)
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- Synergetic activation of CO2by the DBU-organocatalyst and amine substrates towards stable carbamate salts for synthesis of oxazolidinones
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The development of an efficient methodology to transform CO2 into valuable chemicals has attracted increasing attention concerning the challenging issues of CO2-utilization. Herein, an efficient approach for the preparation of oxazolidinones from CO2, primary (aliphatic/aromatic) amines and 1,2-dichloroethane (or its derivatives) catalyzed by DBU organo-superbase was achieved with yields of 47-97% under mild conditions (80-100 °C, 12 h, 1.0 MPa CO2). Control experiments demonstrated that the formation of an ion-pair carbamate salt intermediate IS-B derived from the reaction of CO2, DBU (catalyst) and an amine (substrate) was the key step for this three-component reaction. The available DBU-amine-CO2 adduct intermediate (like IS-B-2) with fair stability will evolve into the thermodynamically stable product oxazolidinones upon attack of 1,2-dichloroethane (or its derivatives), along with the regeneration of the DBU catalyst. Alternatively, the decomposition of the DBU-aryl amine-CO2 adduct (like IS-B-1) with relatively poor stability also could result in the competitive substitution reaction of 1,2-dichloroethane (or its derivatives) with the aryl amine. This work provides insights into synergetic CO2-activation by the DBU-catalyst and a nucleophilic amine-substrate via the formation of robust carbamate salt intermediates responsible for the final production of oxazolidinones. This journal is
- Chen, Xiao-Chao,Liu, Ye,Lu, Yong,Yao, Yin-Qing,Zhao, Kai-Chun
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p. 7072 - 7082
(2021/11/17)
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- Method for synthesizing N - aryl oxazolidine -2 - ketone compound by ionic liquid catalysis
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The invention discloses a method for catalytic synthesis of a N-aryloxazolane-2-one compound or a chiral N-aryloxazolane-2-one compound from an ionic liquid. The process of the preparation method is as follows: a catalytic amount of ionic liquid is added
- -
-
Paragraph 0031-0032; 0061-0062
(2019/10/01)
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- Nickel-catalyzed N-arylation of amines with arylboronic acids under open air
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In this study, a well-defined, novel NHC-Ni complex was developed and used to catalyze the N-arylation of alkyl- and arylamines with arylboronic acids in a rare version of Chan-Lam coupling. Although the same coupling using copper catalysts has been widely studied, the nickel-catalyzed version is rare and normally requires 10–20 mol% catalyst loading. This novel NHC-Ni complex in combination with 4,4′-dimethyl-2,2′-bipyridine, however, proved to be an effective catalyst that lowered the required catalyst loading to only 2.0 mol%.
- Ando, Shin,Hirota, Yurina,Matsunaga, Hirofumi,Ishizuka, Tadao
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supporting information
p. 1277 - 1280
(2019/04/10)
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- Method for synthesizing cyclic amide from carbon dioxide
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The invention discloses a method for synthesizing cyclic amide from carbon dioxide. An aromatic amino compound, 1 atm carbon dioxide and a halogenated compound undergo a one-step reaction under the synergistic action of N-doped TiO2 and an inorganic salt catalyst to generate the cyclic amide. Studies find that visible light has an obvious promoting effect on the conversion process. The chemical selectivity of the cyclic amide compound can be regulated by regulating conditions such as reaction temperature, time and illumination. The catalyst can be recycled for five times after being separatedand dried, and the activity and the chemical selectivity can be well maintained. The synthesis method has the advantages of simple synthetic route, novelty, simple process, high yield and high purityof the product, cheap and easily available catalyst, no influences on the environment, and suitableness for industrial production.
- -
-
Paragraph 0011-0012
(2019/12/29)
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- Spirulina (Arthrospira) platensis Supported Ionic Liquid as a Catalyst for the Synthesis of 3-Aryl-2-oxazolidinones from Carbon Dioxide, Epoxide, Anilines
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Abstract: This study investigates the potential application of the (Ammonio)butane-1-sulfonate modified Spirulina (Arthrospira) platensis biomasses in the synthesis of 3-aryl-2-oxazolidinones from CO2, ethylene oxide, and anilines. High catalytic activity and ease of recovery from the reaction mixture using filtration and several reuse times without significant losses in performance are additional eco-friendly attributes of this catalytic system. The effects of the structure of ionic liquid on the catalytic performance were investigated and the various reaction conditions were optimized. This observation was exploited in the direct and selective chemical fixation of CO2, affording high degrees of CO2 capture and conversion. Graphical Abstract: [Figure not available: see fulltext.].
- Sadeghzadeh, Seyed Mohsen,Zhiani, Rahele,Emrani, Shokufe
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p. 119 - 124
(2017/10/30)
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- Synthesis of N-aryl-2-oxazolidinones from cyclic carbonates and aromatic amines catalyzed by bio-catalyst
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A convenient and effective method of synthesizing 3-aryl-2-oxazolidinones from cyclic carbonates and aryl amines catalyzed by bio-catalyst adenine in the presence of Et3N under solvent-free conditions is described. The protocol is suitable for the wide scope of substrates, e.g. cyclic carbonates with or without substitutes, and aryl amines with either electron-withdrawing or electron-donating group. The products were obtained in good to excellent yields under the optimal conditions, even in steric hindered cases. The effect of reaction time, temperature, loading of catalyst, and amount of starting materials in the reaction were investigated, and the reaction mechanism is discussed.
- Mei, Congmin,Zhao, Yibo,Zou, Ke,Cao, Changsheng,Pang, Guangsheng,Shi, Yanhui
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p. 2179 - 2194
(2017/12/28)
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- Ruthenium-Pincer-Catalyzed Hydrogenation of Lactams to Amino Alcohols
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By using the commercially available ruthenium pincer complex (Ru-MACHO-BH) as a catalyst, the challenging direct hydrogenation of lactams and analogues has been successfully accomplished to deliver corresponding value-added amino alcohols in good-to-excellent yields under mild reaction conditions. Remarkably, in addition to N-protected lactams, unprotected ones could also be readily reduced in the presence of a catalytic amount of weak base or even under neutral reaction conditions, which further highlights the broad substrate scope and the protocol efficiency.
- Chen, Jiangbo,Wang, Jiaquan,Tu, Tao
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p. 2559 - 2565
(2018/07/30)
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- Synthesis of Oxazolidinones and Derivatives through Three-Component Fixation of Carbon Dioxide
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An effective three-component fixation of atmospheric CO2 with readily available 1,2-dichloroethane and aromatic amine toward oxazolidinones catalyzed by in situ NHC was developed. The reaction occurred in good to excellent yields with good gene
- Mei, Congmin,Zhao, Yibo,Chen, Qianwei,Cao, Changsheng,Pang, Guangsheng,Shi, Yanhui
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p. 3057 - 3068
(2018/06/04)
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- Carbon dioxide-based facile synthesis of cyclic carbamates from amino alcohols
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We report herein a straightforward general method for the synthesis of cyclic carbamates from amino alcohols and carbon dioxide in the presence of an external base and a hydroxyl group activating reagent. Utilizing p-toluenesulfonyl chloride (TsCl), the reaction proceeds under mild conditions, and the approach is fully applicable to the preparation of various high value-added 5- and 6-membered rings as well as bicyclic fused ring carbamates. DFT calculations and experimental results indicate a SN2-type reaction mechanism with high regio-, chemo-, and stereoselectivity.
- Niemi, Teemu,Fernández, Israel,Steadman, Bethany,Mannisto, Jere K.,Repo, Timo
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supporting information
p. 3166 - 3169
(2018/03/28)
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- A straightforward one-pot synthesis of bioactive: N -aryl oxazolidin-2-ones via a highly efficient Fe3O4@SiO2-supported acetate-based butylimidazolium ionic liquid nanocatalyst under metal- and solvent-free conditions
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In the present study, we report the fabrication and characterization of novel acetate-based butylimidazolium ionic liquid immobilized silica-coated magnetic nanoparticles (IL-OAc@FSMNP). The synthesized nanocomposite proves its supremacy as an environmentally benign catalyst in the reaction of aniline and its derivatives with ethylene carbonate to form bioactive N-aryl oxazolidin-2-ones under metal-, ligand-, and solvent-free conditions. The catalyst offers excellent assemblies of hydrogen-bond donors and acceptors, which activate the substrates, thereby delivering good-to-excellent product yields with a conversion and selectivity of more than 99%. Additionally, mild reaction conditions, wide substrate scope, effortless catalytic recovery and recyclability of the catalyst up to eight consecutive cycles offer the potential for scale-up in various pharmaceutical applications.
- Gupta, Radhika,Yadav, Manavi,Gaur, Rashmi,Arora, Gunjan,Sharma, Rakesh Kumar
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p. 3801 - 3812
(2017/08/22)
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- Acceleration of Pd-Catalyzed Amide N-Arylations Using Cocatalytic Metal Triflates: Substrate Scope and Mechanistic Study
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The Pd/xantphos-catalyzed cross-coupling of amides and aryl halides is accelerated by cocatalytic metal triflate additives. A survey of nitrogen nucleophiles reveals improved yields for a variety of N-aryl amide products when Al(OTf)3 is employed as a catalytic additive, with some exceptions. Initial rates of catalysis indicate that the Lewis acid acceleration is more pronounced when bromobenzene (PhBr) is used in comparison with iodobenzene (PhI). The observation of an aryl halide dependence on rate and various qualitative kinetic experiments are consistent with a mechanism in which ligand exchange of halide for amide ("transmetalation") is turnover limiting. The mechanism may be different depending on whether PhBr or PhI is used as a coupling partner. Oxidative addition complexes (xantphos)Pd(Ph)(X) (X = Br, I; xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene), likely intermediates in catalysis, have been prepared; their differing interactions with Yb(OTf)3 in solution resemble the halide dependence of the catalytic mechanism, which we propose originates from a reversible Lewis acid mediated halide abstraction during catalysis.
- Becica, Joseph,Dobereiner, Graham E.
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p. 5862 - 5870
(2017/09/15)
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- DBU and DBU-Derived Ionic Liquid Synergistic Catalysts for the Conversion of Carbon Dioxide/Carbon Disulfide to 3-Aryl-2-oxazolidinones/[1,3]Dithiolan-2-ylidenephenyl- Amine
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An intermolecular synergistic catalytic combination of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and a DBU-derived bromide ionic liquid has been developed for the conversion of CO2, epoxides, and amines under metal- And solvent-free conditions. Various 3-aryl-2-oxazolidinones are produced in moderate to excellent yields within a short reaction time. NMR spectroscopy and DFT calculations demonstrate that DBU as a hydrogen bond acceptor and the ionic liquid as a hydrogen bond donor activate the substrates cooperatively by inducing hydrogen bonds to promote the reaction effectively. Based on these results, a possible reaction mechanism on the synergistic catalysis of DBU and the ionic liquid is proposed. In addition, the reaction of CS2, ethylene oxide, and aniline catalyzed by the combination of DBU and the DBU-derived ionic liquid also proceeds smoothly, which opens a hitherto unreported route to [1,3]dithiolan-2-ylidenephenylamine in a straightforward way.
- Wang, Binshen,Luo, Zhoujie,Elageed, Elnazeer H. M.,Wu, Shi,Zhang, Yongya,Wu, Xiaopei,Xia, Fei,Zhang, Guirong,Gao, Guohua
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p. 830 - 838
(2016/03/05)
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- A One-Pot Synthesis of N-Aryl-2-Oxazolidinones and Cyclic Urethanes by the Lewis Base Catalyzed Fixation of Carbon Dioxide into Anilines and Bromoalkanes
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The multicomponent assembly of pharmaceutically relevant N-aryl-oxazolidinones through the direct insertion of carbon dioxide into readily available anilines and dibromoalkanes is described. The addition of catalytic amounts of an organosuperbase such as Barton's base enables this transformation to proceed with high yields and exquisite substrate functional-group tolerance under ambient CO2pressure and mild temperature. This report also provides the first proof-of-principle for the single-operation synthesis of elusive seven-membered ring cyclic urethanes.
- Niemi, Teemu,Perea-Buceta, Jesus E.,Fernández, Israel,Hiltunen, Otto-Matti,Salo, Vili,Rautiainen, Sari,R?is?nen, Minna T.,Repo, Timo
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supporting information
p. 10355 - 10359
(2016/07/22)
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- Selective Synthesis of 5-Substituted N-Aryloxazolidinones by Cycloaddition Reaction of Epoxides with Arylcarbamates Catalyzed by the Ionic Liquid BmimOAc
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A selective procedure for the synthesis of 5-substituted N-aryloxazolidinones by the coupling of epoxides with arylcarbamates catalyzed by ionic liquids has been developed. The effects of reaction time, reactant molar ratio, amount of catalyst, and temper
- Elageed, Elnazeer H. M.,Chen, Bihua,Wang, Binshen,Zhang, Yongya,Wu, Shi,Liu, Xiuli,Gao, Guohua
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supporting information
p. 3650 - 3656
(2016/07/28)
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- Imidazolium and Potassium Hydrogen Carbonate Salts as Ecofriendly Organocatalysts for Oxazolidinone Synthesis
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Although oxazolidinones are valuable intermediate compounds for industrial applications, no synthetic method is suitable for their production on a large scale owing to the use of reagents/catalysts that are hazardous or toxic to human health or ecotoxic for the environment. In this manuscript, we describe new and efficient catalysts, that is, the nontoxic hydrogen carbonate anion in combination with a potassium or diisobutylimidazolium ([iBu2IM]) countercation, for the conversion of β-amino alcohols into cyclic oxazolidinones in high yields of 69 to 90 %. Depending on the catalytic conditions, both catalysts could be easily recovered from the crude reaction products and reused several times without a decrease in their catalytic performance. Furthermore, the imidazolium cation is a renewable catalyst, because its preparation requires less than 10 % of carbon fossil sources.
- Fournier, Antoine H.,de Robillard, Guillaume,Devillers, Charles H.,Plasseraud, Laurent,Andrieu, Jacques
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p. 3514 - 3518
(2016/07/28)
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- Copper(II) incorporated functionalized polystyrene catalyzed: N -arylation of amides under solvent free condition with broad substrate scope
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We demonstrate here, a new polystyrene supported Cu(ii) catalyzed proficient synthetic methodology for the facile N-arylation of aromatic, aliphatic, cyclic and heterocyclic amides with aryl halides under neat conditions. The catalyst, PS-Cu(ii)-ala, was prepared through the grafting of copper metal on a polystyrene-β-alanine imine network. The catalyst shows a wide range of substrate scope and excellent functional group tolerance, and produces the desired anilides in mostly high yields. The material is thoroughly characterized by DRS-UV, FT-IR, AAS, FE-SEM, TGA analysis and energy dispersive X-ray (EDX) studies. The catalyst can be easily recovered from the reaction medium and reused without significant loss of its catalytic activity suggesting future potential of this catalyst.
- Islam, Md. Mominul,Halder, Mita,Roy, Anupam Singha,Chatterjee, Sauvik,Bhaumik, Asim,Islam, Sk. Manirul
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p. 109692 - 109701
(2016/11/30)
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- BmimOAc ionic liquid: A highly efficient catalyst for synthesis of 3-aryl-2-oxazolidinones by direct condensation of 2-(arylamino) alcohols with diethyl carbonate
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An efficient convenient procedure for the synthesis of 3-aryl-2-oxazolidinones from 2-(arylamino) alcohols and diethyl carbonate (DEC) catalyzed by ionic liquids is described. The effects of reaction time, amount of catalyst and temperature were investigated. Excellent yields of products were obtained under the optimized reaction conditions, when using BmimOAc as a catalyst. An intermediate ethyl 2-(phenyl amino) ethyl carbonate was isolated and characterized. 1H NMR spectroscopy and DFT calculations indicated that BmimOAc cooperatively activate the substrates through hydrogen bonding with its anion and cation sites. According to these results, a possible reaction mechanism was discussed.
- Elageed, Elnazeer H.M.,Wang, Binshen,Zhang, Yongya,Wu, Shi,Gao, Guohua
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p. 271 - 277
(2015/09/01)
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- One-pot conversion of carbon dioxide, ethylene oxide, and amines to 3-aryl-2-oxazolidinones catalyzed with binary ionic liquids
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An effective one-pot method for the conversion of carbon dioxide, ethylene oxide, and amines to 3-aryl-2-oxazolidinones has been developed. This one-pot method consists of two parallel reactions and a subsequent cascade reaction between the two products of the corresponding parallel reactions. Notably, the binary ionic liquids of 1-butyl-3-methyl-imidazolium bromide and 1-butyl-3-methyl-imidazolium acetate demonstrate a synergistic catalytic effect on this new strategy. 1-Butyl-3-methyl-imidazolium bromide is essential in two parallel reactions owing to the good nucleophilicity and leaving ability of bromide, and 1-butyl-3-methyl-imidazolium acetate plays a dominant role in the subsequent cascade reaction owing to the strong basicity of acetate. In addition, the binary ionic liquids can be used thrice without significant loss of catalytic activity. Copyright
- Wang, Binshen,Elageed, Elnazeer H.M.,Zhang, Dawei,Yang, Sijuan,Wu, Shi,Zhang, Guirong,Gao, Guohua
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p. 278 - 283
(2014/01/23)
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- Copper-Catalyzed One-Pot Synthesis of N -Aryl Oxazolidinones from Amino Alcohol Carbamates
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An efficient sequential intramolecular cyclization of amino alcohol carbamates followed by Cu-catalyzed cross-coupling with aryl iodides under mild conditions has been developed. The reaction occurred in good yields and tolerated aryl iodides containing functionalities such as nitriles, ketones, ethers, and halogens. Heteroaryl iodides and substituted amino alcohol carbamates were also well tolerated.
- Mahy, William,Plucinski, Pawel K.,Frost, Christopher G.
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supporting information
p. 5020 - 5023
(2015/01/08)
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- C,N-chelated organotin(IV) compounds as catalysts for transesterification and derivatization of dialkyl carbonates
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The potential catalytic activity of selected C,N-chelated organotin(IV) compounds (e.g. halides and trifluoroacetates) for derivatization of both dimethyl carbonate (DMC) and diethyl carbonate (DEC) was investigated. Some tri-, di- and monoorganotin(IV) species (LCN(n-Bu)2SnCl (1), LCN(n-Bu)2SnCl.HCl (1a), LCN(n-Bu) 2SnI (2), LCNPh2SnCl (3), LCNPh 2SnI (4), LCN(n-Bu)SnCl2 (5), L CNSnBr3 (6) and [LCNSn(OC(O)CF 3)]2(μ-O)(μ-OC(O)CF3)2 (7)) bearing the LCN moiety (LCN = 2-(N,N-dimethylaminomethyl) phenyl-) were assessed as catalysts for reactions of both DMC and DEC with various substituted anilines. The catalytic activities of 4 and 7 for derivatization of DMC with p-substituted phenols were studied for comparison with the standard base K2CO3/Silcarbon K835 catalyst (catalyst 8). The composition of resulting reaction mixtures was monitored by multinuclear NMR spectroscopy, GC and GC-MS techniques. In general, catalysts 1, 3 and 7 exhibited the highest catalytic activity for all reactions studied, while some of them yielded selectively carbonates, carbamates, lactam or substituted urea. Copyright
- Weidlich, Tomas,Dusek, Libor,Vystrcilova, Barbora,Eisner, Ales,Svec, Petr,Ruzicka, Ales
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experimental part
p. 293 - 300
(2012/10/07)
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- CuI/N,N-dimethylglycine-catalyzed synthesis of N-aryloxazolidinones from aryl bromides
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CuI/N,N-dimethylglycine catalyzed coupling of aryl bromides with substituted oxazolidinones took place at 120 °C in DMF, affording the corresponding N-arylation products with good to excellent yields. A number of functional groups, such as ketone, nitrile, nitro, methoxy, and hydroxyl were tolerated under these conditions, thereby allowing diversity synthesis of N-aryloxazolidinones.
- Li, Jiaojiao,Zhang, Yihua,Jiang, Yongwen,Ma, Dawei
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supporting information; experimental part
p. 3981 - 3983
(2012/08/27)
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- Intermolecular oxidative C-N bond formation under metal-free conditions: Control of chemoselectivity between aryl sp2 and benzylic sp 3 C-H bond imidation
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A new synthetic approach toward intermolecular oxidative C-N bond formation of arenes has been developed under transition-metal-free conditions. Complete control of chemoselectivity between aryl sp2 and benzylic sp 3 C-H bond imidation was achieved by the choice of nitrogen sources, representatively being phthalimide and dibenzenesulfonimide, respectively.
- Kim, Hyun Jin,Kim, Jiyu,Cho, Seung Hwan,Chang, Sukbok
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supporting information; experimental part
p. 16382 - 16385
(2011/12/13)
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- Efficient copper-catalyzed N-arylation of amides and imidazoles with aryl iodides
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The C-N cross-coupling of amides and imidazoles with aryl iodides is described using CuI in tetrabutylammonium bromide (TBAB) under ligand-free conditions. The reaction is simple, general, and efficient affording the C-N cross-coupled products in shorter time and in high yield. Georg Thieme Verlag Stuttgart ? New York.
- Ali, Md. Ashif,Saha, Prasenjit,Punniyamurthy, Tharmalingam
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supporting information; experimental part
p. 908 - 910
(2010/04/29)
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- Method for forming a carbon-carbon or carbon-heteroatom bond
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The invention relates to a method for forming a carbon-carbon or carbon-heteroatom bond by reacting an unsaturated compound carrying a leaving group and a nucleophilic compound, in the absence of a ligand. The aim of the invention is especially to form carbon-nitrogen bonds according to a method for the arylation of nitrogenated organic derivatives. According to the inventive method, a carbon-carbon or carbon-heteroatom bond is formed by reacting an unsaturated compound carrying a leaving group with a nucleophilic compound donating a carbon atom or a heteroatom (HE) that can substitute the leaving group, thus forming a C—C or C—HE bond, in the presence of a copper-based catalyst and a base. Said metal is characterised in that the reaction takes place in the absence of a ligand and in a nitrile-type solvent.
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Page/Page column 13
(2009/10/01)
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- An eco-friendly, convenient, and practical conversion of arylamines to oxazolidinones
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A one-step procedure for efficient synthesis of oxazolidinone only using ethylene carbonate and arylamines in the presence of 1,4-diazabicyclo[2,2,2] octane (DABCO) was developed. In most cases, moderate to high yield of products were obtained. This reaction can be considered a carbon dioxide fixation reaction since ethylene carbonate was synthesized via reaction of ethylene oxide with carbon dioxide. Copyright
- Gong, Hang,Yang, Nian-Fa,Deng, Guo-Jun,Xu, Guang-Yi
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supporting information; experimental part
p. 584 - 585
(2011/04/21)
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- Novel syntheses of N-aryloxazolidin-2-ones via tandem reactions of vinyl sulfonium salts
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An unprecedented and efficient domino reaction of diphenyl vinyl sulfonium salt with carbamates leading to the syntheses of N-aryloxazolidin-2-ones has been developed. The scope of this transformation has been studied and a plausible mechanism has been pr
- Xie, Chunsong,Han, Deyu,Liu, Jinhua,Xie, Tian
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experimental part
p. 3155 - 3158
(2010/03/26)
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- Copper-TBAF catalyzed arylation of amines and amides with aryl trimethoxysilane
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A copper-catalyzed C-N bond forming reaction among aryl siloxane and primary, secondary amines as well as amides has been described. The reaction was conducted in the presence of P(C6F5)3 and 4 A molecular sieves in CHsub
- Lin, Baoda,Liu, Miaochang,Ye, Zhishi,Ding, Jinchang,Wu, Huayue,Cheng, Jiang
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supporting information; experimental part
p. 869 - 873
(2009/05/30)
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- Reusable Cu2O-nanoparticle-catalyzed amidation of aryl iodides
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The amidation of aryl iodides using Cu2O nanoparticles is described. It is a heterogeneous process, no leaching of the Cu2O species occurs, and the catalyst can be recovered and recycled without loss of activity. Georg Thieme Verlag Stuttgart - New York.
- Jammi, Suribabu,Krishnamoorthy, Sankarganesh,Saha, Prasenjit,Kundu, Dipti S.,Sakthivel, Sekarpandi,Ali, Md Ashif,Paul, Rajesh,Punniyamurthy, Tharmalingam
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experimental part
p. 3323 - 3327
(2010/03/03)
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- CuO nanoparticles catalyzed C-N, C-O, and C-S cross-coupling reactions: Scope and mechanism
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CuO nanoparticles have been studied for C-N, C-O, and C-S bond formations via cross-coupling reactions of nitrogen, oxygen, and sulfur nucleophiles with aryl halides. Amides, amines, imidazoles, phenols, alcohols and thiols undergo reactions with aryl iodides in the presence of a base such as KOH, Cs 2CO3, and K2CO3 at moderate temperature. The procedure is simple, general, ligand-free, and efficient to afford the cross-coupled products in high yield.
- Jammi, Suribabu,Sakthivel, Sekarpandi,Rout, Laxmidhar,Mukherjee, Tathagata,Mandai, Santu,Mitra, Raja,Saha, Prasenjit,Punniyamurthy, Tharmalingam
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supporting information; experimental part
p. 1971 - 1976
(2009/07/01)
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- Copper-catalyzed N-arylation of amides and azoles using phosphine-free hydrazone ligands
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Phosphine-free hydrazone such as 1c was found to be an efficient ligand for the copper-catalyzed Goldberg-type N-arylation of amides and Ullmann-type N-arylation of azoles with aryl halides under mild conditions. A variety of N-arylamides and N-arylazoles were synthesized in good to high yields. Georg Thieme Verlag Stuttgart.
- Mino, Takashi,Harada, Yoshikazu,Shindo, Hiroaki,Sakamoto, Masami,Fujita, Tsutomu
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p. 614 - 620
(2008/12/22)
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- Short and practical synthesis of N′,N′-disubstituted N-aryl-1,2-ethylene-diamines by a decarboxylative ring-opening reaction under nucleophilic conditions
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A straightforward and practical synthesis of N′,N′- disubstituted N-aryl-1,2-ethylenediamines, starting from anilines, via N-aryloxazolidin-2-ones is described. A decarboxylative ring-opening reaction of N-aryloxazolidin-2-ones, using aliphatic secondary
- Morita, Yasuhiro,Ishigaki, Takeshi,Kawamura, Kuniaki,Iseki, Katsuhiko
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p. 2517 - 2523
(2008/02/13)
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- An efficient synthesis of organic carbonates using nanocrystalline magnesium oxide
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An efficient and selective synthesis of organic carbonates using nanocrystalline magnesium oxide has been realized by the direct condensation of alcohols and diethyl carbonate. The catalyst is quantitatively recovered by simple centrifugation and can be reused for four cycles with almost consistent activity.
- Kantam, M. Lakshmi,Pal, Ujjwal,Sreedhar,Choudary
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p. 1671 - 1675
(2008/02/11)
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- 1,1,1-Tris(hydroxymethyl)ethane as a new, efficient, and versatile tripod ligand for copper-catalyzed cross-coupling reactions of aryl iodides with amides, thiols, and phenols
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1,1,1-Tris(hydroxymethyl)ethane was presented as a new, efficient, and versatile tridentate O-donor ligand suitable for the copper-catalyzed formation of C-N, C-S, and C-O bonds. This inexpensive and commercially available tripod ligand has been demonstrated to facilitate the copper-catalyzed cross-coupling reactions of aryl iodides with amides, thiols, and phenols to afford the corresponding desired products in good to excellent yields.
- Chen, Yao-Jung,Chen, Hsin-Hung
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p. 5609 - 5612
(2007/10/03)
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- Ring enlargement and sulfur-transfer processes in SiO2-catalyzed reactions of thiocarbonyl compounds with optically active oxiranes
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The reactions of 1,3-dioxolane-2-thione (3) with (S)-2-methyloxirane ((S)-1) and with (R)-2-phenyloxirane ((R)-2) in the presence of SiO2 in anhydrous dichloroalkanes led to the optically active spirocyclic 1,3-oxathiolanes 8 with Me at C(7) and 9 with Ph at C(8), respectively (Schemes 2 and 3). The analogous reaction of 1,3-dimethylimidazolidine-2-thione (4a) with (R)-2 yielded stereoselectively (S)-2-phenylthiirane ((S)-10) in 83% yield and 97% ee together with 1,3-dimethylimidazolidin-2-one (11a). In the cases of 3-phenyloxazolidine-2-thione (4b) and 3-phenylthiazolidine-2-thione (4c), the reaction with (RS)-2 yielded the racemic thiirane (RS)-10, and the corresponding carbonyl compounds 11b and 11c (Scheme 4 and Table 1). The analogous reaction of 4a with 1,2-epoxycyclohexane (=7-oxabicyclo[4.1.0]heptane; 7) afforded thiirane 12 and the corresponding carbonyl compound 11a (Scheme 5). On the other hand, the BF3-catalyzed reaction of imidazolidine-2-thione (5) with (RS)-2 yielded the imidazolidine-2-thione derivative 13 almost quantitatively (Scheme 6). In a refluxing xylene solution, 1,3-diacetylimidazolidine-2-thione (6) and (RS)-2 reacted to give two imidazolidine-2-thione derivatives, 13 and 14 (Scheme 7). The structures of 13 and 14 were established by X-ray crystallography (Fig.).
- Malaschichin, Sergej,Fu, Changchun,Linden, Anthony,Heimgartner, Heinz
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p. 3253 - 3262
(2007/10/03)
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- Method of forming a carbon-carbon or carbon-heteroatom linkage
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The invention relates to a method of creating a carbon-carbon or carbon-heteroatom linkage by reacting an unsaturated compound bearing a leaving group and a nucleophilic compound. More specifically, the invention relates to the creation of a carbon-nitrogen linkage involving the arylation of nitrogenous organic derivatives. The inventive method consists in creating a carbon-carbon or carbon-heteroatom linkage by reacting an unsaturated compound bearing a leaving group and a nucleophilic compound providing a carbon atom or a heteroatom (HE) capable of being substituted for the leaving group, thereby creating a C—C or C-HE linkage. The invention is characterised in that the reaction is carried out in the presence of an effective quantity of a catalyst based on copper and at least one ligand comprising at least one imine function and at least one additional nitrogen atom as chelating atoms
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Page/Page column 32
(2010/02/14)
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- Highly efficient and mild copper-catalyzed N- and C-arylations with aryl bromides and iodides
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Mild, efficient, copper-catalyzed N-arylation procedures for nitrogen heterocycles, amides, carbamates, and C-arylation procedures for malonic acid derivatives have been developed that afford high yields of arylated products with excellent selectivity. The N-arylation of imidazole with aryl bromides or iodides was found to be greatly accelerated by inexpensive, air-stable catalyst systems, combining catalytic copper salts or oxides with a set of structurally simple chelating ligands. The reaction was shown to be compatible with a broad range of aryl halides, encompassing sterically hindered, electron-poor, and electron-rich ones, providing the arylated products under particularly mild conditions (50-82°C). The lower limit in ligand and catalyst loading and the scope of Ullmann-type condensations catalyzed by complexes bearing those ligands with respect to the nucleophile class have also been investigated. Chelating Schiff base Chxn-Py-Al (1c) generates a remarkably general copper catalyst for N-arylation of pyrrole, indole, 1,2,4-triazole, amides, and carbamates; and C-arylation of diethyl malonate, ethyl cyanoacetate, and malononitrile with aryl iodides under mild conditions (50-82°C). The new method reported here is the most successful to date with regard to Ullmann-type arylation of some of these nucleophiles.
- Cristau, Henri-Jean,Cellier, Pascal P.,Spindler, Jean-Francis,Taillefer, Marc
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p. 5607 - 5622
(2007/10/03)
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- Resin-bound triaryl bismuthanes and bismuth diacetates: Novel multidirectional linkers and novel resin-bound arylation reagents
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A general synthesis of resin-bound triaryl bismuthanes and resin-bound triaryl bismuth diacetates starting from commercially available chloromethyl polystyrene is reported. For the first time resin-bound bismuth has been utilized as part of a multidirectional linker system for solid-phase organic synthesis and as a resin-bound arylation reagent.
- Rasmussen, L. Kyhn,Begtrup, Mikael,Ruhland, Thomas
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p. 6890 - 6893
(2007/10/03)
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- Carboxylation and Mitsunobu reaction of amines to give carbamates: Retention vs inversion of configuration is substituent-dependent
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(Equation Presented) A mild method for the synthesis of carbamates from amino alcohols involves sequential carboxylation with carbon dioxide, followed by a Mitsunobu reaction. Unexpectedly, the stereochemical course of the Mitsunobu reaction is dependent on whether the carbamic acid intermediate is N-substituted with hydrogen (retention) or carbon (inversion).
- Dinsmore, Christopher J.,Mercer, Swati P.
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p. 2885 - 2888
(2007/10/03)
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- Process for arylating or vinylating or alkynating a nucleophilic compound
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The present invention concerns a process for arylating or vinylating or alkynating a nucleophilic compound. More particularly, the invention concerns arylating nitrogent-containing organic derivatives. The arylating or vinylating or alkynating process of the invention consists of reacting a nucleophilic compound with a compound carrying a leaving group and is characterized in that the reaction is carried out in the presence of an effective quantity of a catalyst based on a metallic element M selected from groups (VIII), (Ib) and (IIb) of the periodic table and at least one at least bidentate ligand comprising at least two chelating atoms, namely at least one oxygen atom and at least one nitrogen atom.
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- Process for arylating or vinylating or alkynating a nucleophilic compound
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The present invention concerns a process for arylating or vinylating or alkynating a nucleophilic compound. More particularly, the invention concerns arylating nitrogen-containing organic derivatives. The arylating or vinylating or alkynating process of the invention consists of reacting a nucleophilic compound with a compound carrying a leaving group and is characterized in that the reaction is carried out in the presence of an effective quantity of a catalyst based on a metallic element M selected from groups (VIII), (Ib) and (IIb) of the periodic table and at least one ligand comprising at least one imine function and at least one supplemental nitrogen atom as the chelating atoms.
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- Highly efficient CuI-catalyzed coupling of aryl bromides with oxazolidinones using Buchwald's protocol: a short route to linezolid and toloxatone.
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[reaction: see text] Coupling of a variety of substituted aryl bromides with oxazolidinones has been achieved using the Buchwald protocol for the amidation of aryl halides. This procedure is exemplified by the synthesis of two medicinally important molecules, linezolid and toloxatone.
- Mallesham,Rajesh,Reddy, P Rajamohan,Srinivas,Trehan, Sanjay
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p. 963 - 965
(2007/10/03)
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- Cyclic AMP-specific phosphodiesterase inhibitors
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Novel pyrrolidine compounds that are potent and selective inhibitors of PDE4, as well as methods of making the same, are disclosed. Use of the compounds in the treatment of inflammatory diseases and other diseases involving elevated levels of cytokines, as well as central nervous system (CNS) disorders, also is disclosed.
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- Nickel catalyzed addition of -NH- containing compounds to vinyl and aryl halides
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A process for producing unsaturated nitrogen containing compounds such as enamides, enamines and aryl amines/amides is disclosed. A vinyl halide or aryl halide is reacted with an -NH- containing compound in the presence of a catalytic amount of a catalyst precursor composition comprising zero-valent nickel and an organophosphine ligand. One step coupling of vinyl halides and aryl halides with -NH- containing compounds is made possible by practice of this invention.
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- 3-Aryl-2-oxazolidinones through the palladium-catalyzed N-arylation of 2-oxazolidinones.
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[reaction: see text] 3-Aryl-2-oxazolidinones are obtained in good yields through the palladium-catalyzed N-arylation of 2-oxazolidinones with aryl bromides. The nature of aryl bromides, phosphine ligands, bases, and solvents strongly affects the reaction
- Cacchi,Fabrizi,Goggiamani,Zappia
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p. 2539 - 2541
(2007/10/03)
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- Promotion of reaction of N-H bonds with triarylbismuth and cupric acetate
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Arylation of a diverse group of N-H containing compounds at room temperature with triarylbismuth and cupric acetate in the presence of a tertiary amine promoter, such as triethylamine or pyridine, is described. This mild and highly efficient procedure, which is based on Barton's earlier work on the arylation of amines, can be applied to amides, imides, ureas, carbamates, and sulfonamides. Copyright (C) 1996 Elsevier Science Ltd.
- Chan, Dominic M. T.
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p. 9013 - 9016
(2007/10/03)
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- Aminomethyloxooxazolidinyl arylbenzene derivatives useful as antibacterial agents
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Novel aminomethyloxooxazolidinyl arylbenzene derivatives, wherein the aryl includes the phenyl, substituted phenyl, pyridyl, and substituted pyridyl groups, such as (l)-N-{3-[4-(4'-pyridyl)phenyl]-2-oxooxazolidin-5-ylmethyl{acetamide, possess useful antib
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- gem-cyclodialkylation A facile synthetic route to N-substituted heterocycles
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N-alkylated and N-arylated pyrroles, pyrrolidines, and piperidines are synthesized in high yield by the reaction between cyclic ethers and primary amines over a heterogeneous titania catalyst.
- Hargis, Duane C.,Shubkin, Ronald L.
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p. 2991 - 2994
(2007/10/02)
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- ANOMALOUS RING OPENING OF N-ARYL-2-OXAZOLIDINONES BY ANHYDROUS ALKOXIDE:A CONVENIENT PREPARATION OF N-(ALKOXYETHYL)-2,6-DISUBSTITUTED ANILINES
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N-(2-Alkoxyethyl)anilines may be prepared by acylation of an N-unsubstituted aniline with 2-chloroethyl chloroformate, ring closure to oxazolidinone, ring opening with alkoxide under anhydrous conditions to a carbamic acid salt, and decarboxylation.This unexpected mode of ring opening is especially useful in the preparation of N-(2-alkoxyethyl)-2,6-disubstituted anilines.
- Fancher, L.W.,Gless, R.D.,Wong, R.Y.
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p. 5095 - 5098
(2007/10/02)
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