- Cu(OAc)2·H2O-promoted tandem β-alkynyl elimination of α-or β-hydroxy propargylic alcohols and homocoupling of the resulting alkynyl species
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α or β-hydroxy propargylic alcohols undergo tandem C(sp)-C(sp3) bond cleavage via β-alkynyl elimination and homocoupling of the resulted alkynyl species in the presence of Cu(OAc)2·H2O to produce the corresponding hydroxycarbonyl com
- Xu, Xiangsheng,Huang, Zhenyong,Lu, Yanfeng
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Read Online
- On the comparable activity in plasmonic photocatalytic and thermocatalytic oxidative homocoupling of alkynes over prereduced copper ferrite
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Despite of extensive attention on the copper-based heterogeneous oxidative homocoupling of alkynes (OHA) to 1,3-diynes, the photocatalytic OHA is scarcely investigated. By screening copper-containing spinel catalysts, we discovered that a prereduced coppe
- Zhu, Ying,Deng, Nan,Feng, Meiqing,Liu, Peng
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Read Online
- Synthesis, α-glucosidase inhibition and antioxidant activity of the 7-carbo–substituted 5-bromo-3-methylindazoles
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Series of 7-aryl- (3a–f), 7-arylvinyl- (3g–k) and 7-(arylethynyl)-5-bromo-3-methylindazoles (4a–f) have been evaluated through enzymatic assay in vitro for inhibitory effect against α-glucosidase activity and for antioxidant potential through the 2,2-diph
- Gildenhuys, Samantha,Magwaza, Nontokozo M.,Mphahlele, Malose J.,Setshedi, Itumeleng B.
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Read Online
- Creating Dynamic Nanospaces in Solution by Cationic Cages as Multirole Catalytic Platform for Unconventional C(sp)?H Activation Beyond Enzyme Mimics
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Herein we demonstrate that, based on the creation of dynamic nanospaces in solution by highly charged positive coordination cage of [Pd6(RuL3)8]28+, multirole and multi-way cage-confined catalysis is accomplisha
- Guo, Jing,Hu, Peng,Li, Kang,Lu, Yu-Lin,Su, Cheng-Yong,Wu, Kai
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supporting information
(2021/12/14)
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- Method for preparing conjugated diyne compound by using copper complex
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The invention relates to a method for preparing a conjugated diyne compound by using a copper complex. The method comprises the following step of: in the presence of alkali, carrying out a Glaser coupling reaction at room temperature by using alkyne as a raw material, the copper complex containing ortho-carborane Schiff base ligand as a catalyst and air as an oxidizing agent to prepare the conjugated diyne compound. Compared with the prior art, the copper complex containing the ortho-carborane Schiff base ligand is used for efficiently catalyzing the Glaser coupling reaction of alkyne to prepare the conjugated diyne compound; and the method has the advantages that selectivity is good, a catalyst dosage is low, reaction conditions are mild, a reaction can be performed in an open manner (wherein air is used as an oxidizing agent), a reaction rate is high, yield is relatively high, a substrate range is wide, and the method has wide application prospects in industry.
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Paragraph 0053-0058; 0059-0060; 0065-0066; ...
(2021/07/14)
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- Synthesis of 3,4-bis(Butylselanyl)selenophenes and 4-alkoxyselenophenes promoted by oxone
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We describe herein an alternative transition-metal-free procedure to access 3,4-bis(butylsela nyl)selenophenes and the so far unprecedented 3-(butylselanyl)-4-alkoxyselenophenes. The protocol involves the 5-endo-dig electrophilic cyclization of 1,3-diynes promoted by electrophilic organosele-nium species, generated in situ through the oxidative cleavage of the Se-Se bond of dibutyl diselenide using Oxone as a green oxidant. The selective formation of the title products was achieved by controlling the solvent identity and the amount of dibutyl diselenide. By using 4.0 equiv of dibutyl diselenide and acetonitrile as solvent at 80?C, four examples of 3,4-bis(butylselanyl)selenophenes were obtained in moderate to good yields (40–78%). When 3.0 equiv of dibutyl diselenide were used, in the presence of aliphatic alcohols as solvent/nucleophiles under reflux, 10 3-(butylselanyl)-4-alkoxyselenophenes were selectively obtained in low to good yields (15–80%).
- Hellwig, Paola S.,Guedes, Jonatan S.,Barcellos, Angelita M.,Perin, Gelson,Lenard?o, Eder J.
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- Functionalization of graphene oxide sheets with magnetite nanoparticles for the adsorption of copper ions and investigation of its potential catalytic activity toward the homocoupling of alkynes under green conditions
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This paper deals with the preparation of graphene oxide sheets (GO) modified with magnetite nanoparticles (Fe3O4NPs) for removing Cu(II) ions from aqueous solutions. Moreover, the recovered Cu(II)-based material was recycled as a cat
- Baouab, Mohammed Hassen V.,Beyou, Emmanuel,Chaabane, Laroussi,Luneau, Dominique
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- Transition-metal-free variant of Glaser- and Cadiot-Chodkiewicz-type Coupling: Benign access to diverse 1,3-diynes and related molecules
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Efficient and transition-metal-free transformations towards the synthesis of 1,3-diynes have been described from their corresponding terminal acetylenes or 1,1-dibromo-1-alkenes. The efficiency of molecular iodine as catalyst in aqueous medium, driven the transformation to afford 1,3-diynes in moderate to good yields. The developed reaction conditions revealed appreciable functional group tolerance in aqueous medium. Further, the scope of the transition-metal-free approach for the synthesis of 1,3-enynes has been investigated using terminal alkynes as easy available precursors.
- Kaldhi, Dhananjaya,Vodnala, Nagaraju,Gujjarappa, Raghuram,Kabi, Arup K.,Nayak, Subhashree,Malakar, Chandi C.
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supporting information
(2020/03/13)
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- Tuning of cross-Glaser products mediated by substrate-catalyst polymeric backbone interactions
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Tuning of cross-Glaser products using different polymeric backbones supported by copper oxide nano-catalysts has been demonstrated by tweaking the substrate-catalyst interactions under greener conditions. Further, highly reactive magnetically separable and recyclable catalyst with scalability is demonstrated.
- Ali, Md. Ehesan,Dar, Arif Hassan,Gowri, Vijayendran,Jayamurugan, Govindasamy,Kaur, Sharanjeet,Mukhopadhyaya, Aritra,Neethu, K. M.,Sartaliya, Shaifali,Selim, Abdul
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supporting information
p. 2582 - 2585
(2020/03/10)
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- Synthesis of 8-carbo substituted 2-(trifluoromethyl)-4H-furo[2,3-h]chromen-4-ones and their thienoangelicin derivatives
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Tandem Sonogashira cross-coupling and heteroannulation of 7-hydroxy-8-iodo-2-(trifluoromethyl)chromen-4-one with terminal acetylenes afforded the 8-carbo–substituted 2-(trifluoromethyl)-4H-furo[2,3-h]chromen-4-ones 2a–i. The latter were reacted with methyl mercaptoacetate in the presence of triethylamine to afford the corresponding 7,8-dihydro-5H-furo[2,3-h]thieno[2,3-c]chromen-5-one derivatives 3a–i. The structures of the prepared compounds were characterized using a combination of NMR (1H-, 13C & 19F-), IR and mass spectroscopic techniques, and confirmed by single X-ray crystal structures of 8-(3-fluorophenyl)-2-(trifluoromethyl)-4H-furo[2,3-h]chromen-4-one (2b) and 2-phenyl-7-(trifluoromethyl)-7,8-dihydro-5H-furo[2,3-h]thieno[2,3-c]chromen-5-one (3a). The highlight of this investigation is the conversion of 2-(trifluoromethyl)–substituted 4H-furo[2,3-h]chromen-4-ones into trifluoromethyl–substituted thienoangelicin analogues.
- Olomola, Temitope O.,Mphahlele, Malose J.
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- Chemoselective Cobalt(I)-Catalyzed Cyclotrimerization of (Un)Symmetrical 1,3-Butadiynes for the Synthesis of 1,2,4-Regioisomers
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The cobalt(I)-catalyzed cyclotrimerization of (un)symmetrical 1,4-disubstituted 1,3-butadiynes is presented. In the case of unsymmetrical 1,3-butadiynes, this reaction can generate eight 1,2,4-substituted and four 1,3,5-substituted isomers. A single 1,2,4-substituted isomer was formed in excellent yields (up to 99%) and exclusive regioselectivities (>99:1) when symmetrical or a 1,3-butadiyne with an aryl or alkyl substituent and a trimethylsilyl group were applied. A large number of products accepting a wide variety of functional groups were synthesized.
- Weber, Sebastian M.,Hilt, Gerhard
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supporting information
p. 4106 - 4110
(2019/06/17)
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- Copper (II) catalyzed homocoupling and heterocoupling of terminal alkynes
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Cu(OTf)2 catalyzed homo– and heterocoupling of aromatic and aliphatic terminal alkynes has been developed. Symmetric and unsymmetric 1,3-diynes have been synthesized in good yields under an aerobic condition in the presence of an organic base D
- Holganza, Maria Katrina,Trigoura, Leslie,Elfarra, Suzanne,Seo, Yoona,Oiler, Jeremy,Xing, Yalan
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p. 1179 - 1181
(2019/03/28)
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- Commercial drug norfloxacin as a novel ligand for the copper-catalyzed N-arylation of imidazole with aryl halides
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Norfloxacin was used as an efficient ligand for the CuBr-catalyzed C-N coupling reaction of imidazole and aryl halides. The protocol presented good functional group compatibility, permitting many aryl halides to react with imidazole to form the desired products in good to excellent yields.
- Wu, Fengtian,Nan, Chenlong,Ma, Minyang,Li, Huiqin,Xie, Jianwei
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- Controllable chemoselectivity in the coupling of bromoalkynes with alcohols under visible-light irradiation without additives: Synthesis of propargyl alcohols and α-ketoesters
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The chemoselectivity of visible-light-induced coupling reactions of bromoalkynes with alcohols can be controlled by simple changes to the reaction atmosphere (N2 or O2). A N2 atmosphere favours propargyl alcohols via a direct C-C coupling process, whereas an O2 atmosphere results in the generation of α-ketoesters through the oxidative CC/C-O coupling pathway.
- Ni, Ke,Meng, Ling-Guo,Ruan, Hongjie,Wang, Lei
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p. 8438 - 8441
(2019/07/22)
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- Synergistic effect of bimetallic PdAu nanocrystals on oxidative alkyne homocoupling
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Bimetallic PdAu nanocrystals with different component ratios were obtained to investigate alkyne homocoupling. We found that the synergistic effect of Pd and Au plays an important role in the reaction. Alkynes with a variety of substituent groups could ef
- Chen, Zheng,Shen, Rongan,Chen, Chen,Li, Jinpeng,Li, Yadong
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supporting information
p. 13155 - 13158
(2018/11/30)
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- Copper(II)/Palladium(II) catalysed highly selective cross-coupling of terminal alkynes in supercritical carbon dioxide
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An efficient protocol for the synthesis of unsymmetrical 1,3-diynes was developed using supercritical carbon dioxide (ScCO2) as the solvent. The direct coupling of two different terminal alkynes is catalysed by a bimetallic catalyst, CuCl2·2H2O/Pd(NH3)4Cl2·H2O, in the presence of the base tetramethylethylenediamine (TMEDA) and O2. In pure ScCO2, our bimetallic catalytic system maintains high activity over a wide substrate scope to provide unsymmetrical 1,3-diynes in good to excellent yields. In the proposed reaction mechanism, the synergistic cooperation between copper(II) and palladium(II) centres is responsible for the superior selectivity of the cross-coupling.
- Wang, Yunlong,Suo, Quanling,Han, Limin,Guo, Linlin,Wang, Yaqi,Li, Fawang
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p. 1918 - 1925
(2018/03/12)
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- Ester functionalized hydrophobic task specific ionic liquid for Glaser coupling
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A new hydrophobic ester functionalized task specific ionic liquid has been synthesized and its application explored in the synthesis of conjugated 1,3-diynes through Glaser coupling of terminal alkynes. Terminal alkynes undergo oxidativecoupling smoothly
- Patil, Jayavant D.,Korade, Suyog N.,Chinchkar, Sarika M.,Pore, Dattaprasad M.
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p. 963 - 968
(2018/07/15)
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- Zeolite-based copper catalyst for decarboxylative coupling of alkynyl carboxylic acids with aryl iodides
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A series of nanoporous aluminosilicate materials (zeolite FAU(Y), LTA(A), and mesoporous Al-SBA-15) was prepared to investigate their catalytic performances in decarboxylative coupling reactions of alkynyl carboxylic acids with aryl iodides. The aluminosilicate frameworks were used for binding Cu(II) ions without coordination by organic ligands. Effects of pore size and Cu(II) content of the aluminosilicates on the catalytic activity and product yield were investigated by varying the solvent, base, and functional groups in the reactants. This catalytic system provided high yields and good selectivity for the desired diaryl alkynes. In addition, the Cu(II)-exchanged zeolite Y catalyst which is NaCuY(0.11) exhibited high recyclability, showing no significant change in catalytic performance after six repetitions.
- Park, Jaerim,Jung, Dasom,Kim, Han-Sung,Na, Kyungsu,Lee, Sunwoo
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- Application of the polyacrylonitrile fiber as a novel support for polymer-supported copper catalysts in terminal alkyne homocoupling reactions
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A commercially available synthetic polyacrylonitrile fiber, capable of acting as a novel support for polymer-supported copper catalyst in terminal alkyne homocoupling reactions, is presented. Detailed characterization by inductively coupled plasma (ICP) analysis, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) confirmed the changes and stability of the fiber catalyst during the modification and utilization processes. Moreover, the catalytic reactions proceeded at room temperature using air as a green oxidant to afford nearly quantitative yields (95-99%); the fiber catalyst has shown excellent activity and superior recyclability (over 16 cycles); and the procedure is operationally simple and amenable to the gram scale in continuous-flow processing. Furthermore, the prominent features (high strength, good flexibility, etc.) of the polyacrylonitrile fiber make the fiber-supported catalyst very attractive for fixed-bed reactors in the chemical industry.
- Shi, Xian-Lei,Hu, Qianqian,Wang, Fang,Zhang, Wenqin,Duan, Peigao
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p. 233 - 239
(2016/03/08)
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- Efficient and environmentally friendly Glaser coupling of terminal alkynes catalyzed by multinuclear copper complexes under base-free conditions
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An efficient catalytic system with dinuclear complex [Cu2(ophen)2] 1 and tetranuclear complex [Cu4(ophen)4(tp)] 2 as catalysts has been developed for the Glaser coupling reaction, which adopts environmentally fr
- Zhang, Ling-Juan,Wang, Yan-Hong,Liu, Jie,Xu, Mei-Chen,Zhang, Xian-Ming
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p. 28653 - 28657
(2016/04/09)
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- CuSCN-mediated homocoupling of terminal alkynes to 1,3-diynes using 4-nitrobenzenediazonium tetrafluoroborate as oxidant
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Eleven 1,3-diynes have been prepared by a highly efficient base-catalysed homocoupling of terminal alkynes mediated by a novel combination of CuSCN/4-nitrobenzenediazonium tetrafluoroborate.
- Liu, Haidong,Chen, Bo,Cai, Jin,Chen, Junqing,Ji, Min
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p. 335 - 337
(2016/07/06)
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- Copper porphyrin-catalyzed aerobic oxidative coupling of terminal alkynes with high TON
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Copper porphyrin-catalyzed Glaser-Hay-type couplings of terminal alkynes generating 1,3-diynes are described. This reaction features high TON (up to 950) and is complete in an hour, providing a facile, clean, and efficient protocol to access various 1,3-d
- Sheng, Wen-Bing,Chen, Tie-Qiao,Zhang, Ming-Zhong,Tian, Mi,Jiang, Guo-Fang,Guo, Can-Cheng
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supporting information
p. 1641 - 1643
(2016/04/04)
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- Mesoporous Copper/Manganese Oxide Catalyzed Coupling of Alkynes: Evidence for Synergistic Cooperative Catalysis
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Copper oxide supported on mesoporous manganese oxide (meso Cu/MnOx) was synthesized by an inverse micelle templated evaporation induced self-assembly procedure. Controlled aggregation of nanoparticles and a monomodal size distribution of mesopores with tunable structural properties were observed. The material possessed superior catalytic activity in the aerobic oxidative coupling of terminal alkynes. Excellent conversion (>99% in most cases) and selectivity were observed in both homocoupling and cross-coupling of alkynes using the optimized reaction conditions. Use of air as the sole oxidant, avoidance of any kind of additives, ease of product separation, great functional group tolerability, wide synthetic scope, and superior reusability (up to eighth cycle) are the notable features of our catalytic protocol. While the reaction mechanism was elucidated, a synergistic cooperative effect between the copper and manganese has been established, which is responsible for the superior catalytic activity. The labile lattice oxygen of the meso Cu/MnOx played a vital role in deprotonation of the alkyne proton, as supported by TPD and TGA studies. Moreover, for the first time, we designed model complexes for the active sites of the catalyst by DFT calculations and provided a qualitative description of the coupling mechanism, which supports the experimental findings.
- Biswas, Sourav,Mullick, Kankana,Chen, Sheng-Yu,Kriz, David A.,Shakil, Md,Kuo, Chung-Hao,Angeles-Boza, Alfredo M.,Rossi, Angelo R.,Suib, Steven L.
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p. 5069 - 5080
(2016/08/18)
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- Copper Catalysis for Selective Heterocoupling of Terminal Alkynes
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A Cu-catalyzed selective aerobic heterocoupling of terminal alkynes is disclosed, which enables the synthesis of a broad range of unsymmetrical 1,3-diynes in good to excellent yields. The results disprove the long-held belief that homocouplings are exclusively favored in the Glaser-Hay reaction.
- Su, Lebin,Dong, Jianyu,Liu, Long,Sun, Mengli,Qiu, Renhua,Zhou, Yongbo,Yin, Shuang-Feng
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supporting information
p. 12348 - 12351
(2016/10/07)
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- 3-(Diphenylphosphino)propanoic acid: An efficient ligand for the Pd/Cu-catalyzed homo-coupling of terminal alkynes in the presence of oxygen at room temperature
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A simple, yet efficient system for PdCl2/CuI to catalyze the homo-coupling reactions of various terminal alkynes has been developed using 3-(diphenylphosphino)propanoic acid as ligand in the presence of oxygen. The alkynes, including aromatic, heteroaromatic and aliphatic alkynes, were transformed at room temperature into the corresponding 1,3-diynes in moderate to excellent yields. The turnover number was up to 1.04×103.
- Liu, Yashuai,Gu, Ningning,Liu, Ping,Xie, Jianwei,Ma, Xiaowei,Liu, Yan,Dai, Bin
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p. 736 - 738
(2015/11/09)
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- Formal [4+ 2] reaction between 1,3-diynes and pyrroles: Gold(I)-catalyzed indole synthesis by double hydroarylation
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Indole synthesis by a gold(I)-catalyzed intermolecular formal [4+2] reaction between 1,3-diynes and pyrroles has been developed. This reaction involves the hydroarylation of 1,3-diynes with pyrroles followed by an intramolecular hydroarylation to give the 4,7-disubstituted indoles. This reaction can also be applied to the synthesis of carbazoles when indoles are used as the nucleophiles instead of pyrroles.
- Matsuda, Yuka,Naoe, Saori,Oishi, Shinya,Fujii, Nobutaka,Ohno, Hiroaki
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supporting information
p. 1463 - 1467
(2015/01/30)
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- One-pot green synthesis of enamides and 1,3-diynes
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A green organic synthetic method combining reductive acylation of ketoximes and oxidative coupling of terminal alkynes was developed. This novel process enables enamides and 1,3-diynes to be synthesized simultaneously in high yields and under mild conditions without the use of terminal reductants/oxidants.
- Liang, Hao,Ren, Zhihui,Wang, Yaoyu,Guan, Zhenghui
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p. 113 - 118
(2015/09/28)
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- Copper immobilized on nano-silica triazine dendrimer (Cu(ii)-TD@nSiO 2) catalyzed synthesis of symmetrical and unsymmetrical 1,3-diynes under aerobic conditions at ambient temperature
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A highly efficient route for the synthesis of symmetrical and unsymmetrical 1,3-diynes has been developed by Cu(ii)-TD@nSiO2/DBU catalyzed homocoupling/heterocoupling of aromatic as well as aliphatic terminal alkynes under aerobic conditions at ambient temperature. The catalyst could be easily recovered and reused several times without significant loss of its activity.
- Nasr-Esfahani, Mahboobeh,Mohammadpoor-Baltork, Iraj,Khosropour, Ahmad Reza,Moghadam, Majid,Mirkhani, Valiollah,Tangestaninejad, Shahram,Agabekov, Vladislav,Rudbari, Hadi Amiri
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p. 14291 - 14296
(2014/04/17)
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- Copper-catalyzed homo- and cross-coupling reactions of terminal alkynes in ethyl lactate
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The bio-based chemical ethyl lactate (EL) has been discovered to be an excellent medium for the Glaser-type homo- and cross-coupling reactions of terminal alkynes. Good to excellent yields of conjugate diynes have been obtained under ligand-free and mild
- Wan, Jie-Ping,Cao, Shuo,Jing, Yanfeng
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p. 631 - 634
(2014/08/05)
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- Facile synthesis of 3, 3′-disubstituted 2, 2′-binaphthyls by transition-metal-catalyzed double benzannulation
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3, 3′-Disubstituted 2, 2′-binaphthyls were prepared by the Cuor Re-catalyzed double benzannulation reaction of 2-(phenylethynyl) benzaldehyde with various butadiynes in the presence of trichloroacetic acid, in moderate to good yields. Acceleration of the second benzannulation was clearly observed.
- Umeda, Rui,Tabata, Hiromasa,Tobe, Yoshito,Nishiyama, Yutaka
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supporting information
p. 883 - 884
(2014/06/23)
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- Copper-catalyzed aerobic oxidative transformation of ketone- Derived N-tosyl hydrazones: An entry to alkynes
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A novel strategy involving Cu-catalyzed oxidative transformation of ketone-derived hydrazone moiety to various synthetic valuable internal alkynes and diynes has been developed. This method features inexpensive metal catalyst, green oxidant, good functional group tolerance, high regioselectivity and readily available starting materials. Oxidative deprotonation reactions were carried out to form internal alkynes and symmetrical diynes. Cross-coupling reactions of hydrazones with halides and terminal alkynes were performed to afford functionalized alkynes and unsymmetrical conjugated diynes. A mechanism proceeding through a Cu-carbene intermediate is proposed for the CC triple bond formation.
- Li, Xianwei,Liu, Xiaohang,Chen, Huoji,Wu, Wanqing,Qi, Chaorong,Jiang, Huanfeng
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supporting information
p. 14485 - 14489
(2015/02/05)
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- Efficient and reusable CuI/1,10-phenanthroline-catalyzed oxidative decarboxylative homocoupling of arylpropiolic acids in aqueous DMF
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An efficient method for synthesis of 1,3-diynes through the CuI/1,10-phenanthroline-catalyzed oxidative decarboxylative homocoupling of aryl pioprolic acids in aqueous DMF has been developed. The catalytic system was suitable for a variety of arylpropiolic acids, and the corresponding 1,3-diynes could be prepared in high yields. The catalytic system was recovered from the organic products by filtration and its aqueous DMF filtrate retained good activity even after at least four cycles of use.
- Liu, De-Xian,Li, Fei-Long,Li, Hong-Xi,Gong, Wei-Jie,Gao, Jun,Lang, Jian-Ping
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p. 4817 - 4822
(2014/08/05)
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- Copper-impregnated magnetite as a heterogeneous catalyst for the homocoupling of terminal alkynes
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Copper-impregnated magnetite is a versatile heterogeneous catalytic system for the synthesis of 1,3-diynes by the homocoupling of terminal alkynes. This catalyst does not require the use of pressurized oxygen as the oxidant and it does not need a solvent or harsh conditions to give the expected products. Moreover, the catalyst can be removed from the reaction medium simply by using a magnet. The reaction occurs at the lowest copper loading reported for any heterogeneous catalyst.
- Perez, Juana M.,Cano, Rafael,Yus, Miguel,Ramon, Diego J.
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p. 1373 - 1379
(2013/07/05)
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- The Glaser-Hay reaction: Optimization and scope based on 13C NMR kinetics experiments
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The oxidative Glaser-Hay coupling of two terminal alkynes to furnish a butadiyne is a key reaction for acetylenic scaffolding. Although the reaction is performed under rather simple conditions [CuCl/TMEDA/O2 (air)], the mechanism is still under
- Vilhelmsen, Mie H.,Jensen, Jonas,Tortzen, Christian G.,Nielsen, Mogens B.
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supporting information
p. 701 - 711
(2013/03/13)
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- Rh(I)-catalyzed decarbonylation of diynones via C-C activation: Orthogonal synthesis of conjugated diynes
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Utilization of C-C bond activation as a unique mode of reactivity for constructing C-C bonds provides new strategies for preparing important organic molecules. Development of a Rh(I)-catalyzed C-C activation of diynones to synthesize symmetrical and unsymmetrical conjugated diynes through decarbonylation is reported. This C-C cleavage strategy takes advantage of the innate reactivity of conjugated ynones without relying on any ring strain or auxiliary directing group. This alkynation method also has orthogonal properties compared to typical cross-coupling reactions.
- Dermenci, Alpay,Whittaker, Rachel E.,Dong, Guangbin
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p. 2242 - 2245
(2013/06/05)
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- Homo and heterocoupling of terminal alkynes using catalytic CuCl 2 and DBU
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Homocoupling of terminal alkynes has been efficiently achieved using catalytic amounts of CuCl2 and DBU. This methodology could be extended to couple two different terminal alkynes together by taking one of the alkyne partners, preferably the electron rich alkyne, in five fold excess than the other. CSIRO 2011.
- Balamurugan, Rengarajan,Naveen, Naganaboina,Manojveer, Seetharaman,Nama, Masthan Vali
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experimental part
p. 567 - 575
(2012/01/02)
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- Pseudo five-component synthesis of 2,5-di(hetero)arylthiophenes via a one-pot Sonogashira-Glaser cyclization sequence
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Based upon a consecutive one-pot Sonogashira-Glaser coupling-cyclization sequence a variety of 2,5-di(hetero)arylthiophenes were synthesized in moderate to good yields. A single Pd/Cu-catalyst system, without further catalyst addition, and easily available, stable starting materials were used, resulting in a concise and highly efficient route for the synthesis of the title compounds. This novel pseudo five-component synthesis starting from iodo(hetero)arenes is particularly suitable as a direct access to well-defined thiophene oligomers, which are of peculiar interest in materials science.
- Urselmann, Dominik,Antovic, Dragutin,Mueller, Thomas J. J.
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supporting information; experimental part
p. 1499 - 1503
(2011/12/22)
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- One-pot synthesis of 1,4-diarylsubstituted 1,3-diynes from the sequential coupling reactions of aryl iodides and propiolic acid
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1,4-Disubstituted 1,3-dialkynes were obtained from the one-pot palladium/copper-catalyzed coupling reactions of aryl iodide and propiolic acid. The optimized catalytic system consisted of 5.0 mol % Pd(PPh3) 2Cl2, 10 mol % dppb, 10 mol % CuI, 2.4 equiv of DBU, and 1.2 equiv of K2CO3. The coupling reaction was carried out at 30 °C for 6 h and subsequently at 80 °C for 3 h.
- Kim, Yong,Park, Ahbyeol,Park, Kyungho,Lee, Sunwoo
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experimental part
p. 1766 - 1769
(2011/05/05)
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- Consecutive one-pot sonogashira-glaser coupling sequence- Direct preparation of symmetrical diynes by sequential Pd/Cu catalysis
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Sonogashira coupling and the catalytic Glaser coupling are both catalyzed by the Pd-Cu complex couple and can be concatenated to a consecutive sequentially Pd/Cu-catalyzed process in a one-pot fashion, and air oxygen serves as the only oxidant in the second step. In a pseudo-four-component synthesis, a broad variety of symmetrically substituted 1,4-bis(hetero)aryl-1,3-butadiynes are obtained in good to excellent yields. Interestingly, the presence of iodide ions has been found to be advantageous over other halides to trigger the Pd/Cu-catalyzed Glaser step, and Pd and Cu species, as well as triethylamine as a base, are prerequisite for both couplings, which proceed with higher efficiency if performed in a one-pot sequence. Two catalytic alkyne coupling reactions were combined in a consecutive sequentially Pd/Cu-catalyzed process to furnish a novel pseudo-four-component synthesis of a variety of symmetrically substituted 1,4-bis(hetero)aryl-1,3-butadiynes in goodyields. Pd and Cu species and triethylamine (base) are essential for the couplings, which proceed with higher efficiency if performed in a one-pot sequence. Copyright
- Merkul, Eugen,Urselmann, Dominik,Mueller, Thomas J. J.
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supporting information; experimental part
p. 238 - 242
(2011/03/20)
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- Iron/copper promoted oxidative homo-coupling reaction of terminal alkynes using air as the oxidant
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An inexpensive catalytic system, which used a readily available Fe(acac)3 and trace quantity of Cu(acac)2 as the co-catalyst and air as the oxidant for the homo-coupling of terminal alkynes, has been developed. The catalytic system could also apply to the cross-coupling reaction of two different terminal alkynes.
- Meng, Xu,Li, Chuanbin,Han, Baochun,Wang, Tiansheng,Chen, Baohua
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supporting information; scheme or table
p. 4029 - 4031
(2010/07/06)
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- Nickel-catalyzed oxidative coupling reactions of two different terminal alkynes using O2 as the oxidant at room temperature: Facile syntheses of unsymmetric 1,3-diynes
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(Formula Presented) Two different terminal alkynes now can be coupled together in the presence of NiCl2-6H2O/Cul by using an excess of one of the terminal alkyne substrates. The new method employed 20 mol % TMEDA as the ligand and environmentally benign O2 or air as the oxidant. It is the first example using Ni-salt as catalyst by employing air or O2 as oxidant, which led to efficient heterocoupling of two different alkynes.
- Yin, Weiyan,He, Chuan,Chen, Mao,Zhang, Heng,Lei, Aiwen
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supporting information; scheme or table
p. 709 - 712
(2009/08/12)
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- Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 8. Preparation of symmetrical and unsymmetrical 1,3-diynes from alkynoyl ylides and oxalyl diylides
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Seven examples of the alkynoyl phosphorus ylides 5 have been prepared and are found, upon flash vacuum pyrolysis (FVP) at 750°C, to undergo extrusion of Ph3PO to give the unsymmetrical 1,3-diynes 9 in moderate yield. Six examples of the oxalyl diylides 6 have been prepared and their fully assigned 13C NMR spectra are presented. Upon FVP, those with R = aryl undergo two-fold extrusion of Ph3PO to give symmetrical 1,3-diynes 13 but this requires the unusually severe temperature of 900°C. In contrast those with R = CO2Me, CO2Et or COPh undergo complete reaction at 500°C but afford only Ph3PO and fragmentation products.
- Aitken, R. Alan,Herion, Hugues,Horsburgh, Caroline E. R.,Karodia, Nazira,Seth, Shirley
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p. 485 - 489
(2007/10/03)
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