- Photo-activation of Pd-catalyzed Sonogashira coupling using a Ru/bipyridine complex as energy transfer agent
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The photo-activation of the Pd-catalyzed Sonogashira coupling reaction by using tris(bipyridine)ruthenium(II) complex (TB) as a co-catalyst was demonstrated. TB and its derivatives were used as co-catalysts in the photocatalytic systems composed of a phot
- Osawa, Masahisa,Nagai, Hidetada,Akita, Munetaka
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Read Online
- Phenylethynyl- and phenylethenylmetacyclophanes
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The cyclophanes 6,8,10 and 13-15 were synthesized by cesium assisted ring closure reactions. The main interest in these systems concerns the interaction of the unsaturated bridge with the tolan and the stilbene chromophores, respectively.
- Cao, Derong,Kolshorn, Heinz,Meier, Herbert
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Read Online
- Copper(0) nanoparticle catalyzed Z-Selective Transfer Semihydrogenation of Internal Alkynes
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The use of copper(0) nanoparticles in the transfer semihydrogenation of alkynes has been investigated as a lead-free alternative to Lindlar catalysts. A stereo-selective methodology for the hydrogenation of internal alkynes to the corresponding (Z)-alkenes in high isolated yields (86% average) has been developed. This green and sustainable transfer hydrogenation protocol relies on non-noble copper nanoparticles for reduction of both electron-rich and electron-deficient, aliphatic-substituted and aromatic- substituted internal alkynes. Polyols, such as ethylene glycol and glycerol, have been proven to act as hydrogen sources, and excellent stereo- and chemoselectivity have been observed. Enabling technologies, such as microwave and ultrasound irradiation are shown to enhance heat and mass transfer, whether used alone or in combination, resulting in a decrease in reaction time from hours to minutes. (Figure presented.).
- Moran, Maria Jesus,Martina, Katia,Bieliunas, Vidmantas,Baricco, Francesca,Tagliapietra, Silvia,Berlier, Gloria,De Borggraeve, Wim M.,Cravotto, Giancarlo
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supporting information
p. 2850 - 2860
(2021/05/06)
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- Visible Light-Catalyzed Decarboxylative Alkynylation of Arenediazonium Salts with Alkynyl Carboxylic Acids: Direct Access to Aryl Alkynes by Organic Photoredox Catalysis
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A convenient method mediated by photoredox catalysis is developed for the direct construction of aryl alkynes. Readily available aromatic diazonium salts have been utilized as the aryl radical source to couple alkynyl carboxylic acids to feature the decarboxylative arylation. A wide range of substrates are amenable to this protocol with broad functional group tolerance, and diversely-functionalized aryl alkynes could be synthesized under mild, neutral and transition metal-free reaction conditions using visible light irradiation. Alongside synthetic sustainability associated with the photocatalytic and transition metal-free operation, another key point of this method is that the organic dye catalyst acts as an excited-state reductant, thus establishing the quenching cycle for radical addition and decarboxylative elimination. (Figure presented.).
- Yang, Liangfeng,Li, Haifeng,Du, Yijun,Cheng, Kai,Qi, Chenze
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p. 5030 - 5041
(2019/11/03)
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- Preparation method of aromatics methylation
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The invention relates to the technical field of organic synthesis or pharmaceutical chemistry, in particular to a preparation method of aromatics methylation. Under inert gas protection, a substrate A, a methylation reagent B and a termination agent C are used as starting materials, under the action of a catalyst D, a ligand E, a norborneene derivative G and a base F, the starting materials are subjected to a stirring reaction in an organic solvent H at 30-140 DEG C, and after the reaction, a reaction mixture is sucked and filtered, concentrated and purified to prepare a product of aromatics methylation shown as any formula of a formual I, a formual II and a formual III (please see the specifications for the formual I, the formual II and the formual III). According to the preparation method, related main raw materials are aryl iodide, trimethyl phosphate, methyl sulfonate, deuterated methyl ester sulfoacid, olefin, alkyne, an aryl boron compound, cyanide, bis(pinacolato)diboron and a proton source, the raw materials can be used as a commercial reagent without special treatment, the cost is low, and the variety is great. According to the method, aromatics methylation products can beprepared in large quantities (grams), and a good foundation is laid for industrial production.
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Paragraph 0124; 0125; 0126; 0133; 0134; 0135
(2019/11/20)
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- Preparation method of aryl alkyne catalyzed by visible light
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The invention discloses a simple and convenient method for directly synthesizing an aryl alkyne compound through photoredox catalysis. Aryl fluoroborate diazoate is used as an aryl free radical source, and different types of aryl alkyne are synthesized in situ through a decarboxylation process. A reaction has good functional group tolerability, and a simple domestic visible light source can be used for synthesizing the aryl alkyne of different functional groups under mild, neutral and transition-free metal reaction conditions.
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Paragraph 0050-0053
(2019/11/13)
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- Arylation of Terminal Alkynes by Aryl Iodides Catalyzed by a Parts-per-Million Loading of Palladium Acetate
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Arylation of terminal alkynes (16 varieties) by aryl iodides (28 varieties) was achieved with a mol ppm loading level of palladium catalyst, where a variety of functional groups including heteroarenes were tolerated. Thus, the arylations were carried out in the presence of palladium acetate at ppm loadings and potassium carbonate in ethanol at 80 °C to give the corresponding internal alkynes in good to excellent yields. Synthesis of 2-phenyl-3-(phenylalkynyl)benzofuran was achieved by iterative use of the alkyne arylation under mol ppm catalytic conditions. Reaction-rate analysis, transmission electron microscopic (TEM) examination of the reaction mixture, and mercury-amalgamation test were performed to gain insight into the active species of the highly active ppm catalytic species. TEM examination of the reaction mixture revealed that palladium nanoparticles were generated in situ under the reaction conditions, and their cluster size was variable during the catalytic reaction. A variation in size of palladium particles suggested that the composition-decomposition process of Pd aggregates should take place in situ via monomeric palladium(0) species and/or fine palladium(0) clusters, which might be real catalytic species in this reaction.
- Hamasaka, Go,Roy, David,Tazawa, Aya,Uozumi, Yasuhiro
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p. 11640 - 11646
(2019/12/02)
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- Sonogashira-type cross-coupling reactions catalyzed by copper complexes of pincer N-heterocyclic carbenes
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Copper complexes of N-heterocyclic carbenes (NHC) have recently received great attention in catalysis, however, the application scope has been limited to neutral complexes bearing monodentate ligands. Herein, we report the synthesis and full characterization of a cationic Cu-pincer bis(NHC) complex with bulky tert-butyl wingtips that serves as catalyst for the coupling of aryl iodides and phenylacetylene, alongside its analogs with small alkyl substituents. Unlike other copper catalysts that require an inert atmosphere to prevent alkyne homocoupling, a competing side reaction to Sonogashira reaction, the Cu-pincer bis(NHC) complexes provide good to excellent cross-coupling yields in air. Interestingly, the reaction under argon affords substantially reduced cross-coupling, indicative of the oxygen involvement and its facilitating effect in the mechanism. In our controlled studies, the air-assisted cross-coupling reaction came to a complete stop when using a radical trap, suggesting the presence of a radical in the mechanism. Examining the reaction of Cu-pincer bis(NHC) complexes with oxygen via UV–vis spectroscopy reveals a dark green chromophore formation at ?40 °C with strong absorbance (ε > 400 M?1cm?1) at 460 nm and 500 nm, likely due to a high-valent copper-oxygen adduct.
- Domyati, Doaa,Latifi, Reza,Tahsini, Laleh
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supporting information
p. 98 - 105
(2018/03/06)
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- Pd(NHC)PEPPSI-diazonium salts: An efficient blend for the decarboxylative Sonogashira cross coupling reaction
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An efficient N-heterocyclic carbene based Pd complex is described for the de-carboxylative Sonogashira coupling reaction with diazonium salts under ligand and co-catalyst free conditions. Pd(NHC)PEPPSI not only offers an air and moisture stable pre-cataly
- Bhojane, Jeevan Manohar,Jadhav, Vilas Gangadhar,Nagarkar, Jayashree Milind
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supporting information
p. 6775 - 6780
(2017/07/17)
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- Double-indole methane derivatives promote catalytic CuCl Sonogashira cross-coupling reaction
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The invention discloses a method for promoting CuCl to catalyze Sonogashira cross-coupling reaction by a diindolylmethane derivative. According to the method, by taking the diindolylmethane derivative which are stable in water and air and are cheap and are easily available as a ligand, CuCl is promoted to catalyze Sonogashira cross-coupling reaction of aryl halide and terminal alkyne, so that not only is the use level of CuCl reduced, but also a conventional phosphine ligand needs not to be used. The method disclosed by the invention has good primer applicability, is suitable for aryl alkyne and alkyl terminal alkyne, and is high in yield of target products. The method is an efficient, low-consumption and safe Sonogashira cross-coupling reaction system which is wide in applicability and can be widely applied to constructing Csp-Csp2 bonds.
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Paragraph 0017; 0018; 0029; 0030; 0033; 0034; 0035; 0036
(2017/08/24)
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- Palladium-catalyzed deacetonative coupling of aryl propargylic alcohols with aryl chlorides in water
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A highly efficient and green process for palladium-catalyzed deacetonative coupling of aryl propargylic alcohols with aryl chlorides has been developed. The reaction occurs smoothly in neat water with 2 mol% PdCl2 as catalyst, and various synthetically useful functional groups, including ether, aldehyde, ketone, and heterocyclics, are well tolerated. Moreover, the reaction could proceed through a consecutive Sonogashira/deacetonative process using 2-methyl-3-butyn-2-ol and aryl chlorides as coupling partners, affording the symmetric alkynes in good yields.
- Chang, Feng,Liu, Yanping
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supporting information
p. 961 - 967
(2017/05/04)
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- Sonogashira reaction catalyzed by palladium isocyanide complex modified in situ
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Palladium isocyanide complex modified in situ by addition of benzohydrazide as nucleophile was shown to catalyze Sonogashira reactions of phenylacetylene with iodobenzenes in refluxing ethanol in the presence of potassium carbonate. The reactions were com
- Boyarskii
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p. 1663 - 1666
(2017/09/25)
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- Palladium Nanoparticles Immobilized on Individual Calcium Carbonate Plates Derived from Mussel Shell Waste: An Ecofriendly Catalyst for the Copper-Free Sonogashira Coupling Reaction
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The conversion of waste into high-value materials is considered an important sustainability strategy in modern chemical industries. A large volume of shell waste is generated globally from mussel cultivation. In this work, mussel shell waste (Perna viridis) is transformed into individual calcium carbonate plates (ICCPs) and is applied as a support for a heterogeneous catalyst. Palladium nanoparticles (3–6 nm) are deposited with an even dispersion on the ICCP surface, as demonstrated by X-ray diffraction and scanning electron microscopy. Using this system, Sonogashira cross-coupling reactions between aryl iodides and terminal acetylenes were accomplished in high yields with the use of 1 % Pd/ICCP in the presence of potassium carbonate without the use of any copper metal or external ligand. The Pd/ICCP catalyst could also be reused up to three times and activity over 90 % was maintained with negligible Pd-metal leaching. This work demonstrates that mussel shell waste can be used as an inexpensive and effective support for metal catalysts in coupling reactions, as demonstrated by the successful performance of the Pd-catalyzed, copper-free Sonogashira cross-coupling process.
- Saetan, Trin,Lertvachirapaiboon, Chutiparn,Ekgasit, Sanong,Sukwattanasinitt, Mongkol,Wacharasindhu, Sumrit
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p. 2221 - 2230
(2017/09/06)
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- Method for catalyzing Sonogashira coupling reaction by synergetic catalysis of 1,2,3-triazole monosubstituted1,3,5-triazine
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The invention discloses a method for catalyzing Sonogashira coupling reaction by synergetic catalysis of 1,2,3-triazole monosubstituted1,3,5-triazine. According to the method, CuSO4.5H2O which has good stability and is cheap and easily available and a tri
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Paragraph 0017; 0028; 0029
(2017/01/17)
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- Decarboxylative/Sonogashira-type cross-coupling using PdCl2(Cy?Phine)2
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The PdCl2(Cy?Phine)2 precatalyst containing the meta-terarylphosphine ligand, Cy?Phine, can effectively mediate decarboxylative cross-coupling with a diverse range of (hetero-)aryl, aryl and alkyl chlorides including those with unprotected functionality. Using a facile and robust protocol, this process was extended to the first synthesis of symmetrical di(heteroaryl)alkynes via tandem Sonogashira/decarboxylative cross-coupling of heteroaryl chlorides and propiolic acid.
- Yang, Yong,Lim, Yee Hwee,Robins, Edward G.,Johannes, Charles W.
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p. 72810 - 72814
(2016/08/09)
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- Highly modulated bisindoles: ligands for copper-catalyzed Sonogashira reaction
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Bisindoles (BIMs) were modulated as powerful N,N′ donor ligands for the copper-catalyzed Sonogashira reaction. Ligand screening experiments on 11 BIM compounds found that 3,3′-(4-chlorophenyl)methylenebis(1-methyl-1H-indole) (10%) efficiently accelerated CuCl (5%)-catalyzed cross-coupling of aryl iodides with terminal alkynes. A wide range of substituted aryl iodides and/or alkyl- and aryl-substituted terminal alkynes were examined, leading to the corresponding coupling products with yields up to 99%. An efficient and scalable protocol for the synthesis of BIM ligands on a gram scale, with extremely low catalyst loading of o-ClC6H4NH3 +Cl?, was also developed with a reaction time of 20?min with yields up to 93%. This novel N,N′ ligand was air-stable, easily available and highly modulated with low copper loading. Copyright
- Wang, Xiu,Wang, Zhenhua,Wu, Ya,Luo, Yanlong,Zhang, Guofang,Jian, Yajun,Sun, Huaming,Zhang, Weiqiang,Gao, Ziwei
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p. 831 - 834
(2016/09/20)
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- Regioselective Asao-Yamamoto benzannulations of diaryl acetylenes
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Asao-Yamamoto benzannulations transform diarylalkynes into 2,3-diarylnaphthalenes, and regioselective variants of this reaction are of interest for synthesizing substituted polycyclic aromatic systems. It is shown that regioselective cycloadditions occur when one alkyne carbon preferentially stabilizes developing positive charge. Simple calculations of the relative energies of carbocations localized at each alkyne carbon of a substrate predict the regioselectivity, which is not eroded by bulky substituents, including 2,6-disubstituted aryl groups.
- Arslan, Hasan,Walker, Katherine L.,Dichtel, William R.
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supporting information
p. 5926 - 5929
(2015/02/19)
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- Pd/tetraphosphine catalytic system for Cu-free Sonogashira reaction "on water"
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An efficient copper-free Sonogashira coupling reaction was performed on water at 100 °C with N,N,N′,N′-tetra(diphenylphosphinomethyl) pyridine-2,6-diamine (1) as a ligand, [Pd(η3-C3H 5)Cl]2 as a catalyst precursor and K3PO 4 as a base. Both aryl and heteroaryl halides were successfully alkynylated in this system, and a high turnover number (TON) up to 860000 was obtained with a catalyst loading as low as 1 ppm.
- Zhou, Rong,Wang, Wei,Jiang, Zhi-Jie,Fu, Hai-Yan,Zheng, Xue-Li,Zhang, Chun-Chun,Chen, Hua,Li, Rui-Xiang
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p. 746 - 751
(2014/03/21)
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- Hydrazinoaminocarbene-palladium complexes as easily accessible and convenient catalysts for copper-free Sonogashira reactions
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Two easily accessible hydrazinoaminocarbene complexes of Pd(II) are shown to be efficient catalysts for copper-free Sonogashira cross-couplings of a variety of aryl iodides with aryl- and alkylalkynes under mild conditions, in ethanol as the solvent and u
- Savicheva, Elizaveta A.,Kurandina, Daria V.,Nikiforov, Vladimir A.,Boyarskiy, Vadim P.
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p. 2101 - 2103
(2014/04/03)
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- One-pot synthesis of unsymmetrical diarylacetylenes via Sonogashira/deacetonation/Sonogashira cross-coupling of two different aryl chlorides with 2-methyl-3-butyn-2-ol
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With the assistance of PdCl2/X-Phos as the catalyst system, a green and efficient protocol for one-pot Sonogashira/Deacetonation/Sonogashira coupling reaction of two different aryl chlorides with 2-methyl-3-butyn-2-ol was developed, affording various unsymmetrical diarylacetylenes in mostly moderate to excellent yields. Note that the cheap and economically available aryl chlorides and 2-methyl-3-butyn-2-ol as the starting materials could be added to the catalyst system directly and simultaneously. Moreover, this tandem reaction could tolerate substrates bearing one or even two ortho-sterically hindered groups and was also applicable to the synthesis of symmetrical diarylacetylenes. In addition, the competitive reaction was performed and a possible mechanism was also proposed. This journal is the Partner Organisations 2014.
- Xu, Kai,Sun, Suyan,Zhang, Guodong,Yang, Fan,Wu, Yangjie
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p. 32643 - 32646
(2014/08/18)
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- Stille couplings in water at room temperature
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A nonionic amphiphile, TPGS-750-M, enables efficient Stille couplings between a wide range of substrates to be conducted in water as the only medium, in most cases at room temperature.
- Lu, Guo-Ping,Cai, Chun,Lipshutz, Bruce H.
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supporting information
p. 105 - 109
(2013/02/23)
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- Heck alkynylation (copper-free sonogashira coupling) of aryl and heteroaryl chlorides, using Pd complexes of t -Bu2(p -NMe2C 6H4)P: Understanding the structure-activity relationships and copper effects
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L2Pd(0) and L2Pd(II) complexes, where L= t-Bu 2(p-NMe2C6H4)P, have been identified as efficient catalyst systems for the Heck alkynylation of a variety of aryl bromides (17 examples) and aryl/heteroaryl chlorides (31 examples) with a range of aryl- and alkyl-acetylenes in excellent yields, under relatively low Pd loadings. The single-crystal X-ray structure determination of the presumably active catalytic species, L2Pd(0), was carried out in this study to better understand the superior activity of the current catalyst system from a structure-activity relationship point of view. The P-Pd-P bond angle indicates that the complex is bent (174.7) in comparison to the perfectly linear (180.0) structure of the analogous Pd(t-Bu3P)2. Preliminary mechanistic studies on the negative copper effect and substrate effect of aryl acetylenes were conducted to better understand the cross-coupling pathway of Heck alkynylation.
- Pu, Xiaotao,Li, Hongbo,Colacot, Thomas J.
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p. 568 - 581
(2013/03/13)
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- Gold and palladium combined for the Sonogashira coupling of aryl and heteroaryl halides
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A highly efficient gold and palladium combined methodology for the Sonogashira coupling of a wide array of electronically and structurally diverse aryl and heteroaryl halides is described. The orthogonal reactivity of the two metals shows high selectivity and extreme functional group tolerance in Sonogashira coupling. A brief mechanistic study reveals that the gold acetylide intermediate enters into the palladium catalytic cycle at the transmetalation step. Georg Thieme Verlag Stuttgart.New York.
- Panda, Biswajit,Sarkar, Tarunk.
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p. 817 - 829
(2013/04/10)
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- Copper-free oxime-palladacycle-catalyzed sonogashira alkynylation of deactivated aryl bromides and chlorides in water under microwave irradiation
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Palladium-catalyzed Heck alkynylation cross-coupling reactions between terminal alkynes and deactivated aryl chlorides and aryl bromides can be performed in the absence of copper cocatalyst with water as solvent at 130 °C under microwave irradiation. An oxime-derived chloro-bridged palladacycle is an efficient precatalyst for this transformation with 2- dicyclohexylphosphanyl-2',4',6'-triisopropylbiphenyl (XPhos as ancillary ligand, pyrrolidine as base, and SBDS as surfactant. All of the reactions can be performed under air and with reagent-grade chemicals under low loading conditions (0.1-1 mol-% Pd). Deactivated and hindered aryl bromides and chlorides are cross-coupled with terminal alkynes by using low catalyst loadings of an oxime palladacycle, pyrrolidine as base, sodium dodecylbenzenesulfonate (SBDS as surfactant, water as solvent, and microwave irradiation (40 W at 130 °C. Under these reaction conditions a wide array of tolane derivatives are prepared in moderate-to-good yields. Copyright
- Buxaderas, Eduardo,Alonso, Diego A.,Najera, Carmen
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supporting information
p. 5864 - 5870
(2013/09/23)
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- Decyl(tri- tert -butyl)phosphonium tetrafluoroborate/palladium acetate: An effective catalyst for cross-coupling reaction of arylbromides with phenylacetylene in copper-free conditions
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Abstract The phosphonium salts with sterically hindered cation and noncoordinating anion can be used as phase-transfer reagent in the Sonogashira cross-coupling reaction allowing copper- and amine-free protocol. The reactions proceed under mild conditions
- Ermolaev, Vadim,Miluykov, Vasiliy,Arkhipova, Daria,Zvereva, Elena,Sinyashin, Oleg
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p. 168 - 170
(2013/07/05)
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- Palladacycle-catalyzed deacetonative sonogashira coupling of aryl propargyl alcohols with aryl chlorides
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An efficient and general protocol for the deacetonative Sonogashira coupling of aryl propargyl alcohols with aryl chlorides is described. The reaction proceeded smoothly with the catalyst system of palladacycle/Xphos. This result represents the first succ
- Hu, Hao,Yang, Fan,Wu, Yangjie
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p. 10506 - 10511
(2013/11/06)
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- Palladacycle-catalyzed decarboxylative coupling of alkynyl carboxylic acids with aryl chlorides under air
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A highly efficient and practical protocol for palladacycle-catalyzed decarboxylative coupling of alkynyl carboxylic acids with aryl chlorides was developed. The reaction could proceed smoothly in air within 3 h under optimized reaction conditions (1 mol % of palladacycle, 4 mol % of Xphos, 2.0 equiv of K2CO3 in xylene/H2O), affording the corresponding internal alkynes in mostly good to excellent yields. Remarkably, this result represents the first successful examples of this type of decarboxylative cross-coupling using electron-poor, electron-neutral and even inactive sterically hindered electron-rich aryl chlorides as the starting materials.
- Li, Xi'Ang,Yang, Fan,Wu, Yangjie
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p. 4543 - 4550
(2013/06/05)
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- Mechanistic insights into copper-catalyzed sonogashira-hagihara-type cross-coupling reactions: Sub-mol % catalyst loadings and ligand effects
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An efficient catalytic system for Sonogashira-Hagihara-type reactions displaying ligand acceleration in the copper-catalyzed formation of C(sp 2)-C(sp) bonds is described. The structure of the ligand plays a key role for the coupling efficiency. Various copper sources show excellent catalytic activity, even in sub-mol % quantities. A wide variety of substituents is tolerated in the substrates. Mechanistic details have been revealed by kinetic measurements and DFT calculations. Just a pinch of copper! An efficient system for the formation of C(sp2)-C(sp) bonds has been developed. In sub-mol % quantities various copper sources showed excellent catalytic activity. Different combinations of aryl(hetero) iodides and terminal aryl(hetero) alkynes were applied, leading to the desired products in moderate to excellent yields (see scheme; DMEDA=N,N′-dimethylethylenediamine). Mechanistic details of this process have been revealed by kinetic measurements and DFT calculations. Copyright
- Zou, Liang-Hua,Johansson, Adam Johannes,Zuidema, Erik,Bolm, Carsten
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p. 8144 - 8152
(2013/07/27)
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- Highly efficient Pd/tetraphosphine catalytic system for copper-free sonogashira reactions of aryl bromides with terminal alkynes
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In this study, an easily synthesized polydentate ligand N,N,N',N'-tetra(diphenylphosphinomethyl)-1,2-ethylenediamine (1) in combination with [Pd(C3H5)Cl]2 was found to be an active catalyst in copper-free Sonogashira reactions. Most substrates, including steric hindered phenyl bromides and heteroaryl bromides, could couple efficiently with terminal alkynes in the presence of low catalyst loading (0.1 mol%) and this catalytic system showed excellent functional group tolerance. The influence of water in this system was also preliminarily investigated via 31P NMR in situ; that is, appropriate water favors the reaction while excess hindered this reaction.
- Yi, Tao,Mo, Min,Fu, Hai-Yan,Li, Rui-Xiang,Chen, Hua,Li, Xian-Jun
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experimental part
p. 594 - 600
(2012/08/07)
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- A guide to sonogashira cross-coupling reactions: The influence of substituents in aryl bromides, acetylenes, and phosphines
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The conversion-time data for 168 different Pd/Cu-catalyzed Sonogashira cross-coupling reactions of five arylacetylenes (phenylacetylene; 1-ethynyl-2-ethylbenzene; 1-ethynyl-2,4,6-R3-benzene (R = Me, Et, i-Pr)) and Me3SiCCH with seven
- Schilz, Marc,Plenio, Herbert
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experimental part
p. 2798 - 2807
(2012/05/05)
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- Enhanced catalyst recovery in an aqueous copper-free Sonogashira cross-coupling reaction
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We report the synthesis of a superparamagnetic nanoparticle MNP (γ-Fe2O3/polymer) supported dendritic catalyst based on a bulky electron-rich phosphine Pd(ii) complex. The high reactivity of this catalyst is described in a copper-fre
- Rosario-Amorin, Daniel,Gaboyard, Manuel,Clerac, Rodolphe,Nlate, Sylvain,Heuze, Karine
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experimental part
p. 44 - 46
(2011/02/27)
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- Facile access to sterically hindered aryl ketones via carbonylative cross-coupling: Application to the total synthesis of luteolin
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A general and mild protocol for achieving the carbonylative cross-coupling of sterically hindered, ortho-disubstituted aryl ketones is reported. The commercially available PEPPSI-IPr catalyst is shown to efficiently promote the carbonylative cross-coupling of hindered ortho-disubstituted aryl iodides to give diaryl ketones; traditional phosphine catalysts are less effective. Carbonylative Suzuki-Miyaura cross-couplings provide a diverse array of biaryl ketones in good to excellent yields. The same catalyst is also shown to catalyze a carbonylative Negishi cross-coupling reaction, utilizing a variety of alkynyl-zinc reagents to give the corresponding alkynyl aryl ketones. Application of this new methodology to the synthesis of the natural product luteolin is reported.
- O'Keefe, B. Michael,Simmons, Nicholas,Martin, Stephen F.
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scheme or table
p. 4344 - 4351
(2011/07/29)
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- Highly active palladium catalyst for the sonogashira coupling reaction of unreactive aryl chlorides
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This communication reports on the β-diketiminatophosphane palladium-catalyzed copper-free Sonogashira coupling of aryl chlorides with alkynes. A catalyst loading of 0.5 mol% is sufficient to achieve high performance under relatively mild reaction conditio
- Lee, Dong-Hwan,Kwon, Young-Jun,Jin, Myung-Jong
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supporting information; experimental part
p. 3090 - 3094
(2012/01/03)
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- Gold and palladium combined for the Sonogashira-type cross-coupling of arenediazonium salts
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The Sonogashira-type cross-coupling of arenediazonium salts is reported for the first time using a Pd-Au dual catalytic system. The Royal Society of Chemistry 2010.
- Panda, Biswajit,Sarkar, Tarun K.
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scheme or table
p. 3131 - 3133
(2010/08/20)
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- On the catalytic duo PdCl2(PPh3)2/AuCl(PPh3) that cannot effect a Sonogashira-type reaction: a correction
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In contrast to the observation made by the Laguna group, we report that the combination of PdCl2(PPh3)2 and AuCl(PPh3) makes a unique catalytic system that allows Sonogashira-type cross-coupling of both aryl and alkyl alkynes with aryl halides in excellent yields.
- Panda, Biswajit,Sarkar, Tarun K.
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experimental part
p. 301 - 305
(2010/03/26)
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- Sulfonated N-heterocyclic carbenes for Pd-catalyzed sonogashira and suzuki-miyaura coupling in aqueous solvents
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The reactions of the N, N-diarylimidazolium and N, N-diarylimidazolinium salts with chlorosulfonic acid result in the formation of the respective disulfonated N-heterocyclic carbene (NHC) precursors in reasonable yields (46-77%). Water-soluble palladium catalyst complexes, in situ obtained from the respective sulfonated imidazolinium salt, sodium tetrachloropalladate (Na 2PdCl4) and potassium hydroxide (KOH) in water, were successfully applied in the copper-free Sonogashira coupling reaction in isopropyl alcohol/water mixtures using 0.2 mol% catalyst loading. The preformed (disulfonatedNHC)PdCl(cinnamyl) complex was used in aqueous Suzuki-Miyaura reactions at 0.1 mol% catalyst loading. The coupling protocol reported here is very useful for Sonogashira reactions of N- and 5-heterocyclic aryl bromides and chlorides with aryl- and alkylacetylenes.
- Roy, Sutapa,Plenio, Herbert
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experimental part
p. 1014 - 1022
(2010/06/17)
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- Transition-metal-free sonogashira-type coupling of ortho-substituted aryl and alkynyl grignard reagents by using 2,2,6,6-tetramethylpiperidine-N-oxyl radical as an oxidant
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Cross coupling of aryl, alkenyl, and alkynyl magnesium compounds by using 2,2,6,6-tetramethylpiperidine-N-oxyl radical (TEMPO) as an environmentally benign organic oxidant is described. This coupling reaction can be performed without adding any transition
- Maji, Modhu Sudan,Murarka, Sandip,Studer, Armido
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supporting information; experimental part
p. 3878 - 3881
(2010/11/17)
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- A practical heterogeneous catalyst for the suzuki, sonogashira, and stille coupling reactions of unreactive aryl chlorides
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(Chemical Equation Present) Practical catalyst: A magnetic nanoparticle-supported palladium catalyst was developed for the highly efficient heterogeneous Suzuki, Sonogashira, and Stille couplings of a wide variety of aryl chlorides. Furthermore, the catalyst could be recycled by facile magnetic separation without any loss of activity.
- Jin, Myung-Jong,Lee, Dong-Hwan
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supporting information; experimental part
p. 1119 - 1122
(2010/05/17)
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- Mesityl alkyne substituents for control of regiochemistry and reversibility in zirconocene couplings: New synthetic strategies for unsymmetricalzirconacyclopentadienes and conjugated polymers
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Reaction of 2 equivs of MesC≡CPh with Cp2Zr( η2-Me3SiC≡CSiMe3)(pyr) afforded the zircona-cyclopentadiene Cp2Zr[2,5-Ph2-3,4-Mes2C 4]. The regiochemistry of this isomer (ssss with
- Miller, Adam D.,Tannaci, John F.,Johnson, Samuel A.,Lee, Hyuk,McBee, Jennifer L.,Tilley, T. Don
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experimental part
p. 4917 - 4927
(2009/09/30)
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- Highly convenient, clean, fast, and reliable Sonogashira coupling reactions promoted by aminophosphine-based pincer complexes of palladium performed under additive-and amine-free reaction conditions
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Sequential addition of 1,1',1″-phosphine-triyltripiperidine and 1,3-diaminobenzene or resorci-nol to toluene solutions of (cyclooctadiene) palladium dichloride [Pd(cod)(Cl)2] under nitrogen in "one pot" almost quantitatively yielded the aminophos-phine-based pincer complexes {[C6H3-2,6-(XP{piperi-dinyl}2) 2]Pd(Cl)} (X = NH 1; X = O 2). Complex 1 (and to a minor extent 2) proved to be efficient Sonogashira catalysts, which allow the quantitative coupling of various electronically deactivated and/or sterically hindered and functionalized aryl iodides and aryl bromides with several alkynes as coupling partners within very short reaction times and low catalyst loadings. Importantly, in contrast to most of the Sonogashira catalysts, which either are both air-and moisture-sensitive and/or require the addition of co-catalysts, such as copper(I) iodide [Cul], for ex- ample, or a large excess of an amine, the coupling reactions were carried out without the use of amines, co-catalysts or other aditives and without exclusion of air and moisture. Moreover, the desired products were exclusively formed (no side-products were detected) without employing an excess of one of the substrates. Ethylene glycol and potassium phosphate (K3PO4) were found to be the ideal solvent and base for this transformation. Experimental observations strongly indicate that palladium nanoparticles are not the catalytically active form of 1 and 2. On the other hand, their transformation into another homogeneous catalytically active species cannot be excluded.
- Bolliger, Jeanne L.,Frech, Christian M.
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experimental part
p. 891 - 902
(2009/12/01)
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- Sonogashira couplings of aryl bromides: Room temperature, water only, no copper
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(Chemical Equation Presented) Cross-coupling reactions between lipophilic terminal alkynes and aryl bromides can be catalyzed by ligated Pd, in the absence of copper, In pure water at ambient temperatures. Small amounts of the nonionic amphiphile PTS assi
- Lipshutz, Bruce H.,Chung, David W.,Rich, Brian
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supporting information; experimental part
p. 3793 - 3796
(2009/07/01)
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- New cyclopentadienyl, indenyl or fluorenyl substituted phosphine compounds and their use in catalytic reactions
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The invention is directed to a phosphine compound represented by general formula (1) wherein R' and R" independently are selected from alkyl, cycloalkyl and 2-furyl radicals, or R' and R" are joined together to form with the phosphorous atom a carbon-phosphorous monocycle comprising at least 3 carbon atoms or a carbon-phosphorous bicycle; the alkyl radicals, cycloalkyl radicals, and carbon-phosphorous monocycle being unsubstituted or substituted by at least one radical selected from the group of alkyl, cycloalkyl, aryl, alkoxy, and aryloxy radicals; Cps is a partially substituted or completely substituted cyclopentadien-1-yl group, including substitutions resulting in a fused ring system, and wherein a substitution at the 1-position of the cyclopentadien-1-yl group is mandatory when the cyclopentadien-1-yl group is not part of a fused ring system or is part of an indenyl group. Also claimed is the use of these phosphines as ligands in catalytic reactions and the preparation of these phosphines.
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Page/Page column 46; 47
(2008/06/13)
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- Sterically demanding, zwitterionic trialkylphosphonium sulfonates as air-stable ligand precursors for efficient palladium-catalyzed cross-couplings of aryl bromides and chlorides
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3-(Di-tert-butylphosphonium)propane sulfonate (DTB-PPS) and 3-(diadamantylphosphonium)propane sulfonate (DAPPS) are air-stable pre-ligands for aqueous-phase palladium-catalyzed cross-coupling reactions. Both DTBPPS and DAPPS were found to give active catalysts for the Sonogashira coupling of aryl bromides at room temperature and 4-chloroanisole at 80 °C. These ligands also gave effective catalysts for the aqueous-phase Suzuki coupling of aryl bromides at room temperature.
- Brown, William S.,Boykin, D'Ariel D.,M. Quentin Sonnier Jr.,William D. Clark,Brown, Fallon V.,Shaughnessy, Kevin H.
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experimental part
p. 1965 - 1970
(2009/04/04)
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- Efficient copper-free Sonogashira coupling of aryl chlorides with palladium on charcoal
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Palladium on charcoal serves as an efficient and reusable solid supported catalyst for the Sonogashira coupling of aryl chlorides with terminal acetylenes in the presence of a bulky, electron-rich biphenyl type ligand (XPhos), without copper co-catalyst. The Royal Society of Chemistry.
- Komáromi, Anna,Novák, Zoltán
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supporting information; experimental part
p. 4968 - 4970
(2009/06/05)
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- Rapid and efficient Pd-catalyzed sonogashira coupling of aryl chlorides
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(Chemical Equation Presented) An efficient and effective microwave-assisted cross-coupling of terminal alkynes with various aryl chlorides including sterically hindered, electron-rich, electron-neutral, and electron-deficient aryl chloride is developed. It proceeds faster and generally gives good to excellent yields and also can be extended successfully to the Suzuki coupling and Buchwald-Hartwig amination, as well as the Heck coupling with inert aryl chlorides. The short reaction times and simple reaction conditions coupling with a broad substrate scope render this method particularly attractive for the efficient preparation of biologically and medicinally interesting molecules.
- Huang, He,Liu, Hong,Jiang, Hualiang,Chen, Kaixian
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p. 6037 - 6040
(2008/12/21)
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- 9-Fluorenylphosphines for the Pd-catalyzed Sonogashira, Suzuki, and Buchwald-Hartwig coupling reactions in organic solvents and water
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The lithiation/alkylation of fluorene leads to various 9-alkyl-fluorenes (alkyl = Me. Et, /Pr, -Pr. -C18H25) in > 95% yields, for which lithiation and reaction with R2PCl (R = Cy, iPr, tBu) generates 9-alkyl, 9-PR2fluorenes which constitute electron-rich and bulky phosphine ligands. The in-situ-formed palladium-phosphinc complexes ([Na2PdCl4], phosphonium salt, base, substrates) were tested in the Sonogashira. Suzuki, and Buchwald-Hartwig reactions of aryl chlorides and aryl bromides in organic solvents. The Sonogashira coupling of aryl chlorides at 100-120°C leads to >90% yields with 1 mol % of Pd catalyst. The Suzuki coupling of aryl chlorides typically requires 0.05 mol % of Pd catalyst at 100°C in dioxane for quantitative product formation. To carry out "green" cross-coupling reactions in water, 9-ethylfluorenyldicyclohexylphosphine was reacted in sulphuric acid to generate the respective 2-sulfonated phosphonium salt. The Suzuki coupling of activated aryl chlorides by using this water-soluble catalyst requires only 0.01 mol% of Pd catalyst, while a wide range of aryl chlorides can be quantitatively converted into the respective coupling products by using 0.1-0.5 mol % of catalyst in pure water at 100°C. Difficult substrate combinations, such as naphthylboronic acid or 3-pyridylboronic acid and aryl chlorides are coupled at 100°C by using 0.1-0.5 mol % of catalyst in pure water to obtain the respective N-heterocycles in quantitative yields. The copper-free aqueous Sonogashira coupling of aryl bromides generates the respective tolane derivatives in > 95 % yield.
- Fleckenstein, Christoph A.,Plenio, Herbert
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p. 2701 - 2716
(2008/03/14)
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- The effect of steric bulk in Sonogashira coupling reactions
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The rates of Sonogashira coupling reactions using [Pd-PR3] complexes depend on a combination of the steric bulk of phosphines and substrates; however, below a critical cone angle of ca. 170° the catalytic activity drops drastically. The Royal S
- An Der Heiden, Markus,Plenio, Herbert
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p. 972 - 974
(2007/12/31)
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- Acyclic diaminocarbenes: Simple, versatile ligands for cross-coupling reactions
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Acyclic diaminocarbenes are found to be useful ligands for palladium catalyzed Suzuki-Miyaura, Sonogashira and Heck cross-coupling reactions of aryl/alkenyl bromides and chlorides. The Royal Society of Chemistry 2006.
- Dhudshia, Bhartesh,Thadani, Avinash N.
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p. 668 - 670
(2008/02/10)
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- A convenient high activity catalyst for the Sonogashira coupling of aryl bromides
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A mixture of Na2PdCl4, CuI and (t-Bu) 3PH+BF4- (molar ratio 4:3:8) dispersed in H2N(i-Pr)2 Br can be used as a "single source" precatalyst for the Sonogashira coupling of aryl bromides with various aryl- and alkylacetylenes in HN(i-Pr)2 solvent. Arylacetylenes require just 0.005 mol % of Pd catalyst at 80°C, with TOFs ranging between 3,200 and 10,000 h-1.
- Koellhofer, Axel,Plenio, Herbert
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p. 1295 - 1300
(2007/10/03)
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- Palladium-tetraphosphine complex: An efficient catalyst for the alkynylation of ortho-substituted aryl bromides
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The tetraphosphine cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl) cyclopentane in combination with [Pd(C3H5)Cl]2 affords a very efficient catalyst for the alkynylation of ortho-substituted aryl bromides. A wide variety of substituents such as phenyl, trifluoromethyl, acetyl, formyl or nitrile, are tolerated. High turnover numbers can be obtained with most of these aryl bromides. The coupling of sterically very congested aryl bromides such as 9-bromoanthracene or 2,4,6-triisopropylbromobenzene also proceeds in good yields.
- Feuerstein, Marie,Berthiol, Florian,Doucet, Henri,Santelli, Maurice
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p. 1281 - 1289
(2007/10/03)
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- A copper- and amine-free Sonogashira reaction employing aminophosphines as ligands
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An efficient Pd-catalyzed Sonogashira coupling reaction was achieved in the absence of a copper salt or amine with an inorganic base and easily prepared, air-stable aminophosphine ligands in commonly used organic solvents; good to excellent yields were ob
- Cheng, Jiang,Sun, Yanhui,Wang, Feng,Guo, Minjie,Xu, Jian-Hua,Pan, Yi,Zhang, Zhaoguo
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p. 5428 - 5432
(2007/10/03)
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