- Copper-catalyzed C-N cross-coupling reactions for the preparation of aryl diamines applying mild conditions
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In this work, aryl diamines were prepared by C-N cross-coupling reactions between aryl halides and ethylenediamine. These reactions were successfully catalyzed by low quantities of Cu2O or CuO (1 mol %) employing low reflux temperature and low diamine excess. Products were afforded in good yields (up to 95%).
- Costa, Márcio V.,Viana, Gil M.,De Souza, Thaís M.,Malta, Luiz Fernando B.,Aguiar, Lúcia C.S.
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Read Online
- 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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Read Online
- 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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Read Online
- An efficient and recyclable chitosan supported copper(II) heterogeneous catalyst for C-N cross coupling between aryl halides and aliphatic diamines
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A useful and convenient methodology has been developed for synthesis of mono N-arylated aliphatic 1,2- and 1,3-diamines and amino alcohols. A highly efficient and renewable heterogeneous chitosan supported copper(II) catalyst has been employed for the C-N cross coupling between aryl halides and aliphatic diamines/amino alcohols. The main advantages of this reaction are the high yields of the products, reduced reaction time, convenient work up procedure, renewability of the catalyst, and less metal contamination of the products. All these factors make the present C-N cross coupling reaction economical, green, and sustainable.
- Bodhak, Chandan,Kundu, Ashis,Pramanik, Animesh
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- LIPID NANOPARTICLE COMPOSITION
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Provided herein are lipids that can be used in combination with other lipid components, such as neutral lipids, cholesterol and polymer conjugated lipids, to form lipid nanoparticles for delivery of therapeutic agents (e.g., nucleic acid molecules) for therapeutic or prophylactic purposes, including vaccination.
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Paragraph 00393
(2021/10/15)
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- Visible-Light-Mediated Aerobic Oxidative C(sp3)?C(sp3) Bond Cleavage of Morpholine Derivatives Using 4CzIPN as a Photocatalyst
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Herein, a metal-free strategy for the aerobic oxidative cleavage of the inert C(sp3)?C(sp3) bond was developed. Deconstruction of morpholine derivatives was conducted using visible light as an energy source and O2 as an oxidant under mild conditions. This procedure demonstrated suitable selectivity and functional group tolerance. Moreover, a possible mechanism involving a radical process was proposed based on a series of mechanism exploration and control experiments. (Figure presented.).
- Dong, Chun-Lin,Huang, Lan-Qian,Guan, Zhi,Huang, Chu-Sheng,He, Yan-Hong
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p. 3803 - 3811
(2021/06/28)
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- Green synthesis of N-(2-hydroxyethyl)anilines by the selective alkylation reaction in H2O
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Based on our previous work, a safer and more sustainable protocol for the synthesis of N-(2-Hydroxyethyl)anilines has been developed. The synthesis included the selective alkylation reaction of aniline with 2-chloroethanol in H2O, eliminating the need for any catalysts and solvents during synthesis. Comparing with our previous work, the salient features of this methodology are eco-friendliness, economic benefit, and the ease of obtaining target compounds. The selective alkylation reaction in H2O is amenable to scale-up for the synthesis of N-(2-Hydroxyethyl)anilines.
- Guo, Hui,Hao, Jia,Sun, Tingting,Wang, Zuoyao,Cao, Jian,Zhang, Guobao
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- Scalable preparation of stable and reusable silica supported palladium nanoparticles as catalysts for N-alkylation of amines with alcohols
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The development of nanoparticles-based heterogeneous catalysts continues to be of scientific and industrial interest for the advancement of sustainable chemical processes. Notably, up-scaling the production of catalysts to sustain unique structural features, activities and selectivities is highly important and remains challenging. Herein, we report the expedient synthesis of Pd-nanoparticles as amination catalysts by the reduction of simple palladium salt on commercial silica using molecular hydrogen. The resulting Pd-nanoparticles constitute stable and reusable catalysts for the synthesis of various N-alkyl amines using borrowing hydrogen technology without the use of any base or additive. By applying this Pd-based catalyst, functionalized and structurally diverse N-alkylated amines as well as some selected drug molecules were synthesized in good to excellent yields. Practical and synthetic utility of this Pd-based amination protocol has been demonstrated by upscaling catalyst preparation and amination reactions to several grams-scales as well as recycling of catalyst. Noteworthy, this Pd-catalyst preparation has been up-scaled to kilogram scale and catalysts prepared in both small (1 g) and large-scale (kg) exhibited similar structural features and activity.
- Alshammari, Ahmad S.,Natte, Kishore,Kalevaru, Narayana V.,Bagabas, Abdulaziz,Jagadeesh, Rajenahally V.
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p. 141 - 149
(2020/01/06)
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- Visible light-mediated Smiles rearrangements and annulations of non-activated aromatics
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We report the first examples of radical cation Smiles rearrangements. A series of aryloxy alkylamines underwent spontaneous reaction, with the amino group displacing theipso-alkoxy group through substitution, at ambient temperature and under photoactivation by visible light in the presence of an acridinium catalyst (5 mol%). The study was extended to 3-(2-methoxyphenyl)propan-1-amine derivatives, which lack an appropriateipsoleaving group. Here, efficient cyclisations resulted in displacement of the methoxy group and formation of tetrahydroquinolines.
- Lawson, Connor A.,Dominey, Andrew P.,Williams, Glynn D.,Murphy, John A.
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supporting information
p. 11445 - 11448
(2020/10/12)
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- Ir(bis-NHC)-Catalyzed Direct Conversion of Amines to Alcohols in Aqueous Glycerol
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Sustainable catalytic conversion of amines to alcohols was realized in the presence of iridium catalysts and aqueous glycerol. Iridium catalysts involving bis-N-heterocyclic carbene (bis-NHC) show good reactivity and stability in the conversion of amines into alcohols in aqueous glycerol. The reaction was initiated with the dehydrogenation of amines and followed by hydrolysis and reduction. Iridium catalysts play dual roles in both the dehydrogenation and reduction steps. By employing glycerol as a solvent and hydrogen source, the final reduction was facilitated. The synthesis and characterization of various Ir(bis-NHC) complexes are described along with the catalytic reaction results of the amine into alcohol conversion.
- Cheong, Yeon-Joo,Lee, Seunghyeon,Hwang, Sang Joon,Yoon, Woojin,Yun, Hoseop,Jang, Hye-Young
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supporting information
p. 1940 - 1943
(2019/02/25)
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- The preparation method of the [...] (by machine translation)
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The invention provides a method for preparing [...], using 4 - (4 - aminophenyl) - 3 - morpholone and 5 - chloro - N - (2 - ethylene oxide-based methyl) - 2 - thiophene carboxamide reaction to obtain 5 - [...] - 2 - {(R)- 2 - hydroxy - 3 - [4 - (3 - oxo - 4 - morpholinyl) phenyl amino] - propyl} amide, then adding N, N' - carbonyl di-imidazole, 4 - dimethylamino pyridine, begins to stir, heating reaction to obtain the - 5 - chloro - N - (( (5 S) - 2 - oxo - 3 - (4 - (3 - oxo-morpholine - 4 - yl) phenyl) - 1, 3 - Oxacillin - 5 - yl) methyl) thiophene - 2 - carboxamide. The technique of the invention route after the condition is optimized, mild reaction, high yield. (by machine translation)
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Paragraph 0032; 0033; 0034
(2018/11/22)
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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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- Unmodified Fe3O4 nanostructure promoted with external magnetic field: safe, magnetically recoverable, and efficient nanocatalyst for N- and C-alkylation reactions in green conditions
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Transition metal compounds have emerged as suitable catalysts for organic reactions. Magnetic compounds as soft Lewis acids can be used as catalysts for organic reactions. In this report, the Fe3O4 nanostructures were obtained from Fe2+ and Fe3+-salts, under an external magnetic field (EMF) without any protective agent. The X-ray photoelectron spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy tools were used to characterize these magnetic compounds. The two-dimensional (2-D, it showed nanometric size in the two dimensions, nanorod structure) Fe3O4 compound showed high catalytic activity and stability in N- and C-alkylation reactions. A diverse range of N- and C-alkylation products were obtained in moderate to high yield under green and mild conditions in air. Also the N- and C-alkylation products can be obtained with different selectivity and yield by exposure reactions with EMF. Results of alkylation reactions showed that the presence of Fe(II) and Fe(III) species on the surface of magnetic catalysts (phase structure of magnetic compounds) are essential as very cheap active sites. Also, morphology of magnetic catalysts had influence on their catalytic performances. After the reaction, the catalyst/product(s) separation could be easily achieved with an external magnet and more than 95% of catalyst could be recovered. The catalyst was reused at least four times without any loss of its high catalytic activity for N- and C-alkylation reactions.
- Rafiee, Ezzat,Joshaghani, Mohammad,Abadi, Parvaneh Ghaderi-Shekhi
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p. 2503 - 2522
(2018/01/04)
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- 2,6-Bis(2-methylhydrazine-1-carbonyl)pyridine 1-oxide as an Efficient Ligand for Copper-Catalyzed C–N Coupling Reaction in Water
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Abstract: Cu2O/2,6-bis(2-methylhydrazine-1-carbonyl)pyridine 1-oxide was found to be an efficiently catalytic system for the N-arylation of imidazole, indole, benzimidazole, pyrrole, benzylamine and ethanolamine with aryl iodides and bromides by using NaOH as base in the presence of 20?mol% (n-Bu)4NBr, and water as solvent at 130?°C in 24?h, and giving the N-arylated products in moderate to excellent yields.
- Wang, Xiaochuang,Meng, Fei,Zhang, Jie,Xie, Jianwei,Dai, Bin
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p. 1142 - 1149
(2018/02/22)
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- Electronic effect of substituents on anilines favors 1,4-addition to: Trans -β-nitrostyrenes: Access to N -substituted 3-arylindoles and 3-arylindoles
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A simple and an efficient method for the regioselective synthesis of N-alkyl/aryl/H 3-arylindole derivatives from N-substituted anilines and trans-β-nitrostyrenes has been described using 10 mol% of bismuth(iii) triflate as a catalyst in acetonitrile at 80 °C. The present protocol profits from the formation of new C-C and C-N bonds, broad substrate scope and moderate to good yields.
- Gattu, Radhakrishna,Bhattacharjee, Suchandra,Mahato, Karuna,Khan, Abu T.
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supporting information
p. 3760 - 3770
(2018/05/30)
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- The synthesis of new 1,3-oxazolidines and 1,3-oxazinanes containing (η6-arene)tricarbonylchromium group based on condensation between aldehydes and amino alcohols
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The condensation reactions of β- and γ-amino alcohols containing phenyl or (η6-arene) tricarbonylchromium substituent with formaldehyde, acetaldehyde, benzaldehyde, and (η6-benzaldehyde)tricarbonylchromium were studied. The resulting 1,3-oxazolidine and 1,3-oxazinane products were isolated in a pure form and identified by different physicochemical methods. The effect of (η6-arene)tricarbonylchromium moiety on the reaction process was demonstrated.
- Artemov,Sazonova,Krylova,Zvereva,Pechen,Fukin,Cherkasov,Faerman,Grishina, N. Yu.
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p. 884 - 892
(2018/08/28)
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- An Effective Heterogeneous Copper Catalyst System for C-N Coupling and Its Application in the Preparation of 2-Methyl-4-methoxydiphenylamine (MMDPA)
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A ligand-recyclable, environmentally benign heterogeneous catalyst system composed of CuI and polystyrene-supported N (-(4-(aminomethyl)naphthalen-1-yl)- N (-phenyl-1 H -pyrrole-2-carbohydrazide (PSAP) has been established for Ullmann type C-N coupling based on the homogeneous catalyst system N ′, N ′-diphenyl-1 H -pyrrole-2-carbohydrazide/CuI. This heterogeneous catalyst system maintained the catalytic effectiveness of the homogeneous catalyst. A variety of functionalized aryl bromides can be efficiently aminated with aryl amines and aliphatic amines with high selectivity for amines over alcohols. Moreover, a practical application of this catalyst system to promote the reaction of commercially available 4-methoxy-2-methylaniline and bromobenzene in 10 mmol scale, provided 2-methyl-4-methoxydiphenylamine (MMDPA) with 93% yield with the merit of the approach being simple operation for work-up and purification.
- Yi, Zhou,Huang, Manna,Wan, Yiqian,Zhu, Xinhai
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p. 3911 - 3920
(2018/09/29)
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- METHOD FOR PRODUCING CIS- AND TRANS-ENRICHED MDACH
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A process for preparing trans-enriched MDACH, including: distilling an MDACH starting mixture in the presence of an auxiliary, which is an organic compound having a molar mass of 62 to 500 g/mol, a boiling point at least 5° C. above the boiling point of cis,cis-2,6-diamino-1-methylcyclohexane, and 2 to 4 functional groups, each of which is independently an alcohol group or a primary, secondary or tertiary amino group. The MDACH starting mixture includes 0 to 100% by weight of 2,4-MDACH and 0 to 100% by weight of 2,6-MDACH, based on the total amount of MDACH present in the MDACH starting mixture. The MDACH starting mixture includes both trans and cis isomers. Trans-enriched MDACH includes 0 to 100% by weight of 2,4-MDACH and 0 to 100% by weight of 2,6-MDACH, where the proportion of trans isomers in the mixture is higher than the proportion of trans isomers in the MDACH starting mixture.
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- A method for the preparation of indole compounds and use thereof (by machine translation)
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A method for the preparation of indole compounds and its application, relates to the field of organic synthesis, the preparation method by aniline compound with ethylene oxide in the 1st under the action of catalyst reaction to obtain N - hydroxy ethyl aniline compound, then the N - hydroxy ethyl aniline compound with the aniline of the compounds in the 2nd reaction under the action of catalyst preparation indole compounds. The preparation method step is simple, requires only two-step reaction can efficiently yield to obtain the indole compound, its route is reasonable in design, simple steps, easy operation, low cost, and is suitable for industrial mass production. The preparation method is applied to the preparation of pharmaceutical in the indole structure, can improve the yield of the medicament, the medicine of the large-scale production. (by machine translation)
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Paragraph 0030-0034
(2018/04/01)
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- β-Amino alcohols from anilines and ethylene glycol through heterogeneous Borrowing Hydrogen reaction
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Borrowing Hydrogen (BH), also called Hydrogen Autotransfer (HA), reaction with neat ethylene glycol represents a key step in the preparation of β-amino alcohols. However, due to the stability of ethylene glycol, mono-activation has rarely been achieved. Herein, a combination of Pd/C and ZnO is reported as heterogeneous catalyst for this BH/HA reaction. This system results in an extremely air and moisture stable, and economic catalyst able to mono-functionalize ethylene glycol in water, without further activation of the diol. In this work, different diols and aromatic amines have been explored affording a new approach towards amino alcohols. This study reveals how the combination of two solid species can afford interesting catalytic properties in heterogeneous phase. ZnO activates ethylene glycol while Pd/C is the responsible of the BH/HA cycle. This catalytic system has also been found useful to dehydrogenate indoles affording indolines that undergo in situ BH/HA cycle prior to re-aromatization, representing a tandem heterogeneous process.
- Llabres-Campaner, Pedro J.,Ballesteros-Garrido, Rafael,Ballesteros, Rafael,Abarca, Belén
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supporting information
p. 5552 - 5561
(2017/08/22)
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- Selective C-N coupling reaction of diaryliodonium salts and dinucleophiles
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N-Aryl-α-amino amides including their chiral isomers have demonstrated important applications as pharmaceutical drugs; however, to date, a one-step synthetic route for them still remains to be developed. Herein, an efficient ligand-free copper-catalyzed selective C-N coupling reaction of diaryliodonium salts and dinucleophiles under mild conditions was realized. Diaryliodonium salts prefer to react with dinucleophiles at the site of stronger alkalic amino groups. Thus, a general aliphatic amino-selective N-arylation of α-amino amides was disclosed. Additionally, copper-catalyzed N-arylation of diaryliodonium salts afforded the same products as obtained via palladium-catalyzed reactions of aryl halides.
- Ma, Chang,Wu, Xufeng,Zeng, Qingle,Zhou, Lihong,Huang, Yi
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supporting information
p. 2873 - 2877
(2017/04/14)
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- Transition Metal-Catalysed Intramolecular Carbenoid C?H Insertion for Pyrrolidine Formation by Decomposition of α-Diazoesters
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The use of Pd-, Rh(II)- and Ru(II)-based catalysts has been explored in the transition metal-catalysed intramolecular carbenoid C?H insertion of α-diazoesters leading to pyrrolidines. Although the outcome of the reaction was highly substrate-dependent, in general, it was possible to control the chemoselectivity of the process towards pyrrolidines by adequate catalyst selection. The Pd(0)-catalysts were as efficient as [Rh(Ph3CCO2)2]2 in promoting the C(sp3)?H insertion of ortho-substituted anilines. In contrast, for anilines bearing meta- and para-substituents, the Rh(II)-catalyst provided the best chemoselectivities and reaction yields. On the other hand, [Ru(p-cymene)Cl2]2 was the most efficient catalyst for the insertion reaction of the N-benzyl-N-phenyl and N,N-dibenzyl α-diazoesters, while the C(sp3)?H insertion of the N-benzylsulfonamide substrate was only promoted by [Rh(Ph3CCO2)2]2. According to density functional theory (DFT) calculations, the mechanism involved in the Pd(0)- and Ru(II)-catalysed C(sp3)?H insertions differs considerably from that typically proposed for the Rh(II)-catalysed transformation. Whereas the Pd(0)-catalysed reaction involves a Pd-mediated 1,5-H migration from the C(sp3)?H bond to the carbenoid carbon atom leading to the formal oxidation of the transition metal, a Ru(II)-promoted Mannich type reaction involving a zwitterionic intermediate seems to be operative in the Ru(II)-catalysed transformation. (Figure presented.).
- Solé, Daniel,Amenta, Arianna,Mariani, Francesco,Bennasar, M.-Llu?sa,Fernández, Israel
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supporting information
p. 3654 - 3664
(2017/09/13)
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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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- N-Arylazetidines: Preparation through Anionic Ring Closure
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We report herein an efficient synthesis of diversely substituted N-aryl-2-cyanoazetidines based on an anionic ring-closure reaction. These compounds can be prepared from β-amino alcohols in enantiomerically pure form through a three-step sequence involving (i) copper-catalyzed N-arylation, (ii) N-cyanomethylation of the secondary aniline, and (iii) one-pot mesylation followed by ring closure induced by a base. This high-yielding sequence gives access to azetidines with a predictable and adjustable substitution pattern and also with predictable diastereoselectivity. These compounds are susceptible to multiple further derivatizations through Suzuki coupling or nitrile transformation, thus appearing as valuable new scaffolds for medicinal chemistry. Their rigid shape, featuring an almost planar N-arylamine and a planar four-membered ring, was revealed by both AM1 calculations and X-ray crystallography.
- Quinodoz, Pierre,Drouillat, Bruno,Wright, Karen,Marrot, Jéro?me,Couty, Fran?ois
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p. 2899 - 2910
(2016/04/26)
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- Nano-magnetic Fe3O4@TiO2/Cu2O composite: a simple, effective and reusable heterogeneous catalyst for ligand-free N-arylation of amines and nitrogen heterocycles
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Abstract: A practical and mild synthetic strategy has been investigated for the arylation of aromatic amines and nitrogen heterocycles using nano-magnetic-Fe3O4@TiO2/Cu2O composite and KOH as the base. The protocol does not require the use of expensive ligands. Notably, the catalyst is easily recoverable and reused by magnetic separation up to five runs without appreciable loss of catalytic activity. Graphical Abstract: [Figure not available: see fulltext.]
- Nemati, Firouzeh,Elhampour, Ali
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p. 7611 - 7624
(2016/09/20)
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- Cu2O/nano-CuFe2O4: An efficient and magnetically recoverable catalyst for the ligand-free N-arylation of amines and nitrogen heterocycles with aryl halides
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An efficient strategy has been developed for the N-arylation of azoles and aliphatic amines with aryl halide using a Cu2O/nano-CuFe2O4 magnetic composite as the catalyst and KOH as the base. The methodology is found to be applicable to a variety of nitrogen-containing heterocycles, such as imidazole, indole, and pyrrole, as well as aliphatic amines in high yields with practical simplicity under cost-effective "ligand-free" conditions. The magnetic property of the catalyst allowed its fast separation from the reaction medium by an external magnet. Additionally, the inexpensive catalyst could be recycled for five consecutive runs with small drops in catalytic activity.
- Elhampour, Ali,Nemati, Firouzeh,Kaveh, Mahdieh
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supporting information
p. 223 - 225
(2016/03/01)
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- Room-Temperature Practical Copper-Catalyzed Amination of Aryl Iodides
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An efficient and highly practical procedure is reported for the Ullmann-Goldberg-type copper-catalyzed amination of aryl iodides. By using a combination of copper iodide and proline in the presence of an excess of an amine, a wide range of aryl iodides can be readily aminated at room temperature. The reaction proceeds well regardless of the electronic properties of the starting aryl iodide and the amination products can be obtained without the need for purification by column chromatography in most cases. Owing to its efficiency and the mildness of the reaction conditions, this amination could also be extended to the amination of complex aryl iodides at room temperature.
- Deldaele, Christopher,Evano, Gwilherm
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p. 1319 - 1328
(2016/04/20)
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- Palladium-catalyzed intramolecular carbene insertion into C(sp3)-H bonds
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A palladium-catalyzed carbene insertion into C(sp3)-H bonds leading to pyrrolidines was developed. The coupling reaction can be catalyzed by both Pd0 and PdII, is regioselective, and shows a broad functional group tolerance. This reaction is the first example of palladium-catalyzed C(sp3)-C(sp3) bond assembly starting from diazocarbonyl compounds. DFT calculations revealed that this direct C(sp3)-H bond functionalization reaction involves an unprecedented concerted metalation-deprotonation step. Pd in action: Palladium has been used to catalyze the C(sp3)-H insertion of metal carbenoids derived from α-diazoesters to form pyrrolidines through intramolecular assembly of C(sp3)-C(sp3) bonds. A reaction mechanism involving a metalation-deprotonation step instead of the usual concerted but asynchronous process is proposed.
- Solé, Daniel,Mariani, Francesco,Bennasar, M.-Llu?sa,Fernández, Israel
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supporting information
p. 6467 - 6470
(2016/06/01)
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- N-Alkylation of Alkylolamines with Alcohols Over Mesoporous Solid Acid–Base Cs–B–Zr Catalyst
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Abstract: The mesoporous solid acid–base Cs–B–Zr mixed oxides were synthesized using the co-precipitation method followed by a subsequent thermal treatment. The catalytic activity of solid Cs–B–Zr mixed oxide was tested for solvent free acid–base catalysed direct alkylolamines with alcohols as green alkylating agent. The effects of Cs/B/Zr ratio, calcination temperature, reaction conditions, and reaction substrate on the catalytic performance of the catalysts were investigated. The XRD, N2 adsorption–desorption, ICP-OES, FT-IR and NH3/CO2-TPD results showed that the mesoporous structure and acid–base properties of the catalysts play important roles in the reaction. A suitable number of acid and basic sites on the catalyst lead to a high activity for the N-alkylation reaction. Graphical Abstract: A direct N-alkylation of amino alcohol with alcohols has been developed using mixed oxide Cs–B–Zr as an acid–base bifunctionalized catalyst.[Figure not available: see fulltext.]
- Chen, Aimin,Wang, Houyong,Liu, Rui,Bo, Yingying,Hu, Jun
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p. 1182 - 1193
(2016/07/06)
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- A process for the preparation of intermediates the advantage cuts down Sha Ban
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The invention discloses a synthetic method of rivaroxabanintermediate4-(4-nitrosobenzene)-3-morpholine. The method comprises steps as follows: (1), halogenated benzene (I) and ethanolamine react under the condition of a catalyst and alkali to generate N-ethoxylaniline (II), N-ethoxylaniline (II) and nitrous acid or nitrite react to generate 4-nitroso-N-ethoxylaniline (III), and 4-nitroso-N-ethoxylaniline (III) and chloroacetyl chloride react to generate 4-(4-nitrosobenzene)-3-morpholine (IV). According to the synthetic method of 4-(4-nitrosobenzene)-3-morpholine, required raw materials and reagents are cheap and are easy to obtain, the yield is high, and the cost is low; the reaction condition is mild; fewer three wastes are produced; and the product quality is reliable and stable, and the whole process is very suitable for industrial production.
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Paragraph 0052; 0053; 0054
(2016/10/10)
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- Highly Efficient Mechanochemical N-Arylation of Amino Alcohols and Diamines with Cu0 Powder
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Cu0-catalysed arylations have rightly acquired great importance over the last decade. This paper reports the N-arylation of amino alcohols and diamines with iodobenzene derivatives in a planetary ball mill and an investigation into the procedure. This newly developed solvent-free protocol is fast, efficient and occurs under the mechanochemical activation of metallic copper powder. It does not require additional ligands and gives excellent yields. This paper aims to broaden the scope of mechanochemical Cu0-activation and so a new one-pot, two-step synthesis that combines CuAAC and N-arylation has been successfully performed and reported herein.
- Martina, Katia,Rinaldi, Laura,Baricco, Francesca,Boffa, Luisa,Cravotto, Giancarlo
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p. 2789 - 2794
(2015/12/18)
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- PYRAZOLO-, IMIDAZOLO- AND PYRROLO-PYRIDINE OR -PYRIMIDINE DERIVATIVES AS INHIBITORS O BRUTONS KINASE (BTK)
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The present application discloses compounds that are inhibitors of Btk, compounds that are inhibitors of ΡI3Κδ, and compounds that are dual inhibitors of both Btk and PI3Kδ. Also described are methods for synthesizing such inhibitors and methods for using such inhibitors for the treatment of diseases wherein inhibition of Btk and PI3Kδ provides a therapeutic benefit to a patient having the disease.
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Paragraph 0193
(2015/05/26)
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- Green and efficient protocol for the synthesis of N-(2-hydroxyethyl)anilines by the alkylation reaction in ionic liquid
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A green and efficient protocol for the synthesis of N-(2-hydroxyethyl)anilines by the selective alkylation reaction in ionic liquid [BMIM]BF4 (1-butyl-3-methylimidazolium tetrafluoroborate) has been developed, eliminating the need for toxic and expensive catalysts and volatile organic solvents. The effects of the amount of ionic liquid, temperature, time, and substrate structure on the reaction were investigated. The conversion and selectivity of N-(2-hydroxyethyl)anilines obtained in ionic liquid [BMIM]BF4 are significantly increased in comparison to those traditional methods. Furthermore, the ionic liquid could be easily separated and reused at least five times. It provided a simple and efficient alternative way for the industrial synthesis of N-(2-hydroxyethyl)anilines.
- Guo, Hui,Zhuang, Yuwei,Cao, Jian,Zhang, Guobao
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p. 3368 - 3374
(2014/12/10)
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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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- N-arylation of amines: C-N coupling of amines with arylboronic acids using Fe3O4 magnetic nanoparticles-supported EDTA-Cu(ii) complex in water
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Fe3O4 magnetic nanoparticles-supported EDTA-copper(ii) complex (Fe3O4-EDTA-Cu(ii)) has been prepared and characterized by TEM, SEM, XRD, VSM, TGA, and FT-IR spectrometers. The catalyst was applied for the C-N coupling of arylboronic acids with amines for the preparation of N-aryl compounds. Recovery tests confirm that the catalyst can be easily recovered and reused up to eight times without significant loss of its catalytic activity.
- Mostafalu, Ramin,Kaboudin, Babak,Kazemi, Foad,Yokomatsu, Tsutomu
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p. 49273 - 49279
(2014/12/10)
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- Star-shaped molecules containing both azo chromophores and carbazole units as a new type of photoresponsive amorphous material
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We synthesized a series of star-shaped molecules containing both azo chromophores and carbazole units (nCz-AZ-X), where n is the number of carbazole units (n = 3 and 6) and X represents cyano (CN) and nitro (NT) as the electron-withdrawing groups on the azobenzenes. The azo compounds existed as amorphous solids at room temperature with glass transition temperatures (T g) of 89, 86, 74 and 73 °C for 3Cz-AZ-CN, 3CZ-AZ-NT, 6Cz-AZ-CN and 6Cz-AZ-NT, respectively. Thin solid films of the azo molecular glasses were obtained by spin-coating. The formation of the photoinduced self-structured surface patterns was investigated by irradiating the solid thin films of the azo molecular glasses with a uniform laser beam (532 nm, 200 mW cm-2) at normal incidence. The formation of surface-relief-gratings (SRGs) was studied by exposing the thin films to an interference pattern of the laser beams (532 nm, 80 mW cm-2). The formation of both the self-structured surface patterns and SRGs showed a close correlation with the electron-withdrawing groups of the azo chromophores and the content of the carbazole units in the molecules. The development of these new star-shaped molecules can add a new member to the category of azo molecular glasses and lead to a deeper understanding of the photoinduced effects and their correlation with molecular structures. The Royal Society of Chemistry 2013.
- Yin, Jianjun,Ye, Gang,Wang, Xiaogong
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p. 3794 - 3801
(2013/07/27)
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- NOVEL MOLECULES THAT SELECTIVELY INHIBIT HISTONE DEACETYLASE 6 RELATIVE TO HISTONE DEACETYLASE 1
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The compounds of the present invention are HDAC6 selective inhibitors which are identified on the basis of accumulation of acetylated tubulin without accumulation of acetylated histones. Histone deacetylase or "HDAC" refers to enzymes capable of cleaving an acetyl group (-C(=0)CH3) from proteins, including histone and microtubulins. Compositions comprising the molecules and methods for their use to inhibit the activity of histone deacetylase, including for treatment, are also disclosed.
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Page/Page column 46; 47
(2013/04/24)
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- Substrate-promoted copper-catalyzed N-arylation of amino alcohols with aryl iodides in water
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An efficient method has been developed for the N-arylation of a variety of water-soluble amino alcohols (1.2 mmol) with aryl iodides (1.0 mmol) in water under CuI-catalyzed conditions. The reaction was conducted via substrate-promoted action and did not require an additional ligand or phase-transfer catalyst, and afforded the desired N-aryl amines in acceptable to excellent yields (64%-93%) under mild reaction conditions with a small excess of the amino alcohol.
- Jin, Ming,Zhao, Dan,He, Guozhen,Tong, Yao,Han, Shiqing
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p. 1651 - 1655
(2013/10/21)
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- Solvent-free copper-catalyzed N-arylation of amino alcohols and diamines with aryl halides
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A simple and mild method for the coupling of aryl halides with amino alcohols and diamines is described. The reactions can be performed under ligand-free and solvent-free conditions, and generate the products in good yield.
- Yin, Huiqing,Jin, Ming,Chen, Wei,Chen, Chen,Zheng, Likang,Wei, Ping,Han, Shiqing
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supporting information; experimental part
p. 1265 - 1270
(2012/03/27)
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- Free-radical hydroxymethylation of ketimines generated in situ: A one-pot multicomponent synthesis of β,β-disubstituted-β-aminoalcohols
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We report how an acidic TiCl4-Zn/t-BuOOH system is able to promote the one-pot multicomponent synthesis of β,β-disubstituted- β-aminoalcohols via nucleophilic addition of a hydroxymethyl radical to activated ketimines generated in situ in methanol solvent. While ketimines are generally recognized as less reactive and less stable when compared with aldimines, Ti(IV) plays a key role in facilitating their formation and in enhancing their electrophilic character. As a consequence, the reaction occurs at room temperature and under non-anhydrous conditions in just 1 h, without requiring either the preformation of the ketimine or protection of the amino group. The scope of the reaction is widely explored and a possible mechanism is discussed.
- Rossi, Bianca,Pastori, Nadia,Clerici, Angelo,Punta, Carlo
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p. 10151 - 10156,6
(2020/09/02)
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- A ligand-free and base-free copper catalyzed reaction: Arylation of ammonia and primary amines as their acetate salts
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A ligand-free, base-free copper catalyzed arylation of ammonia and primary amines as their corresponding acetate salts are established. The Carboxylate group is believed to be catalyzing the arylation of ammonia. This reaction is specific for primary amines.
- Siddegowda, Maravanahalli S.,Yathirajan, Hemmige S.,Ramakrishna, Ramesha A.
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p. 5219 - 5222
(2012/11/07)
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- Prodrug strategy for PSMA-targeted delivery of TGX-221 to prostate cancer cells
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TGX-221 is a potent, selective, and cell membrane permeable inhibitor of the PI3K p110β catalytic subunit. Recent studies showed that TGX-221 has antiproliferative activity against PTEN-deficient tumor cell lines including prostate cancers. The objective of this study was to develop an encapsulation system for parenterally delivering TGX-221 to the target tissue through a prostate-specific membrane aptamer (PSMAa10) with little or no side effects. In this study, PEG-PCL micelles were formulated to encapsulate the drug, and a prodrug strategy was pursued to improve the stability of the carrier system. Fluorescence imaging studies demonstrated that the cellular uptake of both drug and nanoparticles was significantly improved by targeted micelles in a PSMA positive cell line. The area under the plasma concentration time curve of the micelle formulation in nude mice was 2.27-fold greater than that of the naked drug, and the drug clearance rate was 6.16-fold slower. These findings suggest a novel formulation approach for improving site-specific drug delivery of a molecular-targeted prostate cancer treatment.
- Zhao, Yunqi,Duan, Shaofeng,Zeng, Xing,Liu, Chunjing,Davies, Neal M.,Li, Benyi,Forrest, M. Laird
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experimental part
p. 1705 - 1716
(2012/09/11)
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- SELECTIVE HDAC INHIBITORS
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This disclosure is related to compounds having the structure (I) wherein Ar1, Ar2, R1 - R6, Z, m, n, o, and p are defined herein. This disclosure also relates to pharmaceutical compositions comprising the above compounds and methods for their use.
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Page/Page column 97-98
(2011/12/04)
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- Regioselectivity of the hydrolysis of 2-(1-alkoxyvinyl)-substituted imidazolidines, 1,3-thiazolidines, and 1,3-oxazolidines
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2-(1-Alkoxyvinyl)-1,3-thiazolidines reacted with H2O or D 2O in the presence of 105 mol % of p-toluenesulfonic acid or trifluoroacetic acid (20°C, 1 h) to give 2-acetyl-1,3-thiazolidine in quantitative yield. 2-(1-Alkoxyvinyl)-3,5-diphenylimidazolidines underwent hydrolysis in the presence of 20 mol % of an acid (20°C, 24 h) at the vinyloxy group with high regioselectivity yielding 2-acetylimidazolidines. Hydrolysis of 2-(1-alkoxyvinyl)-3-phenyl-1,3-oxazolidines in the presence of 10 mol % of p-toluenesulfonic acid (20°C, 5 days) takes two pathways, one of which involves the endocyclic C-O bond with ring opening and the other involves the vinyloxy group to produce 2-acetyl-3-phenyl-1,3-oxazolidine. Unlike phenyl-substituted 1,3-thiazolidines and imidazolidines, hydrolysis of their 3-methyl- and 3,5-dimethyl-substituted analogs in acid medium occurs mainly via ring opening. The observed hydrolysis pathways were interpreted in terms of B3PW91/6-311G(d,p) quantum-chemical calculations.
- Keiko,Funtikova,Vchislo,Larina,Frolov
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experimental part
p. 1832 - 1840
(2012/03/27)
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- CuII-β-cyclodextrin complex as a nanocatalyst for the homo-and cross-coupling of arylboronic acids under ligand-and base-free conditions in air: Chemoselective cross-coupling of arylboronic acids in water
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We report here the transition-metal-catalyzed chemoselective cross-coupling of arylbroronic acids in high yields without using ligand or base. We have developed an efficient copper-catalyzed protocol for the homocoupling and cross-coupling of arylboronic acids. The protocol is also suitable for the cross-coupling of aliphatic primary amines with arylboronic acids. Aminophenols and primary amines bearing an alcoholic substituent on the aliphatic chain were coupled with arylboronic acids, and the products were obtained with high C-N coupling selectivity. An effective catalyst was Cu2-β- cyclodextrin, which is readily available and structurally simple, but has not previously been explored as a catalyst.
- Kaboudin, Babak,Abedi, Yaghoub,Yokomatsu, Tsutomu
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experimental part
p. 6656 - 6662
(2012/01/06)
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- Kinetic parameter estimation of solvent-free reactions monitored by 13C NMR spectroscopy, a case study: Mono- and di-(hydroxy)ethylation of aniline with ethylene carbonate
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The kinetics of solvent-free reactions can be followed in situ by 13C nuclear magnetic resonance (NMR) spectroscopy, provided that the reaction mixture can be maintained liquid at the monitoring temperature. The pros and cons of the technique and the correct translation of the signal intensities into concentrations are discussed. A good model for this investigation is the reaction of ethylene carbonate (1) with aniline (2) at 140°C, two alkylation products of N-mono- and N, N-bis-(2-hydroxy)ethylation of aniline form (compounds 3 and 4, respectively). The overall reaction occurs with heavy volume shrinking, so that the physical as well as the chemical features evolve during the course of the process. The chemical evolution is described by the kinetic constants k1 and k2 of the two N-alkylation steps, the physical evolution by the time-dependent activity coefficients α(t). Two complementary procedures are utilized for the determination of these parameters.
- Lucchini, Vittorio,Fabris, Massimo,NoE, Marco,Perosa, Alvise,Selva, Maurizio
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scheme or table
p. 154 - 160
(2011/10/02)
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- The reaction of primary aromatic amines with alkylene carbonates for the selective synthesis of bis-N-(2-hydroxy)alkylanilines: The catalytic effect of phosphonium-based ionic liquids
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At T ≥ 140 °C, different primary aromatic amines (pX-C 6H4NH2; X = H, OCH3, CH3, Cl) react with both ethylene- and propylene-carbonates to yield a chemoselective N-alkylation process: bis-N-(2-hydroxyalkyl)anilines [pX-C 6H4N(CH2CH(R)OH)2; R = H, CH 3] are the major products and the competitive formation of carbamates is substantially ruled out. At 140 °C, under solventless conditions, the model reaction of aniline with ethylene carbonate goes to completion by simply mixing stoichiometric amounts of the reagents. However, a class of phosphonium ionic liquids (PILs) such as tetraalkylphosphonium halides and tosylates turn out to be active organocatalysts for both aniline and other primary aromatic amines. A kinetic analysis monitored by 13C NMR spectroscopy, shows that bromide exchanged PILs are the most efficient systems, able to impart a more than 8-fold acceleration to the reaction. The reactions of propylene carbonate take place at a higher temperature than those of ethylene carbonate, and only in the presence of PIL catalysts. A mechanism based on the Lewis acidity of tetraalkylphosphonium cations and the nucleophilicity of halide anions has been proposed to account for both the reaction chemoselectivity and the function of the catalysts.
- Selva, Maurizio,Fabris, Massimo,Lucchini, Vittorio,Perosa, Alvise,Noe, Marco
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experimental part
p. 5187 - 5198
(2010/12/25)
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- One-pot synthesis of unsymmetrical N-heterocyclic carbene ligands from N-(2-iodoethyl)arylamine salts
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Image Presented An approach that provides symmetrical, unsymmetrical, and asymmetric N-heterocyclic carbene (NHC) ligands is reported. Reaction of iodoethanol with aniline provides N-(2-iodoethyl)arylamine salts that are then converted to the corresponding iodide. Reaction with aliphatic or aromatic amines followed by triethyl orthoformate was used to provide 26 different NHC ligands.
- Bhanu Prasad,Gilbertson, Scott R.
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supporting information; experimental part
p. 3710 - 3713
(2011/02/28)
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- A new one-pot, four-component synthesis of 1,2-amino alcohols: TiCl 3/t-BuOOH-mediated radical hydroxymethylation of imines
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(Chemical Equation Presented) An amine, an aldehyde, and methanol can be readily assembled in one pot under very mild conditions through a free-radical multicomponent reaction by using an aqueous acidic TiCl3/t-BuOOH system to afford 1,2-amino alcohols in fair to excellent yields.
- Clerici, Angelo,Ghilardi, Alessandra,Pastori, Nadia,Punta, Carlo,Porta, Ombretta
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supporting information; experimental part
p. 5063 - 5066
(2009/05/31)
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