- A facile protocol for copper-free palladium-catalyzed Sonogashira coupling in aqueous media
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The combination of a readily available palladium catalyst and an eco-friendly basic aqueous solution of room-temperature ionic liquid, choline hydroxide (ChOH), was used in a facile protocol alternative to the Sonogashira coupling reaction, alkynylation of aryl halides in the absence of a copper cocatalyst and an external base. The dual nature of ChOH to act as a base and a green solvent played a crucial role in the catalytic cycle. The coupling reaction progressed efficiently to form a Csp-Csp2 bond under the identified conditions although the reaction outcome depended significantly on the substrates.
- Jung, Da-Young,Park, Soo Youl,Kim, Seung-Hoi
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supporting information
p. 110 - 116
(2021/11/09)
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- Magnetic chitosan-functionalized cobalt-NHC: Synthesis, characterization and catalytic activity toward Suzuki and Sonogashira cross-coupling reactions of aryl chlorides
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Aryl chlorides are one of the most stable and available electrophiles, however, their coupling with nucleophiles remains a challenge in organic synthesis. Herein, we prepared a Cobalt-NHC (N-Heterocyclic carbene) complex anchored on magnetic chitosan nanoparticles and assayed its catalytic activity for the reactions of substituted phenylboronic acid and also phenlacetylene with derivatives of aryl chlorides. These reactions are of great importance since they are employed for the synthesis of unsymmetrical diarylethynes and biphenyls, which belong to a prime class of building blocks. The synthesized nanocatalyst was found to be highly efficient in Suzuki and Sonogashira coupling in terms of their activity and recyclability in polyethylene glycol (PEG) as a green reaction media under conditions of temperatures (70 and 100 °C) and Co loading (3 and 6 mol%). To the best of our knowledge, this is the first attempt of using cobalt-NHC complex for catalyzing the abovementioned reactions. Moreover, replacing the earth-abundant Cobalt-based catalyst as an alternative to high cost palladium make this approach promising from sustainable chemistry view.
- Hajipour, Abdol R.,Malek, Shaghayegh Sadeghi
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- Nickel-Catalyzed Sonogashira C(sp)-C(sp2) Coupling through Visible-Light Sensitization
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An efficient method for visible-light-initiated, nickel-catalyzed Sonogashira C(sp)-C(sp2) coupling has been developed via an energy-transfer mode. Thioxanthen-9-one as a photosensitizer could significantly accelerate the arylation of alkynes with a wide
- Zhu, Da-Liang,Xu, Ruijie,Wu, Qi,Li, Hai-Yan,Lang, Jian-Ping,Li, Hong-Xi
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p. 9201 - 9212
(2020/08/14)
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- A transition metal catalytic nitro aromatic hydrocarbon with the end aryl alkyne cross-coupling for preparing aromatic of alkynes (by machine translation)
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The invention disclosed a kind of transition metal catalytic nitro aromatic hydrocarbon with the end aryl alkyne cross-coupling for preparing aromatic alkyne of the method, the method is under protective atmosphere, nitro aromatic aryl alkyne in the tail end of the palladium-containing catalyst, copper-containing catalyst, phosphine and an amine ligand solution system in the cross-coupling reaction, to obtain the aromatic alkyne product. The synthetic method is cheap and easy to materials and the polarity of the nitro arene as electrophilic reagent synthetic aromatic alkyne, can make up for the deficiency of the traditional Sonogashira coupling of the series, has the following advantages: (1) can avoid using the difficult preparation of the more expensive halogenated hydrocarbon; (2) when the multi-coupling reaction, the polarity of nitro can be a coupling product with the raw materials and the by-product with different polarity easily through the column chromatography separation; (3) adopts the transition metal homogeneous catalysis, is expected to be carried out smoothly under mild conditions, functional group tolerance range is wide. (by machine translation)
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Paragraph 0027; 0054; 0056; 0057; 0058
(2018/10/19)
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- DBU-Mediated Efficient Synthesis of Diaryl Ethynes and Enynes from 1,1-Dibromoalkenes at Room Temperature
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The reaction of 1,1-dibromoalkenes and aryl iodides in the presence of DBU and a PdII/CuI catalytic system afforded diaryl alkynes and enynes at ambient temperature. Control experiments demonstrated the essential ligand role of DBU i
- Thummala, Yadagiri,Morri, Ashok K.,Karunakar, Galla V.,Doddi, Venkata Ramana
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supporting information
p. 6280 - 6285
(2018/11/23)
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- Cross-coupling reactions using porous multipod Cu2O microcrystals as recoverable catalyst in aqueous media
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Porous multipod Cu2O microcrystals were found to be an efficient, highly recyclable and eco-friendly catalyst for the cross-coupling reactions of aryl halides and terminal alkynes with high yields in aqueous media. Noteworthy, the Cu2O catalyst can be reused for several times without significant decrease in catalytic activity.
- Tang, Lin,Wu, Chaoting,Hu, Qiyan,Li, Qian,Zhang, Wu
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- A polystyrene supported [PdCl-(SeCSe)] complex: A novel, reusable and robust heterogeneous catalyst for the Sonogashira synthesis of 1,2-disubstituted alkynes and 1,3-enynes
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3,5-Bis((phenylselanyl)methyl)phenol has been synthesized as a novel SeCSe pincer type pre-ligand from commercially available 5-hydroxy isophthalic acid through a multistep synthesis. Then, a polystyrene-supported SeCSe pincer ligand and its corresponding palladium complex were prepared and characterized using different techniques including FT-IR, SEM/EDX, TG/DTG, and XPS. The amount of palladium incorporated into the polymer matrix as determined by ICP analysis was obtained to be 3.64 wt% (0.34 mmol g-1). The PS[PdCl-SeCSe] catalytic activity has been evaluated in the Sonogashira coupling of diverse aryl halides with aromatic and aliphatic terminal alkynes. It was also noted that less reactive and inexpensive aryl bromides and aryl chlorides have been successfully cross-coupled with terminal alkynes using low catalyst loading. Moreover, the developed methodology is effective for the stereoselective preparation of substituted 1,3-enynes.
- Mohammadi, Elmira,Movassagh, Barahman
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supporting information
p. 11471 - 11479
(2018/07/25)
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- Palladium-Catalyzed Desulfitative Cross-Coupling of Arylsulfonyl Hydrazides with Terminal Alkynes: A General Approach toward Functionalized Internal Alkynes
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A palladium-catalyzed Sonogashira-type coupling between arylsulfonyl hydrazides and terminal alkynes via Ar(C)-S bond cleavage is disclosed, which enables the general synthesis of functionalized internal alkynes, especially the Br-substituted ones, in good to excellent yields under acid- and base-free conditions.
- Qian, Liang-Wei,Sun, Mengli,Dong, Jianyu,Xu, Qing,Zhou, Yongbo,Yin, Shuang-Feng
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supporting information
p. 6764 - 6769
(2017/07/15)
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- Formation of C-C, C-S and C-N bonds catalysed by supported copper nanoparticles
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Transition-metal catalysed cross-coupling reactions are still dominated by palladium chemistry. Within the recent past, copper has gained ground against palladium by virtue of its cheaper price and equivalent function in certain reactions. Four catalysts consisting of copper nanoparticles on zeolite, titania, montmorillonite and activated carbon have been tested in three palladium- and ligand-free cross-coupling reactions to form carbon-carbon, carbon-sulfur and carbon-nitrogen bonds. CuNPs/zeolite has been found to be the best one in the Sonogashira reaction of aryl iodides and arylacetylenes, as well as in the coupling of aryl halides with aryl and alkyl thiols, being reusable in both cases. However, the arylation of nitrogen-containing heterocycles (imidazole, pyrazole, benzimidazole and indole) has been better accomplished with CuNPs/titania, albeit CuNPs/activated carbon showed better recycling properties. The catalytic activity of the nanostructured catalysts has been compared with that of twelve commercial copper catalysts, with the former outperforming the latter in the three types of reactions studied.
- Mitrofanov, Alexander Yu.,Murashkina, Arina V.,Martín-García, Iris,Alonso, Francisco,Beletskaya, Irina P.
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p. 4401 - 4412
(2017/10/13)
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- Using Anilines as Masked Cross-Coupling Partners: Design of a Telescoped Three-Step Flow Diazotization, Iododediazotization, Cross-Coupling Process
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The conversion of commercially available anilines into biaryl and biarylacetylene products was realized by using a telescoped, three-reactor flow diazotization/iododediazotization/cross-coupling process. The segmented flow stream created by off-gassing during the Sandmeyer sequence was restored to a continuous column of reaction solution by using a specially designed continuous-flow unit controlled by custom software created in-house. The resultant aryl iodide was then combined with a stream of cross-coupling solution that fed into the final reactor. The system proved versatile as modifications to the diazotization/iododediazotization sequence could be made rapidly to account for any substrate specificity (e.g., solubility problems), leading to a wide substrate scope of Suzuki–Miyaura and Sonogashira cross-coupled products.
- Teci, Matthieu,Tilley, Michael,McGuire, Michael A.,Organ, Michael G.
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p. 17407 - 17415
(2016/11/23)
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- Nickel-catalyzed oxidative decarboxylative coupling reactions between alkynyl carboxylic acids and arylboronic acids
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Nickel-catalyzed decarboxylative coupling reactions between aryl alkynyl carboxylic acids and arylboronic acids were developed. When aryl alkynyl carboxylic acids were reacted with arylboronic acids in the presence of NiCl2(10?mol?%), 2,2′-bipy
- Lee, Ju-Hyeon,Raja, Gabriel Charles Edwin,Son, Yujeong,Jang, Jisun,Kim, Jimin,Lee, Sunwoo
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p. 4824 - 4828
(2016/10/05)
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- A Merrifield resin supported Pd-NHC complex with a spacer(Pd-NHC@SP-PS) for the Sonogashira coupling reaction under copper- and solvent-free conditions
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Synthetic applications of a polymer supported air-stable palladium NHC complex with a spacer (catalyst 6, Pd-NHC@SP-PS) and without a spacer (catalyst 7, Pd-NHC@PS) have been studied for the Sonogashira cross-coupling reaction. The catalysts were prepared
- Jadhav, Sanjay N.,Kumbhar, Arjun S.,Mali, Sawanta S.,Hong, Chang Kook,Salunkhe, Rajashri S.
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p. 2333 - 2341
(2015/03/18)
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- Copper- and Phosphane-Free Sonogashira Coupling of Arenediazonium o-Benzenedisulfonimides
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Arenediazonium o-benzenedisulfonimides can be used as efficient reagents in Sonogashira coupling reactions. In this work, reactions were carried out in DMSO under very mild conditions (without copper or phosphanes), and gave rise to arylated alkynes in good to excellent yields (25 examples, average yield 83 %). o-Benzenedisulfonimide could be recovered from all the reactions in yields of >80 %, so it could be recycled for the preparation of other diazonium salts. Mechanistic insights revealed the fundamental roles of DMSO and the anion of o-benzenedisulfonimide in the formation of the catalyst, and also the importance of DMSO in the catalytic cycle. The Sonogashira coupling between are diazonium o-benzenedisulfonimides and terminal alkynes is a powerful method for the formation of arylated alkynes. No copper, phosphanes, bases, or co-catalysts are needed. Mechanistic insights highlighted the fundamental roles of DMSO and o-benzenedisulfonimide in the formation of the catalyst, and also the important role of DMSO in the catalytic cycle.
- Barbero, Margherita,Cadamuro, Silvano,Dughera, Stefano
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p. 598 - 605
(2015/10/05)
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- Copper- and phosphane-free sonogashira coupling of arenediazonium o-benzenedisulfonimides
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Arenediazonium o-benzenedisulfonimides can be used as efficient reagents in Sonogashira coupling reactions. In this work, reactions were carried out in DMSO under very mild conditions (without copper or phosphanes), and gave rise to arylated alkynes in good to excellent yields (25 examples, average yield 83 %). o-Benzenedisulfonimide could be recovered from all the reactions in yields of >80 %, so it could be recycled for the preparation of other diazonium salts. Mechanistic insights revealed the fundamental roles of DMSO and the anion of o-benzenedisulfonimide in the formation of the catalyst, and also the importance of DMSO in the catalytic cycle. The Sonogashira coupling between are diazonium o-benzenedisulfonimides and terminal alkynes is a powerful method for the formation of arylated alkynes. No copper, phosphanes, bases, or co-catalysts are needed. Mechanistic insights highlighted the fundamental roles of DMSO and o-benzenedisulfonimide in the formation of the catalyst, and also the important role of DMSO in the catalytic cycle. Copyright
- Barbero, Margherita,Cadamuro, Silvano,Dughera, Stefano
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p. 598 - 605
(2014/02/14)
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- Cross-coupling reactions catalyzed by an N-heterocyclic carbene-Pd(ii) complex under aerobic and CuI-free conditions
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A Pd-complex, (Cat. 3), has been successfully employed as a highly efficient and recyclable catalyst for the Sonogashira and Heck reactions of aryl bromides with various terminal acetylenes and olefins. The catalytic reactions proceed with excellent yields with a low catalyst loading (1.0 mol%) under aerobic and CuI-free conditions. A plausible mechanism has also been proposed for the reaction. the Partner Organisations 2014.
- Lu, Hongfei,Wang, Lin,Yang, Feifei,Wu, Runze,Shen, Wei
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p. 30447 - 30452
(2014/08/05)
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- Sonogashira/hydroarylation sequential reactions: Catalyzed by NHC-Pd complexes
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It was found that an air-stable NHC-palladium complex of Pd[(s)-3-C 3H5-4-(C5H5CH2)-1-(2,6- iPr2C6H3)-C3H 3N2](C5H5N)Br2 derived from l-phenylalanine is an effective pre-catalyst for copper-free and phosphine-free Sonogashira reaction of alkynes under aerobic conditions in short reaction time. Moreover, the palladium compound would be reused to catalyze the hydroarylation of alkyne prepared from Sonogashira reaction, which makes firstly Sonogashira/Hydroarylation sequential reactions successful. The arylation of alkynes underwent with a high regio- and stereoselectivity and only trans-arylation of alkyne was observed. No Z/E isomerization of the olefin was observed in the system.
- Yang, Longguang,Li, Yunfei,Chen, Qian,Du, Yufeng,Cao, Changsheng,Shi, Yanhui,Pang, Guangsheng
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p. 5178 - 5184
(2013/06/27)
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- Copper-catalyzed synthesis of internal alkynes via domino coupling between 1,1-dihalo-1-alkenes and arylboronic acids
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We have developed the practical copper-catalyzed formation of various internal alkynes via domino couplings between 1,1-dihalo-1-alkenes and arylboronic acids in the presence of low-cost 8-hydroxylquinoline as the ligand.
- Yan, Hong,Lu, Linhua,Sun, Peng,Zhu, Yan,Yang, Hailong,Liu, Defu,Rong, Guangwei,Mao, Jincheng
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p. 377 - 381
(2013/04/10)
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- Iron-catalyzed oxidative coupling of terminal alkynes with arylboronic acids
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Abstract: Iron-catalyzed cross-coupling of terminal alkynes with arylboronic acids under mild conditions has been developed. Although the reaction gave only moderate yields, the advantage of this method was its use of convenient and inexpensive iron catal
- You, Xiu L.,Xu, Lai,Hu, Tao
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experimental part
p. 300 - 304
(2012/07/14)
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- A Suzuki-type cross-coupling reaction of arylacetylene halides with arylboronic acids
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A PdCl2-catalyzed direct alkynylation of arylboronic acids to give diarylacetylenes is described. The optimal conditions using PdCl 2 as catalyst, MeOH-PhMe-H2O as solvent and K 2CO3 as base effectively suppressed the formation of homo-coupling product and afforded moderate to good yield of the desired unsymmetrical coupling product. This reaction represents a Suzuki-type sp 2(C-B)-sp(C-X) cross-coupling. Copyright
- Shi, Yu,Li, Xiaoyu,Liu, Jianhui,Jiang, Wenfeng,Sun, Licheng
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experimental part
p. 514 - 520
(2012/04/04)
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- PdCl2-catalyzed cross-coupling reaction of arylacetylene iodides with arylboronic acids to diarylacetylenes
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A new Suzuki-type cross-coupling reaction between 1-iodo-2-arylalkynes and arylboronic acids to afford a wide variety of functionalized diarylacetylenes in a mild reaction condition was developed. The reaction was catalyzed by a small amount of a structurally simple, commercially available, and stable PdCl 2. This unique sp-sp2 carbon-carbon bond formation provides a new protocol for the synthesis of diarylacetylenes, which is a new addition to the Suzuki cross-coupling reaction.
- Shi, Yu,Li, Xiaoyu,Liu, Jianhui,Jiang, Wenfeng,Sun, Licheng
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supporting information; experimental part
p. 3626 - 3628
(2010/08/13)
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- Pd-catalyzed domino synthesis of internal alkynes using triarylbismuths as multicoupling organometallic nucleophiles
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Figure presented The domino coupling reaction of 1,1-dibromo-1-alkenes with triarylbismuth nucleophiles has been demonstrated to furnish disubstituted alkynes directly under catalytic palladium conditions. The couplings of triarylbismuths as multicoupling nucleophiles with 3 equiv of 1,1-dibromo-1-alkenes are very fast, affording high yields of alkynes in a short reaction time. Thus, an efficient domino process has been accomplished using 1,1-dibromo-1-alkenes as surrogates for internal alkyne synthesis in couplings with triarylbismuths in a one-pot operation.
- Rao, Maddali L. N.,Jadhav, Deepak N.,Dasgupta, Priyabrata
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supporting information; experimental part
p. 2048 - 2051
(2010/07/03)
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- Microwave-promoted hydrogenation and alkynylation reactions with palladium-loaded multi-walled carbon nanotubes
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Multi-walled carbon nanotubes loaded with Pd(0) clusters (average size distribution 9 nm) have been used under microwave irradiation as catalysts in hydrogenation and alkynylation reactions under "eco-friendly" conditions; reduced cinnamic esters and cross-coupled products were obtained in good yields; use of piperidine as the base provided, in a regiospecific process, novel doubly alkynylated compounds unambiguously characterized by NMR correlation experiments and X-ray diffraction. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
- Olivier, Jean-Hubert,Camerel, Franck,Ziessel, Raymond,Retailleau, Pascal,Amadou, Julien,Pham-Huu, Cuong
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p. 920 - 924
(2008/12/20)
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