1008-89-5Relevant articles and documents
Thin film formation of Pd/reduced-graphene oxide and Pd nanoparticles at oil-water interface, suitable as effective catalyst for Suzuki-Miyaura reaction in water
Jafar Hoseini,Dehghani, Modarres,Nasrabadi, Hasan
, p. 1078 - 1083 (2014)
A facile and efficient route was used to synthesise Pd nanoparticles by reduction of an organopalladium(ii) complex, [PdCl2(cod)] (cod = cis,cis-1,5-cyclooctadiene), at the oil-water interface. Pd/reduced-graphene oxide and Pd free stabilizer n
Azacycle-Directed Formal Aromatic C(sp2)-H Insertion with Cr(0) Fischer Carbene Complex via Oxidative Hydrogen Migration
Qu, Shuanglin,Tong, Wen-Yan,Wang, Jianbo,Wang, Kang,Yao, Xing-Qi
, p. 3526 - 3534 (2021)
An azacycle-directed intermolecular aromatic C(sp2)-H functionalization of Cr(0) Fischer carbene complexes under catalyst-free conditions is reported. Arenes with pyridines, pyrimidine, and pyrazole as directing groups reacted with chromium(0) carbene com
Cyclometalated Palladium NHC Complexes Bearing PEG Chains for Suzuki-Miyaura Cross-Coupling in Water
Schroeter, Felix,Soellner, Johannes,Strassner, Thomas
, p. 4267 - 4275 (2018)
We present the synthesis and characterization of four new polyethylene glycol (PEG) substituted palladium complexes bearing a cyclometalated 2-phenylimidazole ligand and an N-heterocyclic carbene (NHC) ligand. A solid-state structure reveals the chelating binding mode and the coiling of the PEG chain in the auxiliary ligand. The PEG substitution significantly increased the solubility of the complexes in several solvents, enabling the efficient Suzuki-Miyaura cross-coupling reaction of aryl chlorides in an aqueous medium. Under optimized reaction conditions, sterically demanding biphenyl compounds with up to three ortho substituents were accessible in good to excellent yields.
Silica-coated magnetic nanoparticles functionalized cobalt complex: a recyclable and efficient catalyst for the C?C bond formation
Haqjow, Hanif,Raoufi, Farveh
, p. 4113 - 4128 (2021)
In this study, the Co-based catalyst was prepared by cobalt immobilization on the surface of functionalized silica-coated magnetic NPs (Fe3O4@SiO2-CT-Co) as a magnetically core–shell nanocatalyst and characterized by FT-IR, TGA, XRD, VSM, SEM, TEM, EDX, EDX mapping, and ICP techniques and appraised in the Suzuki–Miyaura cross-coupling reaction under mild reaction conditions. The results displayed the superparamagnetic behavior of the Fe3O4 NPs core encapsulated by SiO2 shell, and the size of the particles was estimated about 30?nm. Compared with the previously reported catalysts, the engineered Fe3O4@SiO2-CT-Co catalyst provided perfect catalytic performance for the Suzuki–Miyaura cross-coupling reaction in water as a green solvent and it was much cheaper in the comparison with the traditional Pd-based catalysts. Importantly, the durability of magnetic nanocatalyst was studied and observed that it is stable under the reaction conditions and could be easily reused for at least six successive cycles without any significant decrease in its catalytic activity. Graphic abstract: [Figure not available: see fulltext.]
A phosphine-free, atom-efficient cross-coupling of aryl iodides with triarylindiums or trialkynylindiums catalyzed by immobilization of palladium(0) in MCM-41
Lei, Zhiwei,Liu, Haiyi,Cai, Mingzhong
, p. 54 - 63 (2017)
The first phosphine-free heterogeneous atom-efficient cross-coupling reaction of aryl iodides with triarylindiums or trialkynylindiums was achieved in THF at 68 °C by using 1 mol% of MCM-41-immobilized palladium(0)-Schiff base complex [MCM-41-N,N-Pd(0)] as catalyst, yielding a variety of unsymmetrical biaryls and arylalkynes in good to excellent yields. The heterogeneous palladium(0) catalyst could easily be prepared via a simple procedure from commercially readily available reagents, and recovered by filtration of the reaction solution and recycled at least 10 times without significant loss of activity.
Transition-metal-free highly chemo- and regioselective arylation of unactivated arenes with aryl halides over recyclable heterogeneous catalysts
Liu, Hongli,Yin, Biaolin,Gao, Zhiqiang,Li, Yingwei,Jiang, Huanfeng
, p. 2033 - 2035 (2012)
A novel heterogeneous catalysis system using metal-organic frameworks as catalyst demonstrated excellent chemo- and regioselectivity for the direct arylation of unactivated arenes with aryl iodides/bromides without the assistance of any transition metals.
Pyridine ring formation through the photoreaction of arenecarbothioamides with diene-conjugated carbonyl compounds
Oda, Kazuaki,Nakagami, Rikiji,Nishizono, Naozumi,Machida, Minoru
, p. 2371 - 2372 (1999)
Irradiation of arenecarbothioamides with hexa-2,4-dienal in benzene solution gives 2-arylpyridines in moderate yields.
Development of a palladium-catalyzed decarboxylative cross-coupling of (2-azaaryl)carboxylates with aryl halides Dedicated to Professor Melanie Sanford on receipt of the Tetrahedron Young Investigator Award
Haley, Christopher K.,Gilmore, Christopher D.,Stoltz, Brian M.
, p. 5732 - 5736 (2013)
A catalytic method for the decarboxylative coupling of 2-(azaaryl) carboxylates with aryl halides is described. The decarboxylative cross-coupling presented is mediated by a system catalytic in both palladium and copper without requiring stoichiometric amounts of organometallic reagents or organoboronic acids. This method circumvents additional synthetic steps required to prepare 2-azaaryl organometallics and organoborates as nucleophilic coupling partners, which are prone to protodemetallation and protodeborylation and produce potentially toxic byproducts.
Cobalt-catalyzed cross-coupling reaction of chloropyridines with grignard reagents
Ohmiya, Hirohisa,Yorimitsu, Hideki,Oshima, Koichiro
, p. 1240 - 1241 (2004)
Treatment of 2-chloropyridine with benzylmagnesium chloride in the presence of a catalytic amount of cobalt(II) acetylacetonate in dioxane afforded the corresponding cross-coupling product in excellent yield. Trimethylsilylmethyl and phenyl Grignard reagents also participated in similar cross-coupling reactions.
(Diphosphine)Nickel-catalyzed negishi cross-coupling: An experimental and theoretical study
Nicolas, Emmanuel,Ohleier, Alexia,D'Accriscio, Florian,Pécharman, Anne-Frédérique,Demange, Matthieu,Ribagnac, Philippe,Ballester, Jorge,Gosmini, Corinne,Mézailles, Nicolas
, p. 7690 - 7694 (2015)
The use of a strongly donating "(bis-dialkylphosphine)Ni" fragment promotes the catalytic coupling of a large range of ArCl and ArZnCl derivatives under mild conditions. Stoichiometric mechanistic investigations and DFT calculations prove that a Ni0/NiII cycle is operative in this system.
Preparation of unsymmetrical biaryls via palladium-catalyzed coupling reaction of aryl halides
Hassan, Jwanro,Hathroubi, Chokri,Gozzi, Christel,Lemaire, Marc
, p. 7845 - 7855 (2001)
The synthesis of unsymmetrical biaryls is achieved using Pd(OAc)2 as the catalyst. A great variety of aryl halides having electron withdrawing and electron donating functional groups in para, meta and ortho positions have been successfully coupled.
NC Palladacycles and C,C-chelating phosphorus ylide complexes: Synthesis, X-ray characterization, and comparison of the catalytic activity in the Suzuki-Miyaura reaction
Karami, Kazem,Hosseini-Kharat, Mahboubeh,Shirani-Sarmazeh, Zahra,Zahedi-Nasab, Reza,Rizzoli, Corrado,Lipkowski, Janusz
, p. 763 - 778 (2016)
Six secondary amine palladacycles bearing monodentate ligands (1a, 2a), 1,2-bis(diphenylphosphino)ethane (dppe) and 1,3-bis(diphenylphosphino)propane (dppp) containing bridging and bidentate ligands (1b, 2b-d), and four C,C-type phosphorus ylide complexes containing thiourea (tu) (3a), phenyl isothiocyanate (4a), and bridging and terminal azide groups (5 and 5a) have been synthesized. Resulting complexes have been characterized by elemental analyses, IR, 1H-, 13C{1H}-, and 31P{1H}-NMR spectroscopy with single crystal X-ray structure determination of 1a and 2a. The Pd in 1a and 2a occupies the center of a slightly distorted square planar environment formed by Caryl, Namine, Npyridine, and Cl. The catalytic efficiency of complexes showed that in most cases, amine palladacycles display better catalytic activities than the phosphorus ylide Pd(II) complexes. Comparison between bidentate and bridging dppe complexes showed that dppe-bridged dimer 2d has higher catalytic activity than dppe bidentate complex.
Visible-Light-Driven C4-Selective Alkylation of Pyridinium Derivatives with Alkyl Bromides
Hong, Sungwoo,Jung, Sungwoo,Park, Seongjin,Shin, Sanghoon
, p. 11370 - 11375 (2020)
Reported herein is a general strategy for the photochemical cross-coupling between N-amidopyridinium salts and various alkyl bromides under photocatalyst-free conditions, granting facile access to various C4-alkylated pyridines. This approach exploits the intriguing photochemical activity of electron donor-acceptor (EDA) complexes between N-amidopyridinium salts and bromide, which provides a photoactive handle capable of generating silyl radicals and driving the alkylation process. The robustness of this protocol was further demonstrated by the late-stage functionalization of complex compounds under mild and metal-free conditions.
A practical synthesis of biaryls and aromatic acetylenes by stille coupling in room-temperature ionic liquids
Hao, Wenyan,Xi, Zhiwen,Cai, Mingzhong
, p. 2396 - 2406 (2012)
The Stille cross-coupling reactions of aryl halides with aryl or alkynylstannanes have been achieved under mild conditions in 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), affording the corresponding biaryls and aromatic acetylenes in good yields. Use of this solvent allows for facile recycling of the solvent and catalyst system, which can be used at least five times without loss of activity.
Immobilization of Pd(II) on MOFs as a highly active heterogeneous catalyst for Suzuki-Miyaura and Ullmann-type coupling reactions
Chen, Liyu,Gao, Zhiqiang,Li, Yingwei
, p. 122 - 128 (2015)
Palladium chloride was successfully immobilized on MOF-253, a MOF material with un-coordinated 2,2′-bipyridine moieties, through post-synthetic modification. The coordination interaction between the 2,2′-bipyridine moieties and Pd cations in the MOF-253·PdCl2 material was demonstrated by X-ray photoelectron spectroscopy (XPS) analysis. The prepared MOF-253·0.05PdCl2 was shown to be highly active, selective, and recyclable for the Suzuki-Miyaura cross-coupling and Ullmann homocoupling of a wide range of aryl halides including electron-rich and electron-poor aryl iodides/bromides, heteroaryl iodides, and even aryl chlorides, affording the corresponding biaryl compounds in good to excellent yields under mild reaction conditions. It is suggested that the 2,2′-bipyridine moieties in MOF-253 provide electron-rich environment for Pd(II) cations, and thus facilitate the initial adsorption and insertion of aryl halides molecules to Pd active sites during the carbon-carbon coupling reactions. Moreover, MOF-253·PdCl2 showed remarkably higher activity than the homogeneous Pd(bpy)Cl2 and PdCl2(CH3CN)2, which might be due to the presence of charge transfers between adjacent ligands and metals in the MOF catalyst. The superior catalytic performances of metal ions immobilized on MOFs to their homogenous counterparts might bring new opportunities in the development of highly efficient metal catalysts combining advantages of both homogeneous and heterogeneous catalysis.
Efficient cross-coupling reactions of aryl chlorides and bromides with phenyl- or vinyltrimethoxysilane mediated by a palladium/imidazolium chloride system
Lee, Hon Man,Nolan, Steven P.
, p. 2053 - 2055 (2000)
diagram presented A combination of palladium acetate and the imidazolium salt IPr-HCI (1, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) has proven to be highly efficient in the cross coupling reactions of aryl bromides and electron-deficient aryl chlorides with phenyltrimethoxysilane or vinyltrimethoxysilane. The catalytic performance of this system was found to be comparable to that of systems using PCy3 and P(o-tol)3.
Polystyrene-anchored Palladium(II) complex as an efficient and reusable catalyst for suzuki cross-coupling reaction in water medium
Islam, Maninil,Mondal, Paramita,Tuhina, Kazi,Hossain, Dildar,Roy, Anupam Singha
, p. 1200 - 1202 (2010)
A new polystyrene-anchored palladium(II) catalyst has been prepared and characterized by conventional spectroscopic methods and elemental analyses. The catalyst was found to be highly effective for the Suzuki cross-coupling reactions of aryl halides with arylboronic acid in water medium under phosphinefree reaction conditions. The optimal reaction conditions of the coupling were determined. The present heterogeneous Pd(II) catalyst was reusable as well as air-stable to allow easy use.
Pd(0)-catalyzed Cu(I)-thiophene-2-carboxylate-mediated cross-coupling of heteroaromatic thioethers and boronic acids - First Liebeskind-Srogl reaction in water
Koley, Moumita,Wimmer, Laurin,Schnuerch, Michael,Mihovilovic, Marko D.
, p. 1368 - 1373 (2013)
The first example of a Liebeskind-Srogl cross-coupling reaction in water as sole reaction solvent is reported. 2-(Methylthio)pyridine and 2-(methylthio)benzothiazole were reacted in the presence of a Pd(0) catalyst and copper(I) thiophene-2-carboxylate with a series of arylboronic acids. These cross coupling reactions in water proceeded well with electron-rich boronic acids and gave comparable yields to literature examples using organic solvents. Electron-poor boronic acids gave somewhat lower yields in aqueous medium.
Cross-coupling reaction of organobismuth dialkoxides with aryl bromides and iodides catalyzed by Pd(PPh3)4
Rao, Maddali L.N.,Shimada, Shigeru,Yamazaki, Osamu,Tanaka, Masato
, p. 117 - 120 (2002)
Cross-coupling reaction of organobismuth compounds bearing 2,6-pyridinedimethoxide ligands with aryl bromides and iodides was efficiently catalyzed by Pd(PPh3)4. Addition of two equivalents of Cs2CO3 or CsF impr
Rhodium-catalyzed cross-coupling of aryl carbamates with arylboron reagents
Nakamura, Keisuke,Yasui, Kosuke,Tobisu, Mamoru,Chatani, Naoto
, p. 4484 - 4489 (2015)
A new method has been developed for the rhodium-catalyzed cross-coupling of aryl carbamates with organoboron reagents. The use of an NHC ligand bearing a 2-adamantyl group, i.e., I(2-Ad), is essential to the success of the reaction. The reaction involves the rhodium-mediated activation of the relatively inert C(aryl)-O bond of aryl carbamates.
Electrochemical synthesis of Pd nano particles on pencil- graphite and application for suzuki coupling reactions
Balsane, Kishor E.,Shelkar, Radheshyam S.,Nagarkar, Jayashree M.
, p. 1817 - 1824 (2015)
Synthesis of Pd nano particles by electrochemical deposition on pencil graphite has been carried out. Catalytic activity of these nanoparticles was tested for Suzuki coupling reactions. The heterogeneous catalyst was synthesized in 10 s and without use of hazardous reducing reagent. The catalyst showed excellent catalytic performance towards Suzuki cross coupling reaction in aqueous medium. The catalyst was characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy dispersive X-ray analysis, thermo gravimetric analysis, inductively coupled plasma and EDX mapping techniques. Pd nano particles were found to have monodispersed nature with average particle size of 9-10 nm in diameter. The developed catalyst can be recycled up to five cycles without significant decrease in the product yield.
β-Oxo amides: Inexpensive and efficient ligands for the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction
Li, Jin-Heng,Zhang, Yue-Hua,Song, Ren-Jie,Xie, Ye-Xiang,Deng, Chen-Liang,Liang, Yun
, p. 2957 - 2966 (2007)
β-Oxo amides were found to be inexpensive and efficient ligands for the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction. In the presence of palladium(II) acetate and N-(4-methoxyphenyl)-3-oxobutanamide (L7), a variety of aryl halides, including deactivated aryl chlorides and heteroaryl halides, were successfully coupled to arylboronic acids in moderate to excellent yields providing very high turnover numbers (maximum TON 950,000 and TOF 79,167). It is noteworthy that the reaction is conducted under mild and aerobic conditions. Georg Thieme Verlag Stuttgart.
Selectivity in palladium(0)-catalyzed cross-coupling reactions: Application to a tandem Stille reaction
Hitchcock,Mayhugh,Gregory
, p. 9085 - 9088 (1995)
A tandem palladium-catalyzed cross-coupling reaction between a pyridyl triflate 1a and a variety of aryl bromides mediated by hexamethylditin is described. The reaction apparently proceeds via the intermediacy of the labile pyridylstannane 1b indicating that the oxidative addition of palladium(0) to the triflate, subsequent transmetalation with hexamethylditin and reductive elimination occurs selectively in the presence of the aryl halide.
Towards environmentally friendlier Suzuki-Miyaura reactions with precursors of Pd-NHC (NHC = N-heterocyclic carbene) complexes
Zinser, Caroline M.,Warren, Katie G.,Meadows, Rebecca E.,Nahra, Fady,Al-Majid, Abdullah M.,Barakat, Assem,Islam, Mohammad S.,Nolan, Steven P.,Cazin, Catherine S. J.
, p. 3246 - 3252 (2018)
The preparation of [NHC·H][Pd(η3-R-allyl)Cl2] complexes is disclosed and represents a facile, atom-economical, environmentally friendly and rapid synthesis. These palladates are immediate synthetic precursors to the well-known [Pd(NHC)(η3-R-allyl)Cl] complexes. Their activation leading to catalytically relevant species has been studied in the Suzuki-Miyaura reaction. The need for an activation step prior to the catalysis was examined. The reaction scope showcases its ease and breadth in terms of functional group tolerance. Electron-donating and electron-withdrawing aryl chlorides and bromides were coupled effectively as well as heteroatom-containing and sterically hindered aryl halides. The catalytic reaction was conducted in ethanol with a weak and inexpensive inorganic base.
Reduced graphene oxide supported Ni nanoparticles: A high performance reusable heterogeneous catalyst for Kumada-Corriu cross-coupling reactions
Bhowmik, Koushik,Sengupta, Debasish,Basu, Basudeb,De, Goutam
, p. 35442 - 35448 (2014)
Reduced graphene oxide (RGO) has emerged as an excellent 2D catalyst support. A high concentration of air stable Ni(0) nanoparticles (～40 wt%) of average size 11 nm can be loaded on reduced graphene oxide. In this article Kumada-Corriu cross-coupling reactions have been studied extensively using RGO supported 40 wt% Ni nanoparticles (Ni/RGO-40) as a heterogeneous catalyst. The reaction conditions were optimized by performing the cross-coupling between 4-iodoanisole and phenylmagnesium chloride in the presence of a catalytic amount of Ni/RGO-40. A detailed study of the catalysis was performed by varying the haloarenes and Grignard reagents under the optimized conditions with yields of 91-72%. The products were characterized by 1H and 13C NMR spectroscopy. The catalyst was found to be significantly reusable. Finally the recovered Ni/RGO-40 was characterized by X-ray diffraction (XRD) and Raman spectroscopy and found to be unaffected. Considering the catalytic performance, reusability and economic reasons, Ni/RGO-40 can be of technological importance.
Triptycene ring metal palladium compound and application thereof
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Paragraph 0093-0101, (2021/02/24)
The invention discloses a triptycene cyclometalated palladium compound and an application thereof. The triptycene cyclometalated palladium compound has the following general formula, wherein three RAscan be the same or different and are respectively and independently expressed as R1-(Z1-A1-Z2)x-,wherein the three RBs can be the same or different and are respectively and independently expressed asR2-(Z3-A2-Z4)y-, the two RCs may be the same or different, each independently expressed as R3-(Z5-A3-Z6)z-. The triptycene cyclometalated palladium compound provided by the invention has a triptycenelarge-steric-hindrance group, and can stabilize a zero-valent palladium intermediate in a catalytic cycle, so that the catalytic efficiency is improved, the use amount of a catalyst can be reduced tobe less than ten thousandth, and the compound is simple in synthesis step, high in yield, relatively low in cost and suitable for various substrates, and the method has an important application valuefor researching the progress and application of the coupling reaction.
Complexes: Easily Synthesized, Highly Active Pd(II)-NHC Precatalysts for Cross-Coupling Reactions
Xia, Qinqin,Shi, Shicheng,Gao, Pengcheng,Lalancette, Roger,Szostak, Roman,Szostak, Michal
, p. 15648 - 15657 (2021/10/25)
We report the synthesis, characterization, and reactivity of [(NHC)PdCl2(aniline)] complexes. These well-defined, air- and moisture-stable catalysts are highly active in the Suzuki-Miyaura cross-coupling of amides by N-C(O) activation as well as in the Suzuki-Miyaura cross-coupling of esters, aryl chlorides, and Buchwald-Hartwig amination. Most crucially, this study introduces broadly available anilines as stabilizing ligands for well-defined Pd(II)-NHC catalysts. The availability of various aniline scaffolds, including structural and electronic diversity, has a significant potential in fine-tuning of challenging cross-couplings by Pd-NHCs. The parent catalyst in this class, [Pd(IPr)(AN)Cl2], has been commercialized in collaboration with Millipore Sigma, offering broad access for reaction screening and optimization.
2-Phosphinoimidazole Ligands: N-H NHC or P-N Coordination Complexes in Palladium-Catalyzed Suzuki-Miyaura Reactions of Aryl Chlorides
Martinez, Erin E.,Larson, Alexandra J. S.,Fuller, Sydney K.,Petersen, Kathryn M.,Smith, Stacey J.,Michaelis, David J.
supporting information, p. 1560 - 1564 (2021/05/29)
We report the synthesis of two palladium 2-(dialkylphosphino)imidazole complexes and demonstrate their activity as catalysts for Suzuki-Miyaura reactions with (hetero)aryl chlorides at room temperature. Our mechanistic studies demonstrate that these palladium complexes exist as an equilibrium mixture between the P-N coordinated and N-H NHC forms of ligand. Our studies suggest that the N-H NHC form may be important for high catalytic activity in Suzuki-Miyaura reactions with aryl chlorides. These reactions proceed at or near room temperature in good to excellent yields. Heteroaryl chlorides are also reactive at lower catalyst loadings.
