- Base- and phosphine-free palladium-catalyzed homocoupling of arylboronic acid derivatives under air
-
In the presence of a catalytic amount of Pd(OAc)2, various arylboronic acids underwent homocoupling in MeOH at ambient temperature under air to give rise to symmetrical biaryls. The homocoupling of arylboronic acids was also carried out using polyurea-encapsulated Pd(OAc)2 as a recyclable catalyst. Georg Thieme Verlag Stuttgart.
- Yamamoto, Yoshihiko,Suzuki, Ryo,Hattori, Kozo,Nishiyama, Hisao
-
-
Read Online
- A facile method for the dechlorination of mono- and dichlorobiphenyls using Raney Ni-Al alloy in dilute aqueous solutions of alkali hydroxides or alkali metal carbonates
-
Raney Ni-Al alloy in a dilute aqueous alkaline solution of NaOH, KOH, CsOH, LiOH, or Ca(OH) 2 or of alkali metal carbonates such as Na2CO3, K2CO3 becomes a very powerful reducing agent and dechlorinates the polychlorobiphenyl(PCB) congeners mono- and dichlorobiphenyls effectively to afford biphenyl and/or phenylcyclohexane, respectively. The reactions are run under mild conditions without the use of organic solvents. The reductive dechlorination of dichlorobiphenyls with a Raney Ni-Al alloy under ultrasonication was investigated, also.
- Liu, Guo-Bin,Tashiro, Masashi,Thiemann, Thies
-
-
Read Online
- Rhodium-catalyzed oxidative homocoupling of boronic acids
-
Oxidative homocoupling of aryl- and alkenylboronic acids was achieved with Wilkinson's catalyst. Commercially available 2,2,6,6-tetramethylpiperidine-N- oxyl radical (TEMPO) was used as a stoichiometric oxidant.
- Vogler, Thomas,Studer, Armido
-
-
Read Online
- Synthesis of new 2-arylbenzo[b]thiophenes using 'Heck-type' technology
-
Direct 3-substituted benzothiophene arylation using a Heck-type reaction with Pd(OAc)2/n-Bu4NBr as a catalytic system is reported. This reaction was found to perform relatively fast whatever the electron-donating or the electron-withdrawing group at position 3. We also extended this reaction to several aromatic halides, such as benzene, naphthalene and pyridine derivatives, synthesising new 2-arylbenzo[b]thiophenes in moderate to good yields.
- Fournier Dit Chabert, Jérémie,Gozzi, Christel,Lemaire, Marc
-
-
Read Online
- Pd-catalyzed oxidative homocoupling of arylboronic acids in WEPA: A sustainable access to symmetrical biaryls under added base and ligand-free ambient conditions
-
Symmetrical and unsymmetrical biaryls comprises a diverse class of biologically eloquent organic compounds. We herein report, a quick and eco-friendly protocol for the synthesis of biaryls by an oxidative (aerobic) homocoupling of arylboronic acids (ABAs) using Pd(OAc)2 in water extract of pomogranate ash (WEPA) as an efficient agro-waste(bio)-derived aqueous (basic) media. The reactions were executed at ambient aerobic conditions in the absence of external base and ligand to result symmetrical biaryls in excellent yields. The use of renewable media with an effective exploitation of waste, short reaction times, excellent yields of products, easy separation of the products, unnecessating the external base, oxidant, ligand or volatile organic solvents and ambient reaction conditions are the vital insights of the present protocol.
- Appa, Rama Moorthy,Lakshmidevi, Jangam,Naidu, Bandameeda Ramesh,Venkateswarlu, Katta
-
-
- Sustainable Synthesis of Biaryls Using Silica Supported Ferrocene Appended N-Heterocyclic Carbene-Palladium Complex
-
Abstract: A novel silica supported ferrocene appended N-heterocyclic carbene-palladium complex (SilFemBenzNHC@Pd) has been prepared and characterized by using fourier transform infrared (FT-IR), fourier transform Raman (FT-Raman), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and energy dispersive X-ray analysis (EDX). This novel complex served as a robust heterogeneous catalyst for the synthesis of biaryls via homocoupling of aryl boronic acids under base-free conditions in water. Recyclability experiments were executed successfully for six successive runs. Graphic Abstract: [Figure not available: see fulltext.]
- Khanapure, Sharanabasappa,Pore, Dattaprasad,Jagadale, Megha,Patil, Vaishali,Rashinkar, Gajanan
-
p. 2237 - 2249
(2021/01/11)
-
- Synthesis of biaryl compounds via Suzuki homocoupling reactions catalyzed by metal organic frameworks encapsulated with palladium nanoparticles
-
Heterogeneous homocoupling reactions of phenylboronic acids were greatly accelerated via Suzuki homocoupling reactions. In this work, a tandem route was designed which firstly one part of phenylboronic acids reacted with iodine to form iodobenzenes, then another part of phenylboronic acids coupled with iodobenzenes to produce biaryl compounds. The tandem reaction were catalyzed by a bifunctional heterogeneous catalyst of metal organic frameworks encapsulated with palladium nanoparticles (Pd?MOFs). This strategy for forming symmetric C-C bond between benzene rings has obvious advantages such as high efficiency, easy separation, good recyclability and no addition of toxic halogenated benzene.
- Bao, Yan-Sai,Cui, Xin-Yu,Han, Zheng-Bo,Li, Xin,Tang, Hong,Yang, Ming,Zhang, Yu-Yang,Zhao, Kun,Zhou, Mei-Li
-
-
- Cobalt-catalyzed cross-coupling reactions of aryl- And alkylaluminum derivatives with (hetero)aryl and alkyl bromides
-
A simple cobalt complex, such as Co(phen)Cl2, turned out to be a highly efficient and cheap precatalyst for a host of cross-coupling reactions involving aromatic and aliphatic organoaluminum reagents with aryl, heteroaryl and alkyl bromides. New C(sp2)-C(sp2) and C(sp2)-C(sp3) bonds were formed in good to excellent yields and with high chemoselectivity, under mild reaction conditions.
- Dilauro, Giuseppe,Messa, Francesco,Bona, Fabio,Perrone, Serena,Salomone, Antonio
-
supporting information
p. 10564 - 10567
(2021/10/19)
-
- Porphyrin n-pincer pd(Ii)-complexes in water: A base-free and nature-inspired protocol for the oxidative self-coupling of potassium aryltrifluoroborates in open-air
-
Metalloporphyrins (and porphyrins) are well known as pigments of life in nature, since representatives of this group include chlorophylls (Mg-porphyrins) and heme (Fe-porphyrins). Hence, the construction of chemistry based on these substances can be based on the imitation of biological systems. Inspired by nature, in this article we present the preparation of five different porphyrin, meso-tetraphenylporphyrin (TPP), meso-tetra(p-anisyl)porphyrin (TpAP), tetra-sodium meso-tetra(p-sulfonatophenyl)porphyrin (TSTpSPP), meso-tetra(m-hydroxyphenyl)porphyrin (TmHPP), and meso-tetra(m-carboxyphenyl)porphyrin (TmCPP) as well as their N-pincer Pd(II)-complexes such as Pd(II)-meso-tetraphenylporphyrin (PdTPP), Pd(II)-meso-tetra(p-anisyl)porphyrin (PdTpAP), Pd(II)-tetrasodium meso-tetra(p-sulfonatophenyl)porphyrin (PdTSTpSPP), Pd(II)-meso-tetra(m-hydroxyphenyl)porphyrin (PdTmHPP), and Pd(II)-meso-tetra(m-carboxyphenyl)porphyrin (PdTmCPP). These porphyrin N-pincer Pd(II)-complexes were studied and found to be effective in the base-free self-coupling reactions of potassium aryltrifluoroborates (PATFBs) in water at ambient conditions. The catalysts and the products (symmetrical biaryls) were characterized using their spectral data. The high yields of the biaryls, the bio-mimicking conditions, good substrate feasibility, evading the use of base, easy preparation and handling of catalysts, and the application of aqueous media, all make this protocol very attractive from a sustainability and cost-effective standpoint.
- Prasad, Sana Siva,Naidu, Bandameeda Ramesh,Hanafiah, Marlia M.,Lakshmidevi, Jangam,Marella, Ravi Kumar,Lakkaboyana, Sivarama Krishna,Venkateswarlu, Katta
-
-
- Ligand and Base Free Synthesis of Biaryls from Aryl Halides in Aqueous Media with Recyclable Ti0.97Pd0.03O1.97 Catalyst
-
Abstract: Facile protocol for the synthesis of biaryls from aryl halides in presence of magnesium metal without prior formation of organometallic intermediate has been exploited. Irrespective of aqueous medium, Ti0.97Pd0.03O1.97 catalyst supports C–C bond formation reaction in presence of metals rather than dehalogenation without any additives. Homocoupling of 16 different aryl halides furnished corresponding biphenyls in good yield with better functional group tolerance. The recovery of the catalyst was carried out by employing catalyst coated cordierite monolith up to 7th cycle with high yields. A new approach for the cross-coupling reaction is also attempted. Graphic Abstract: [Figure not available: see fulltext.]
- Prasanna,Bhat, Shrikanth K.,Usha,Hegde
-
p. 3313 - 3322
(2021/03/04)
-
- Efficient photocatalytic chemoselective and stereoselective C-C bond formation over AuPd@N-rich carbon nitride
-
Heterogeneous chemoselective or stereoselective C-C coupling reactions remain extremely challenging in traditional organic synthesis. Here, we constructed a AuPd@N-rich carbon nitride (NRCN) photocatalyst through simple ammonia solution heat treatment of carbon nitride and then AuPd NP loading. AuPd@NRCN exhibited extraordinary light color promoted catalytic performance in C-C bond formation under visible light in air. Surprisingly, both high chemoselectivity to unsymmetrical Ullmann biaryl products and satisfactory stereoselectivity to Z-type Heck reaction products could be achieved by changing the light source color. Various substrates exhibited great potential for the economical synthesis of unsymmetrical biaryl products and Z-type olefins. Efficient visible light promoted C-I bond activation accompanied with improved photocatalytic coupling reaction efficiency over AuPd@NRCN was verified firstly by in situ DRIFTS. Considering that the Ullmann cross-coupling reaction is a multi-photon reaction, the improved photocatalytic performance in the Ullmann cross-coupling reaction using a combination of light sources with different colors might be due to the activation of different substrates and/or steps requiring different energies, and the combination of the two energy sources was beneficial for improving the activation efficiency of different substrates and/or steps. The activation of iodobenzene and styrene in the Heck reaction with light was also beneficial to the formation of the stilbene product. The light color promoted chemoselectivity and stereoselectivity are expected to have profound impact on organic synthetic methodology improvement. This journal is
- Jiang, Heyan,Xu, Jie,Zhang, Sishi,Cheng, Hongmei,Zang, Cuicui,Bian, Fengxia
-
p. 219 - 229
(2021/01/28)
-
- Palladium Ion Catalysed Oxidative C–C Bond Formation Reactions in Arylboronic Acid: Application of Cordierite Monolith Coated Catalyst
-
Abstract: Catalytic efficiency of palladium ion substituted in TiO2, Ti0.97Pd0.03O1.97 is successfully exploited for the oxidative homocoupling of arylboronic acid and oxidative Heck coupling reactions between arylboronic acid and olefins. The reaction protocol provides direct approach to synthesize biphenyls and cinnamates from moderate to good yield with good functional group tolerance. As a result, 11 symmetrical biaryls and 14 cinnamates were synthesized from readily available arylboronic acids. Ti0.97Pd0.03O1.97 powder catalyst is synthesized by solution combustion method and characterized by powder X-ray diffraction. The C–C bond formation reactions were carried out by catalyst cartridge method using Ti0.97Pd0.03O1.97 catalyst coated cordierite monolith. Coating of the catalyst on a cordierite monolith enhanced the applicability of the catalyst and made handling and recycling of the catalyst very easy. Catalyst was recovered and recycled for eight times in both homocoupling and oxidative Heck coupling reactions. The turnover number for both the reactions found to be 443 and 424, respectively. Graphic Abstract: [Figure not available: see fulltext.].
- Bhat, Shrikanth K.,Prasanna,Dasappa, Jagadeesh Prasad,Hegde
-
p. 2911 - 2927
(2020/03/31)
-
- Exploring the coordination confinement effect of divalent palladium/zero palladium doped polyaniline-networking: As an excellent-performance nanocomposite catalyst for C-C coupling reactions
-
A pre-formed catalyst Pd2+/PANI composite for C-C coupling reaction was synthesized by combining the self-stabilized dispersion polymerization method with the in-situ composite material. Experiments have confirmed that the relatively high reduced structure (75%) in the polyaniline carrier is more favorable for the coupling reaction. Raman spectroscopy, solid nuclear magnetic, and X-ray photoelectron spectroscopy were performed to characterize the structures. The pre-formed catalyst has uniform coordination of divalent palladium and nitrogen in different valence states of the carrier polyaniline, which shows a good synergistic effect in the catalytic Ullmann reaction, and greatly reduces the use of reducing agents such as hydrazine hydrate. Compared with other studies, we analyzed the catalytic reaction mechanism in detail through real-time online infrared and XPS characterization. The results show that the divalent palladium in the catalyst and the zero-valent palladium generated by the in-situ reaction synergistically promote the reaction, while the polyaniline support acts as a stabilizer and dispersant, which prevents the agglomeration of the metal particles and prolongs increased catalyst life. The prepared Pd2+/PANI composites will become the most attractive alternative to traditional organic materials due to their wide applicability, high catalytic activity, stable recycling and relatively low price. This work provides a new theoretical basis for the understanding of the essential driving force of PANI catalytic activity and the cognition of the micro mechanism of action.
- Liang, Yanping,Liu, Wanyi,Song, Manrong,Sun, Yanyan,Wang, Gang,Wu, Zhiqiang,Zhan, Haijuan
-
p. 177 - 188
(2020/03/17)
-
- Desulfurization of Diaryl(heteroaryl) Sulfoxides with Benzyne
-
Two benzyne-enabled desulfurization reactions have been demonstrated which convert diaryl sulfoxides and heteroaryl sulfoxides to biaryls and desulfurized heteroarenes, respectively. The reaction accessing biaryls tolerates a variety of functional groups, such as halides, pseudohalides, and carbonyls. Mechanistic studies reveal that both reactions proceed via a common assembly process but divergent disassemblies of the generated tetraaryl(heteroaryl) sulfuranes.
- Chen, De-Li,Sun, Yan,Chen, Mengyuan,Li, Xiaojin,Zhang, Lei,Huang, Xin,Bai, Yihui,Luo, Fang,Peng, Bo
-
supporting information
(2019/06/13)
-
- Site-Selective Ruthenium-Catalyzed C-H Bond Arylations with Boronic Acids: Exploiting Isoindolinones as a Weak Directing Group
-
Biologically relevant N-arylisoindolinones efficiently underwent arylation reactions under ruthenium catalysis via C-H bond functionalization. The reactions exclusively led to monoarylated products, and only ortho selectivity was observed in the aromatic ring connected to the nitrogen atom. Interestingly, no C-H bond functionalization was observed in the other benzene ring in the ortho position with respect to the carbonyl group. This ruthenium-catalyzed reaction displayed a high functional group tolerance, and it employed readily available and benchmark stable boronic acid and potassium aryltrifluoroborate derivatives as coupling partners. An appealing late-stage functionalization of indoprofen applying this methodology is showcased.
- Yuan, Yu-Chao,Bruneau, Christian,Roisnel, Thierry,Gramage-Doria, Rafael
-
p. 12893 - 12903
(2019/09/13)
-
- Aerobic and Ligand-Free Manganese-Catalyzed Homocoupling of Arenes or Aryl Halides via in Situ Formation of Aryllithiums
-
Ligand-free manganese-catalyzed homocoupling of arenes or aryl halides can be carried out under aerobic conditions via the in situ formation of the corresponding aryllithiums. A wide range of biaryls and derivatives has been obtained, and a mechanism involving monomeric manganese-oxo complexes has been proposed on the basis of DFT calculations.
- Liu, Yujia,Bergès, Julien,Zaid, Yassir,Chahdi, Fouad Ouazzani,Van Der Lee, Arie,Harakat, Dominique,Clot, Eric,Jaroschik, Florian,Taillefer, Marc
-
p. 4413 - 4420
(2019/03/26)
-
- Highly stable polyphenylene ionomer membranes from dichlorobiphenyls
-
A simple, cost-effective synthetic strategy for highly stable, proton conductive polyphenylene membranes is reported. The title polyphenylene ionomer (SPP-BP) is easily prepared from dichlorobenzenesulfonic acid and dichlorobiphenyls. The SPP-BP membrane with an optimized m-biphenylene/p-biphenylene ratio (i.e., 4: 1) for a hydrophobic moiety exhibits outstanding chemical stability as well as high proton conductivity.
- Shiino, Keisuke,Miyake, Junpei,Miyatake, Kenji
-
supporting information
p. 7073 - 7076
(2019/06/19)
-
- Iron-Catalyzed Isopropylation of Electron-Deficient Aryl and Heteroaryl Chlorides
-
Traditional methods for the preparation of secondary alkyl-substituted aryl and heteroaryl chlorides challenge both selectivity and functional group tolerance. This contribution describes the use of statistical design of experiments to develop an effective procedure for the preparation of isopropyl-substituted (hetero)arenes with minimal isopropyl to n-propyl isomerization. The reaction tolerates electronically diverse aryl chloride coupling partners, with excellent conversion observed for strongly electron-deficient aromatic rings, such as esters and amides. Electron-rich systems, including methyl- and methoxy-substituted aryl chlorides, were found to be less reactive. Furthermore, the reaction was found to be most successful when heteroaryl chlorides were submitted to the cross-coupling protocol. By mapping substituent effects on reaction selectivity, we were able to show that electron-deficient aryl chlorides are essential for efficient coupling, and use electronic structure calculations to predict the likelihood of successful coupling through the estimation of the electron affinity of each aryl chloride. Moderate isolated yields were achieved with selected aryl chlorides, and moderate to good isolated yields were obtained for all the heteroaryl chlorides coupled. Excellent selectivity was observed when a 2,6-dichloroquinoline was used, allowing mono-substitution on a challenging substrate. (Figure presented.).
- Sanderson, James N.,Dominey, Andrew P.,Percy, Jonathan M.
-
p. 1007 - 1017
(2017/03/27)
-
- Synthesis, characterization and crystal structure of Cu(II) complex of trans-cyclohexane-1,2-diamine: Application in synthesis of symmetrical biaryls
-
A new Cu(II) complex [Cu(cyhxn)2(H2O)2][OTf]2 was synthesised by the reaction of ligand cyhxn (cyhxn?=?trans-cyclohexane-1,2-diamine) with Cu(OTf)2 in methanol at room temperature. The complex was fully characterized by elemental analysis (CHN), FT-IR, UV–Vis and EPR spectroscopic techniques. The structure of the complex was confirmed by single crystal X-ray diffraction study. The EPR spectrum is isotropic type having giso?=?2.078, which indicates a distorted octahedral geometry of the complex. The complex was found to be an active homogeneous catalyst for the homocoupling reactions of arylboronic acid to obtain symmetrical biaryls at room temperature in methanol without the use of any additives such as a base and or an oxidant.
- Agrahari, Bhumika,Layek, Samaresh,Kumari, Shweta,Anuradha,Ganguly, Rakesh,Pathak, Devendra D.
-
-
- Bimetallic Au-Pd nanochain networks: Facile synthesis and promising application in biaryl synthesis
-
A simple and facile method is described for the morphology-controlled synthesis of bimetallic Au-Pd alloyed nanochain networks (NNCs) that show high catalytic performance for the Ullmann intermolecular homocoupling of aromatic or alkyl halides (X = I, Br, Cl) in aqueous media and can be reused at least five times, which can also be applied to intramolecular homocoupling.
- Wang, Zheng-Jun,Wang, Xia,Lv, Jing-Jing,Feng, Jiu-Ju,Xu, Xinhua,Wang, Ai-Jun,Liang, Zhiwu
-
p. 3894 - 3899
(2017/07/12)
-
- Homocoupling reactions of terminal alkynes and arylboronic compounds catalyzed by in situ formed Al(OH)3-supported palladium nanoparticles
-
Palladium nanoparticles supported on newly generated Al(OH)3was found to be a highly efficient catalyst in oxidative homo-couplings of (Het)aryl alkynes, (Het)arylboronic acids and potassium (Het)aryltrifluoroborates, respectively. Moderate to excellent yields of symmetrical 1,3-diynes and biaryls were obtained under mild conditions.
- Li, Xing,Li, Dongjun,Bai, Yana,Zhang, Congxia,Chang, Honghong,Gao, Wenchao,Wei, Wenlong
-
supporting information
p. 6996 - 7002
(2016/10/14)
-
- Solvent-Induced Single Crystal-Single Crystal Transformation of an Interpenetrated Three-Dimensional Copper Triazole Catalytic Framework
-
The 2-fold interpenetrated 3D framework 1 can be solvent-induced to noninterpenetrated framework 1′ in a reversible single crystal-single crystal transformation fashion. In addition, 1′ represents the first catalyst based on triazole to catalyze the aerobic homocoupling of various substituted arylboronic acids.
- Wang, Ying,Meng, Shan-Shan,Lin, Peng-Xiang,Xiao, Yi-Wei,Ma, Qing-Qing,Xie, Qiong,Chen, Yuan-Yuan,Zhao, Xiao-Jun,Chen, Jun
-
supporting information
p. 4069 - 4071
(2016/05/24)
-
- Ligand- and Base-Free Access to Diverse Biaryls by the Reductive Coupling of Diaryliodonium Salts
-
A ligand- and base-free, Pd-catalyzed protocol to access a wide range of symmetrical and unsymmetrical biaryls from stable diaryliodonium salts was developed. The reaction involved the use of an effective and recyclable Pd/polyethylene glycol-400 catalyst system to harness the aryl moieties of two diaryliodonium salts; the ensuing biaryls may be utilized to synthesize an array of useful compounds, including 5-aryluracils, carbazoles, chromenones, fluorenones, phenathridines, and boscalid analogues.
- Arun,Reddy, P. O. Venkataramana,Pilania, Meenakshi,Kumar, Dalip
-
supporting information
p. 2096 - 2100
(2016/05/09)
-
- Pd(OAc)2 catalyzed homocoupling of arenediazonium salts in ionic liquids: Synthesis of symmetrical biaryls
-
A facile, high yielding, and simple method for the synthesis of a library of symmetrical biaryls by homocoupling of arenediazonium salts is reported, employing catalytic amounts of Pd(OAc)2 and the readily available imidazolium ionic liquids (ILs), without oxidants, ligands, additives, or volatile solvents. Simple product isolation and recycling/reuse of the IL represent additional advantages of this method.
- Savanur, Hemantkumar M.,Kalkhambkar, Rajesh G.,Laali, Kenneth K.
-
p. 663 - 667
(2016/01/26)
-
- Ligand-, base-, co-catalyst-free copper fluorapatite (CuFAP) as a versatile, ecofriendly, heterogeneous and reusable catalyst for an efficient homocoupling of arylboronic acid at ambient reaction conditions
-
This paper describes the first report in which copper species containing copper fluorapatite (CuFAP) acts as a versatile, eco-friendly, recyclable, heterogeneous catalyst for an efficient synthesis of symmetric biaryls from the homo-coupling of arylboronic acids in methanol solvent at ambient reaction conditions. The developed protocol is ligand-, base-, and co-catalyst-free, sustainable, mild, inexpensive, and compatible with a wide range of aromatic/heterocyclic boronic acids and provides the corresponding products in excellent yields without purification. The catalyst was easily recovered from the reaction mixture and reused several times without loss of activity.
- Mulla, Shafeek A. R.,Chavan, Santosh S.,Pathan, Mohsinkhan Y.,Inamdar, Suleman M.,Shaikh, Taufeekaslam M. Y.
-
p. 24675 - 24680
(2015/03/30)
-
- HOLE TRANSPORTING MATERIAL
-
PROBLEM TO BE SOLVED: To provide a novel compound that has a wide bandgap, is excellent in electrical stability, thermal stability and charge transporting performance and can also be used for hole transporting layers of an organic EL element, and to provide a material that gives good quality of film obtained by applying to form a film and can be insolubilized after forming the film. SOLUTION: There is provided a compound represented by following formula (1), which has a wide bandgap, is excellent in electrical stability, thermal stability and charge transporting performance and can be used for hole transporting layers of an organic EL element. In the formula, at least one of X1 to X6 represents a polymerizable functional group; n represents an integer of 2 to 8; R represents H, an alkyl group or the like; Z1 and Z2 represent an optionally substituted aromatic cyclic group; substituents of the aromatic cyclic group in the Z1 and the Z2 include a linear or cyclic alkyl group, alkoxy group, halogen group, amino group, nitro group or cyano group. COPYRIGHT: (C)2015,JPO&INPIT
- -
-
-
- Clay encapsulated Cu(OH)x promoted homocoupling of arylboronic acids: An efficient and eco-friendly protocol
-
Cu(OH)x has been encapsulated over montmorillonite-KSF by simple ologomeric deposition strategy. The resulting catalyst has been employed for selective homocoupling of arylboronic acids under ambient conditions without requirement of any ligand or base. This catalyst is easy to recover and shows excellent reusability without losing its activity. Techniques like XRD, SEM, TPR, IR, BET surface area measurement and XPS were used to characterize the catalyst. The present method promises for the simple and clean homocoupling of arylboronic acids.
- Dar, Bashir Ahmad,Singh, Snehil,Pandey, Nalini,Singh,Sharma, Priti,Lazar, Anish,Sharma, Meena,Vishwakarma, Ram A.,Singh, Baldev
-
p. 232 - 238
(2014/01/06)
-
- Aerobic homocoupling of arylboronic acids catalysed by copper terephthalate metal-organic frameworks
-
Copper terephthalate MOF is utilised as an environmentally benign, efficient and reusable heterogeneous catalyst to effect the aerobic homocoupling of arylboronic acids yielding the corresponding symmetrical biphenyls under mild reaction conditions. This method tolerates various substituents present in arylboronic acids such as halogens, cyano and nitro groups. The catalytic performance has been compared with that of other copper based MOFs namely MOF-101, [Cu(pdc)2]NH2Me2, [Cu 2(ndc)2ted]n and [Cu(H2L)] n as well as with other copper salt catalysts. Sheldon test confirmed the heterogeneity of the catalyst, which can be reused under optimized conditions with only a minor loss in its activity. A mechanism for the homocoupling reaction is also proposed. The simplicity of catalyst preparation, its stability, substrate selectivity, easy recovery and regeneration designate possible utilization of this catalytic system in a multitude of catalytic reactions and industrial processes. the Partner Organisations 2014.
- Puthiaraj, Pillaiyar,Suresh, Palaniswamy,Pitchumani, Kasi
-
p. 2865 - 2875
(2014/05/06)
-
- Palladium-catalyzed synthesis of symmetrical biaryls under microwave irradiation and conventional heating
-
The activity of the [Pd{C6H4(CH2N(CH 2Ph)2)}(μ-Br)]2 complex was investigated in the synthesis of symmetrical biaryls under both conventional and microwave irradiation conditions, and their results were compared. This complex is efficient, stable, and not sensitive to air or moisture and is a catalyst for the homo-coupling reaction of aryl iodides, bromides, and even chlorides. The products were produced in excellent yields in short reaction times using a catalytic amount of [Pd{C6H4(CH2N(CH 2Ph)2)(μ-Br)]2 complex in N-methylpyrolidine (NMP) at 130 °C. In comparison to conventional heating conditions, the reactions under microwave irradiation gave better yields in shorter reaction times.
- Hajipour, Abdol Reza,Rafiee, Fatemeh
-
p. 1314 - 1327
(2013/04/10)
-
- Synthesis of substituted biaryls via Suzuki, Stille and Hiyama cross-coupling and homo-coupling reactions by CN-dimeric and monomeric ortho-palladated catalysts
-
The catalytic activity of dimeric [Pd{C6H2(CH 2CH2NH2)-(OMe)2,2,3}(μ-Br)] 2 and monomeric [Pd{C6H2(CH2CH 2NH2)-(OMe)2,2,3}Br(PPh3)] complexes as efficient, stable and air- and moisture-tolerant catalysts was investigated in the Suzuki, Stille and Hiyama cross-coupling and homo-coupling reactions of various aryl halides. Substituted biaryls were produced in excellent yields in short reaction times using catalytic amounts of these complexes. The monomeric complex was demonstrated to be more active than the corresponding dimeric catalyst for the cross-coupling reaction of unreactive aryl bromides and chlorides. The combination of homogeneous metal catalysts and microwave irradiation gave higher yields of products in shorter reaction times. Copyright
- Hajipour, Abdol R.,Rafiee, Fatemeh
-
p. 412 - 418
(2013/07/26)
-
- Palladium-catalyzed reductive homocoupling of N′-tosyl arylhydrazines
-
A novel procedure for the preparation of biaryl compounds by Pd-catalyzed homocoupling of N′-tosyl arylhydrazine has been described. N′-Tosyl arylhydrazine, as a readily available and stable coupling partner, demonstrated its generality in the homocoupling reactions. The scope of the reaction and possible mechanism have also been investigated.
- Liu, Jin-Biao,Nie, Lin,Yan, Hui,Jiang, Li-Hua,Weng, Jiang,Lu, Gui
-
supporting information
p. 8014 - 8017
(2013/12/04)
-
- Palladium-catalyzed Suzuki cross-coupling of N′-tosyl arylhydrazines
-
The first palladium-catalyzed Suzuki cross-coupling of N′-tosyl arylhydrazines with various organoboron reagents has been developed for the preparation of biaryl compounds in high yields. N′-Tosyl arylhydrazine as a readily available and stable electrophile also demonstrated its generality in a number of coupling reactions. The Royal Society of Chemistry 2013.
- Liu, Jin-Biao,Yan, Hui,Chen, Hui-Xuan,Luo, Yu,Weng, Jiang,Lu, Gui
-
supporting information
p. 5268 - 5270
(2013/07/04)
-
- Nickel-catalyzed synthesis of diarylamines via oxidatively induced C-N bond formation at room temperature
-
A nickel-catalyzed oxidative coupling of zinc amides with organomagnesium compounds selectively produces diarylamines under mild reaction conditions, with tolerance for chloride, bromide, hydroxyl, ester, and ketone groups. A diamine is bis-monoarylated. A bromoaniline undergoes N-arylation followed by Kumada-Tamao-Corriu coupling in one pot. The reaction may proceed via oxidatively induced reductive elimination of a nickel species.
- Ilies, Laurean,Matsubara, Tatsuaki,Nakamura, Eiichi
-
supporting information
p. 5570 - 5573,4
(2012/12/12)
-
- Supported Au nanoparticles as efficient catalysts for aerobic homocoupling of phenylboronic acid
-
Au nanoparticles with small sizes (1-4 nm) were effectively formed on Mg-Al mixed oxides (Au/MAO), which showed superior catalytic performances and good recyclability in aerobic homocoupling of phenylboronic acid.
- Wang, Liang,Zhang, Wei,Sheng Su, Dang,Meng, Xiangju,Xiao, Feng-Shou
-
supporting information; experimental part
p. 5476 - 5478
(2012/07/02)
-
- Palladium-catalyzed cross-couplings of functionalized 2-bromobenzofurans for atom-economic synthesis of 2-arylbenzofurans using triarylbismuth reagents
-
The palladium catalyzed, atom-economic synthesis of various functionalized 2-arylbenzofurans was achieved through cross-coupling reaction of 2-bromobenzofurans with triarylbismuth reagents. The palladium catalytic protocol is very efficient to furnish various cross-coupled functionalized 2-arylbenzofurnas in high yields using triarylbismuth reagents with three aryl couplings as multi-coupling organometallic nucleophiles in one-pot operation. All the coupling reactions were completed in 1 h short reaction time involving three couplings from triarylbismuths under heating condition.
- Rao, Maddali L.N.,Awasthi, Dheeraj K.,Talode, Jalindar B.
-
supporting information; experimental part
p. 2662 - 2666
(2012/07/02)
-
- Coupling reactions of aromatic halides with palladium catalyst immobilized on poly(vinyl alcohol) nanofiber mats
-
Nanoporous poly(vinyl alcohol) (PVA) nanofiber mats prepared by means of electrospinning have been used for the immobilization of palladium catalyst. Thermal treatment of the palladium-loaded PVA nanofiber mats results in the cross-linking of the matrix PVA molecules as well as the reduction of the divalent palladium (Pd2+) into zerovalent palladium (Pd0) species. The palladium oxidation states were examined by X-ray photoelectron spectroscopic (XPS) analysis. The PVA nanofiber morphology was characterized by scanning electron microscopy (SEM). The catalytic activity and recyclability of the prepared heterogeneous palladium catalysts have been evaluated for the Ullmann, Heck-Mizoroki and Sonogashira coupling reactions of aromatic halides. The large structure of the Pd/PVA nanofiber mats can greatly facilitate its separation and recycling, and the high catalytic activity and stability of the prepared Pd/PVA nanofiber mats have been attributed to the chelation of palladium species with the abundant hydroxyl functional groups on the PVA matrix surface area.
- Shao, Linjun,Ji, Weixin,Dong, Pengdu,Zeng, Minfeng,Qi, Chenze,Zhang, Xian-Man
-
experimental part
p. 267 - 272
(2012/03/26)
-
- A comparative homocoupling reaction of aryl halides using monomeric orthopalladated complex of 4-methoxybenzoylmethylenetri-phenylphosphorane under conventional and microwave irradiation conditions
-
The activity of [Pd(C6H4CH2NH 2-K2-C-N)PPh3MOBPPY]OTf complex, A (MOBPPY = 4-methoxybenzoylmethylenetriphenylphosphoraneylide) was investigated in the homocoupling reaction of a vast range of aryl halides under both conventional and microwave irradiation conditions and their results were compared. The complex was active and showed high efficiency in the formation of new C-C bonds. The yields were excellent using a catalytic amount of [Pd(C6H 4CH2NH2-K2-C-N)PPh 3MOBPPY]OTf complex in N, N-dimethylformamide at 120 °C. In comparison to conventional heating conditions, the reactions under microwave irradiation gave higher yields in shorter reaction times.
- Hajipour, Abdol R.,Karami, Kazem,Tavakoli, Ghazal
-
experimental part
p. 567 - 576
(2011/10/18)
-
- Synthesis of functionalized 2-arylthiophenes with triarylbismuths as atom-efficient multicoupling organometallic nucleophiles under palladium catalysis
-
Atom-efficient cross-coupling reactions of functionalized 2-bromo- and 2-iodothiophenes have been demonstrated using triarylbismuths as atom-efficient multicoupling organometallic nucleophiles under palladium-catalyzed conditions. These couplings with various functionalized triarylbismuths proceeded smoothly to afford the corresponding functionalized 2-arylthiophenes in high yields. Georg Thieme Verlag Stuttgart · New York.
- Rao, Maddali L. N.,Banerjee, Debasis,Dhanorkar, Ritesh J.
-
supporting information; experimental part
p. 1324 - 1330
(2011/07/07)
-
- Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: A non-product specific route to C-8 substituted analogues
-
Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO4 oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.
- Berezin, Andrey A.,Koutentis, Panayiotis A.
-
experimental part
p. 4069 - 4078
(2011/06/24)
-
- Phosphine ligand triggered oxidative decarbonylative homocoupling of aromatic aldehydes: Selectively generating biaryls and diarylketones
-
A novel rhodium-catalyzed oxidative decarbonylative homocoupling of aromatic aldehydes to generate biaryls and diarylketones selectively and efficiently, triggered by the choice of different phosphine ligands.
- Yang, Luo,Zeng, Tieqiang,Shuai, Qi,Guo, Xiangyu,Li, Chao-Jun
-
supporting information; experimental part
p. 2161 - 2163
(2011/03/22)
-
- An efficient and recyclable heterogeneous palladium catalyst utilizing naturally abundant pearl shell waste
-
An efficient and recyclable ligand-free heterogeneous catalyst has been prepared by the immobilization of palladium onto ground pearl shell powders (Pd/shell powders, Pd/SP). The catalytic activity and recyclability of the prepared Pd/SP along with the charcoal and calcium carbonate supported palladium (Pd/C and Pd/CaCO3) catalysts have been evaluated using the reductive homocoupling of aromatic halides. Pd/SP not only has higher catalytic activity, but also exhibits much stronger stability than Pd/C and Pd/CaCO 3. The remarkable Pd/SP stability has been attributed to the chelation of palladium species with the surface chitin and protein molecules of the supported pearl shell powders. The X-ray photoelectron spectroscopy (XPS) studies show that the reductive Pd0 species can be regenerated in situ from the oxidative Pd2+ species for the Pd/SP catalyzed reductive homocoupling of aromatic halides in ethanol/DMSO solution, suggesting that the heterogeneous and homogeneous palladium catalysis proceeds through a similar Pd0/Pd2+ cycle catalytic mechanism.
- Zeng, Minfeng,Du, Yijun,Qi, Chenze,Zuo, Shufeng,Li, Xiudong,Shao, Linjun,Zhang, Xian-Man
-
experimental part
p. 350 - 356
(2011/04/17)
-
- Palladium-catalyzed reductive homocoupling of aromatic halides and oxidation of alcohols
-
Palladium-catalyzed reductive homocoupling of aromatic halides can be performed in alcohol solutions without any auxiliary reducing reagents. Pd(dppf)Cl2 [dppf = 1,1′-bis(diphenylphosphino)ferrocene] has been shown as the most effective catalyst among the palladium catalysts screened for the model reductive homocoupling of iodobenzene in alcoholic solutions. The reduction of iodobenzene is stoichiometrically coupled with the oxidation of solvent alcohol (3-pentanol). The X-ray photoelectron spectroscopic (XPS) studies clearly indicate that the oxidation of solvent alcohol molecules is involved with the in situ regeneration of the reductive Pd0(dppf) active species, indicating that the solvent alcohol also reacts as a reducing reagent for the reductive homocoupling of aromatic halides. Elimination of the external reducing reagents will simplify the product separation and purification. Base is essential for the success of the Pd(dppf)Cl 2-catalyzed redox reaction as 2 molar equiv of base is needed to neutralize the acid byproduct formed. Biaryls are the predominant products for the Pd(dppf)Cl2-catalyzed reductions of the unsubstituted aromatic halides in 3-pentanol solution, whereas the dehalogenation products are predominant for the Pd(dppf)Cl2-catalyzed reductions of the substituted aromatic halides. The reaction mechanisms have been discussed for the palladium-mediated concomitant reduction of aromatic halides and oxidation of alcohols without any auxiliary reductants and oxidants.
- Zeng, Minfeng,Du, Yijun,Shao, Linjun,Qi, Chenze,Zhang, Xian-Man
-
experimental part
p. 2556 - 2563
(2010/09/11)
-
- Pd-catalyzed synthesis of α-aryl ketones through couplings of α-arylacetyl chlorides with triarylbismuths as multi-coupling nucleophiles
-
The cross-coupling reaction of α-arylacetyl chlorides with triarylbismuths was studied under Pd-catalyzed conditions. The reaction was found to be facile under the established protocol and furnished high yields of α-aryl ketones in short reaction times. T
- Rao, Maddali L.N.,Giri, Somnath,Jadhav, Deepak N.
-
experimental part
p. 6133 - 6138
(2010/02/27)
-
- Stille cross-coupling reactions with tin reagents supported on ionic liquids
-
New ionic-liquid-supported tin reagents were synthesized and used in Stille cross-coupling reactions. High yields of biaryls were obtained under low-temperature, solvent-free, ligand-free conditions, with simple purification techniques. Moreover, the tin compound could be recycled up to five times without significant loss of reactivity. An expanded catalytic cycle for the Stille cross coupling reaction is proposed in order to explain side products that were formed under certain reaction conditions.
- Pham, Phuoc Dien,Vitz, Juergen,Chamignon, Cecile,Martel, Arnaud,Legoupy, Stephanie
-
experimental part
p. 3249 - 3257
(2009/12/24)
-
- Pd/TEMPO-catalyzed electrooxidative synthesis of biaryls from arylboronic acids or arylboronic esters
-
A facile electrooxidative method for synthesizing biaryls from arylboronic acids or arylboronic esters is described. In the presence of a catalytic amount of Pd(OAc)2 and TEMPO, the electrooxidation of arylboronic acids or arylboronates gave the corresponding biaryls in moderate to excellent yields.
- Mitsudo, Koichi,Shiraga, Takuya,Kagen, Daisuke,Shi, Deqing,Becker, James Y.,Tanaka, Hideo
-
supporting information; experimental part
p. 8384 - 8388
(2009/12/24)
-
- Preparation of unsymmetrical biaryls by pd(II)-catalyzed cross-coupling of aryl iodides
-
The Ullmann homo-and cross-couplings of aryl iodides are carried out to afford symmetrical and unsymmetrical biaryls in moderate to good yields in a catalytic system of Pd(OAc)2/K2CO3/MeCOEt. The high selectivity of unsymmetrical biaryl products in cross-couplings mainly depends on the reactivity difference between two iodoarene substrates and their employed ratios.
- Wang, Liqiang,Lu, Wenjun
-
supporting information; experimental part
p. 1079 - 1082
(2009/07/25)
-
- Electrooxidative homo-coupling of arylboronic acids catalyzed by electrogenerated cationic palladium catalysts
-
An electrochemical method for generating cationic palladium complexes was integrated into an electrooxidative homo-coupling of arylboronic acids. In the presence of a catalytic amount of TEMPO, the homo-coupling reaction proceeded efficiently under argon to afford symmetric biaryls.
- Mitsudo, Koichi,Shiraga, Takuya,Tanaka, Hideo
-
scheme or table
p. 6593 - 6595
(2009/04/06)
-
- Copper(I)-catalysed homo-coupling of aryldiazonium salts: synthesis of symmetrical biaryls
-
Copper(I) triflate acts as an efficient stoichiometric reagent for the homo-coupling of aryldiazonium salts bearing electron-withdrawing group(s), to yield symmetrical biaryls in acetonitrile under mild reaction conditions. Aryldiazonium salts bearing electron-donating groups undergo the reaction by using catalytic amounts of a copper complex prepared in situ from copper(II) triflate and 2,2′-bipyridine with metallic copper as an ultimate reductant.
- Cepanec, Ivica,Litvi?, Mladen,Udikovi?, Josipa,Pogoreli?, Ivan,Lovri?, Marija
-
p. 5614 - 5621
(2007/12/29)
-
- Homocoupling of arylboronic acids with a catalyst system consisting of a palladium(II) N-heterocyclic carbene complex and p-benzoquinone
-
In the presence of 1-3 mol% SIPr-ligated Pd(OAc)2 and 0.6 equivalent of p-benzoquinone, various arylboronic acids underwent homocoupling in MeOH at ambient temperature to produce symmetrical biaryls in 38-96% yields. Georg Thieme Verlag Stuttgart.
- Yamamoto, Yoshihiko
-
p. 1913 - 1916
(2008/03/13)
-
- Phosphine oxides as stabilizing ligands for the palladium-catalyzed cross-coupling of potassium aryldimethylsilanolates
-
The palladium-catalyzed cross-coupling reaction of potassium (4-methoxyphenyl)dimethylsilanolate (K+1-) with aryl bromides has been demonstrated using triphenylphosphine oxide as a stabilizing ligand. Unsymmetrical biaryls can be prepared from a variety of aryl bromides in good yield with short reaction times. Qualitative kinetic studies compared effects of different phosphine oxides on the rate of cross-coupling and established the beneficial effect of these ligands in the reaction of electron-rich arylsilanolates. The improved yield and reproducibility of the cross-coupling of several bromides was demonstrated by direct comparison of reactions performed with and without triphenylphosphine oxide under non-rigorous exclusion of oxygen.
- Denmark, Scott E.,Smith, Russell C.,Tymonko, Steven A.
-
p. 5730 - 5738
(2008/02/07)
-
- Process of heterocoupling by electrolytic microbattery, use of cobalt for implementing said coupling and composition for doing so
-
This invention has as its object a process for preparation of vinyl aryl derivatives by an electrochemical path. This process is defined in that it consists in subjecting a composition that comprises a cobalt salt, an aromatic halide and a vinyl ester to the action of a metal that is at least as reducing as zinc. Application to organic synthesis.
- -
-
-