13141-42-9Relevant articles and documents
Sonogashira (Cu and amine free) and Suzuki coupling in air catalyzed: Via nanoparticles formed in situ from Pd(ii) complexes of chalcogenated Schiff bases of 1-naphthaldehyde and their reduced forms
Bhaskar, Renu,Sharma, Alpesh K.,Yadav, Manoj K.,Singh, Ajai K.
, p. 15235 - 15248 (2017)
The reaction of 1-naphthaldehyde with 2-(phenylthio/seleno)ethylamine afforded air- and moisture-insensitive Schiff bases: C10H7-1-CHN-CH2CH2EPh (L1: E = S; L2: E = Se). Then, on treatment with NaOAc and Li2PdCl4, palladacycles, [Pd(L1-H/L2-H)Cl] (1/2) were formed at room temperature, in which L1/L2 are ligated as an unsymmetric (C-, N, E) pincer. The reduction of >CN bonds of L1 and L2 with sodium borohydride gave C10H7-1-CH2NH-CH2CH2EPh (L3: E = S; L4: E = Se). The reactions of L3/L4 at room temperature, similar to those of L1/L2, resulted in the formation of complex [Pd(L3/L4)Cl2] (3/4), in which the ligand is coordinated in a bidentate (N, E) mode. The yield of all the complexes was >85%. Characterization by HR-MS, 1H, 13C{1H} and 77Se{1H} NMR spectra of L1-L4 and their complexes 1-4 were performed. The structures of L1 and 1-4 were established with single-crystal X-ray diffraction. In all the complexes, the geometry of palladium was distorted square planar. The Pd-S bond distances in 1 and 3 were 2.426(12) and 2.259(2) ?, respectively, whereas Pd-Se bond lengths (?) were 2.523(11) (2) and 2.369(10) (4) ?. The catalytic activities of 1-4 were explored for copper- and amine-free Sonogashira and Suzuki-Miyaura coupling (SMC) of aryl halides under aerobic conditions. The amount of catalyst required for achieving good conversion was 0.01 and 0.05 mol% for SMC and Sonogashira coupling, respectively. The conversion of some substrates reached a maximum in 1 and 2 h for Sonogashira coupling and SMC, respectively. The palladacycles as catalysts gave good conversion efficiency. The generation of palladium-containing nanoparticles (NPs) during both coupling reactions was observed. These were isolated and HR-TEM studies were performed on them and revealed their size as ～2-7 nm. The SEM-EDX analysis indicated the presence of organochalcogen ligands or their fragments in the samples. They independently catalyzed both reactions. Therefore, the role of 1-4 in catalysis undoubtedly exists. For Sonogashira coupling, the formation and role of such Pd-based NPs under aerobic conditions were observed for the first time. The complexes 1-4 showed the potential for reuse, as in the eighth cycle, conversion dropped by only 20%.
A mesoionic bis(Py-tzNHC) palladium(II) complex catalyses "green" Sonogashira reaction through an unprecedented mechanism
Gazvoda, Martin,Virant, Miha,Pevec, Andrej,Urankar, Damijana,Bolje, Aljo?a,Ko?evar, Marijan,Ko?mrlj, Janez
, p. 1571 - 1574 (2016)
A novel bis(pyridyl-functionalized 1,2,3-triazol-5-ylidene)-palladium(ii) complex [Pd(Py-tzNHC)2]2+ catalyses the copper-, amine-, phosphine-, and additive-free aerobic Sonogashira alkynylation of (hetero)aryl bromides in water as the only reaction solvent. The catalysis proceeds along two connected Pd-cycles with homogeneous bis-carbene Pd0 and PdII species, as demonstrated by electrospray ionization mass spectrometry.
Synthesis and characterization of nickel inverse 9-metallacrown-3, palladium-silver, and dinuclear platinum complexes containing pyrazole-functionalized NHC ligands
Chen, Chao,Qiu, Huayu,Chen, Wanzhi
, p. 8671 - 8678 (2011)
Three metallacrown nickel complexes [Ni3(μ-OH)(L1) 3](PF6)2 (1, L1 = 3-((N-methylimidazolylidenyl) methyl)-5-methylpyrazolate), [Ni3(μ-OH)(L2)3](PF 6)2 (2, L2 = 3-((N-mesitylimidazolylidenyl)methyl)-5- methylpyrazolate), and [Ni3(μ-OH)(L3)3](PF 6)2 (3, L3 = 3-((N-pyrimidin-2-ylimidazolylidenyl)methyl)- 5-methylpyrazolate) were obtained by the reactions of corresponding silver-NHC complexes with Raney nickel powder at 45 °C. The same reaction at 80 °C afforded [Ni3(L2)4](PF6)2 (4). The carbene-transfer reaction of the silver-carbene complex with [(η3-C3H5)PdCl]2 yielded the heterotrimetallic complex [AgPd2(η3-C 3H5)2(L2)2](PF6) (5), whereas the carbene-transfer reaction with Pt(cod)Cl2 gave [Pt 2(L3)2](PF6)2 (6). All of these complexes have been fully characterized by ESI-MS, NMR spectroscopy, and elemental analysis. The molecular structures of 1-6 were also studied by X-ray diffraction analysis. In 1-3, three nickel centers are bridged together by three pyrazole-NHC ligands and a hydroxide group, forming a 9-metallacrown-3 topology. Complex 4 is paramagnetic, consisting of two square-planar nickel(II) ions and one tetrahedral nickel ion in which three Ni ions are bridged by four pyrazolate units. In the mixed Pd-Ag complex 5, two palladium and one silver centers are bridged by two pyrazole-NHC ligands. Complex 5 showed good catalytic activity in the Sonogashira coupling reaction of aryl bromides and phenylacetylene under mild conditions typically catalyzed by Pd-Cu systems.
Recyclable and reusable NiCl2(PPh3)2/CuI/PEG-400/H2O system for the sonogashira coupling reaction of aryl iodides with alkynes
Wei, Ting,Zhang, Tingli,Huang, Bin,Tuo, Yuxin,Cai, Mingzhong
, p. 846 - 849 (2015)
A stable and highly efficient NiCl2(PPh3)2/CuI/PEG-400/H2O catalytic system for the Sonogashira reaction has been developed. In the presence of NiCl2(PPh3)2 and CuI, the coupling reaction of aryl iodides with terminal alkynes was carried out smoothly in a mixture of poly(ethylene glycol) (PEG-400) and water at 100C with K2CO3 as base to afford a variety of arylacetylenes in good to excellent yields. The isolation of the products was readily performed by extraction with petroleum ether, and the NiCl2(PPh3)2/CuI/PEG-400/H2O system could be easily recycled and reused six times without significant loss of catalytic activity. Our system not only avoids the use of easily volatile organic solvents but also solves the basic problem of catalyst reuse.
Blue fluorescent 4a-aza-4b-boraphenanthrenes
Bosdet, Michael J. D.,Jaska, Cory A.,Piers, Warren E.,Sorensen, Ted S.,Parvez, Masood
, p. 1395 - 1398 (2007)
Figure presented Phenanthrene analogues with internalized B-N moieties were found to afford blue light emission with good quantum efficiencies, whereas the isomeric species with peripheral B-N moieties displayed only UV emission behavior, like the all-carbon framework.
Mesoporous Carbon Supporting Pd (0) as a Highly Efficient and Stable Catalyst for Sonogashira Reaction in Aqueous Media
Wang, Peng,Wang, Guang-Yu,Qiao, Wen-Long,Feng, Yi-Si
, p. 1792 - 1799 (2016)
Abstract: In this study, palladium (0) nanoparticle supported on mesoporous carbon (Pd/MPC) is prepared by impregnation and H2 reduction. Characterization by XRD, XPS and TEM reveals the mesoporous structure and a high dispersion of palladium nanoparticles (about 4.8?nm) in the mesopores. The catalyst has excellent catalytic activity and stability for Sonogashira reactions of aryl halide (–I, –Br) in aqueous solution. It is noteworthy that Sonogashira reactions of aryl halide (–Cl) can occur by using the novel Pd/MPC catalyst. Meanwhile, the catalyst can be recovered and reused without loss of efficiency until the fifth cycle in water. The fresh catalyst would be of major significance for industrial applications. Graphical Abstract: [Figure not available: see fulltext.]
Copper- and base-free Sonogashira-type cross-coupling reaction of triarylantimony dicarboxylates with terminal alkynes under an aerobic condition
Wang, Xuan,Qin, Weiwei,Kakusawa, Naoki,Yasuike, Shuji,Kurita, Jyoji
, p. 6293 - 6297 (2009)
A simple copper- and base-free palladium-catalyzed Sonogashira-type cross-coupling by the use of triarylantimony dicarboxylates is described. Reaction of triarylantimony diacetates with terminal alkynes in the presence of 1 mol % of PdCl2(PPhs
Influence of pendent alkyl chains on Heck and Sonogashira C-C coupling catalyzed with palladium(II) complexes of selenated Schiff bases having liquid crystalline properties
Rao, Gyandshwar Kumar,Kumar, Arun,Singh, Mahabir Pratap,Kumar, Ajay,Biradar, Ashok Manikrao,Singh, Ajai K.
, p. 42 - 47 (2014)
The effect of pendent alkyl chain lengths on Heck and Sonogashira coupling has been investigated for the first time using air and moisture insensitive complexes, [PdLCl] (1-4), of selenated Schiff bases (L = L1-L4), differing in length and number of pendent alkyl chain(s) and behaving as a (Se, N, O -) type of ligand. Differential scanning calorimetric (DSC) and polarized optical microscopic (POM) investigations show liquid crystalline nature of L1 and L2, which have one pendent alkyl chain of size C18 and C10 respectively. The yields of coupled products in catalytic Heck and Sonogashira coupling reactions were found good when amount of 1-4 used for them was 1.0 and 0.5 mol% respectively. The catalytic efficiency decreases with alkyl chain length of pendent arm of ligand for Heck coupling but remains unaffected in case of Sonogashira coupling. The in situ generation of palladium nanoparticles (NPs) protected with organoselenium species occurs in the case of Heck coupling. The length of pendent alkyl chain appears to control the dispersion and composition of these NPs and consequently the catalytic efficiency for Heck coupling. The black residues formed in the case of Sonogashira coupling catalyzed with 1 and 4 were found to have small fraction of NPs and a large proportion of big size aggregates. Their compositions for both the catalysts have been found nearly the same and due to predominance of aggregates, the efficiency remains almost unchanged on varying length of pendent alkyl chain. The two phase test for Heck coupling indicates that catalysis is largely heterogeneous.
Palladium-catalyzed deacetonative coupling of aryl propargylic alcohols with aryl chlorides in water
Chang, Feng,Liu, Yanping
, p. 961 - 967 (2017)
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.
Towards to the trans-bromination of 2-styrylpyridine with a palladacycle intermediary and structure analysis for trans-1,2-dibromo-2-styrylpyridine
Mafud, Ana Carolina,Gambardella, Maria Teresa Do Prado,Caires, Antonio Carlos Fávero
, p. 87 - 90 (2011)
The simple halogenation of alkynes in conventional organic reactions gives a blend of cis and trans isomers. It is proposed then, a synthesis of stereospecific halogenation of alkynes in trans position, using palladacycle as intermediaries. The recrystallization of the compound obtained by bromination of 2-Styrylpyridine, with cyclepalladium intermediary results in a single crystal, which is subjected to X-ray diffraction. The crystal packing is established through weak interactions of three types. The first one is of the type π × π interactions, from symmetry operation, between the centroids. The second one is of the type C-X?π interactions. And the last type is an anomalous intermolecular interaction between halogens, C-X?X-C, with bond distances smaller than the sum of the van der Waals radii. The conformation on the C=C bond is trans and the dihedral angle between the aromatic rings is (with esd approximate) 18.1(3)°.
Pd-grafted porous metal-organic framework material as an efficient and reusable heterogeneous catalyst for C-C coupling reactions in water
Roy, Anupam Singha,Mondal, John,Banerjee, Biplab,Mondal, Paramita,Bhaumik, Asim,Islam, Sk. Manirul
, p. 320 - 327 (2014)
Palladium nanoparticles (Pd NPs) have been grafted at the surfaces of a Co-containing metal-organic framework material MCoS-1. The Pd NPs grafted material Pd(0)/MCoS-1 has been characterized by HR TEM, XPS and EPR spectroscopic analyses. Pd(0)/MCoS-1 showed excellent catalytic activities in Suzuki-Miyaura cross-coupling reaction for the synthesis of a diverse range of biaryl organics in water. Sonogashira cross-coupling between terminal alkynes and aryl halides has also been carried out over this Pd-nanocatalyst in water without the addition of any Cu co-catalyst. In both reactions the catalyst is easily recoverable and can be reused for several times without appreciable loss of catalytic activity. No evidence of the leaching of Pd from the catalyst during the course of reaction has been observed, suggesting true heterogeneity in our catalytic systems.
Sonogashira cross-coupling reactions with heteroaryl halides in the presence of a tetraphosphine-palladium catalyst
Feuerstein, Marie,Doucet, Henri,Santelli, Maurice
, p. 1717 - 1720 (2005)
Heteroaryl halides undergoes cross-couplings with alkynes in good yields in the presence of [PdCl(C3H5)]2/cis,cis,cis-1,2, 3,4-tetrakis(diphenylphosphinomethyl)cyclopentane as catalyst. A variety of heteroaryl halides such as pyridines, quinolines, a pyrimidine, an indole, a thiophene, or a thiazole have been used successfully. The reaction also tolerates several alkynes such as phenylacetylene and a range of alk-1-ynols. Furthermore, this catalyst can be used at low loading with some substrates.
Palladium nanoparticles immobilized on magnetic methionine-functionalized chitosan: A versatile catalyst for Suzuki and copper-free Sonogashira reactions of aryl halides at room temperature in water as only solvent
Hajipour, Abdol R.,Tavangar-Rizi, Zeinab
, (2017)
The preparation of an efficient heterogeneous catalyst system based on the immobilization of palladium nanoparticles on a magnetic nanoparticle core (ImmPd(0)-MNPs) is described. The new catalytic system was characterized using transmission and scanning electron microscopies, X-ray diffraction, energy-dispersive X-ray and Fourier transform infrared spectroscopies, thermogravimetric analysis, vibrating sample magnetometry and inductively coupled plasma analysis. We have demonstrated that ImmPd(0)-MNPs is an efficient and reusable catalyst for the Suzuki–Miyaura and Sonogashira coupling reactions of various types of aryl halides in water as a green and environmentally acceptable solvent. Moreover, the reactions were carried out efficiently at room temperature. The catalyst was easily separated using an external magnet from the reaction mixture and recycled ten times without significant loss of activity.
Substituent effect of diimino-palladium (II) pincer complexes on the catalysis of Sonogashira coupling reaction
Zhang, Jin-Hua,Li, Ping,Hu, Wen-Ping,Wang, Hong-Xing
, p. 107 - 112 (2015)
Three NCN diimine ligands 4-6 were synthesized after condensation of isophthalaldehydes 1-3 and anilines. Treatment of 4-6 with Pd2(dba)3 in toluene resulted in the corresponding PdII-NCN-But (7), PdII-NCN-H (8) and PdII-NCN-NO2 (9) pincer complexes, respectively with high yields. Palladium pincers 7-9 and their precursors 4-6 were fully characterized by elemental analysis, IR, 1H NMR and 13C NMR spectroscopy. The molecular structures of 7b and 9b were also determined by X-ray single crystal diffraction. Sonogashira coupling of phenyl acetylene and 3-nitrobenzene catalyzed by 7-9 show that 9 exhibits the highest catalytic activity, suggesting that the electron withdrawing groups at the position-4 of palladium atom in palladium pincers will enhance their catalytic activity.
Cyclopalladated ferrocenylimines: efficient catalysts for homocoupling and Sonogashira reaction of terminal alkynes
Yang, Fan,Cui, Xiuling,Li, Ya-nan,Zhang, Jinli,Ren, Ge-rui,Wu, Yangjie
, p. 1963 - 1969 (2007)
A novel pathway for homocoupling of terminal alkynes has been described using cyclopalladated ferrocenylimine 1 or 2/CuI as catalyst in the air. This catalytic system could tolerate several functional groups. The palladacycle 2 in the presence of n-Bu4NBr as an additive could be applied to Sonogashira cross-coupling reaction of aryl iodides, aryl bromides, and some activated aryl chlorides with terminal alkynes under amine- and copper-free conditions, mostly to give moderate to excellent yields.
Sonogashira couplings catalyzed by collaborative (N-heterocyclic carbene)-copper and -palladium complexes
Gallop, Christopher W. D.,Chen, Ming-Tsz,Navarro, Oscar
, p. 3724 - 3727 (2014)
A general protocol for the Sonogashira reaction using a 100:1 combination of (N-heterocyclic carbene)-Cu and (N-heterocyclic carbene)-Pd complexes is presented. Catalyst loadings of 1 mol % (NHC)-Cu and 0.01 mol % (NHC)-Pd allow for the coupling of aryl bromides and aryl alkynes, in air and in a non-anhydrous solvent, in high yields.
Ligand-free Fe-Cu cocatalyzed cross-coupling of terminal alkynes with aryl halides
Panda, Niranjan,Jena, Ashis Kumar,Mohapatra, Sasmita
, p. 956 - 958 (2011)
Copper ferrite-nanoparticle-mediated cross-coupling of terminal alkynes with aryl halides under ligand-free conditions was demonstrated. The magnetic nature of the copper ferrite nanoparticles was exploited for easy and quantitative separation of the catalyst. Leaching of Fe and Cu to the reaction medium was found to be within permissible limit and the activity of the catalyst was almost unaltered up to three consecutive cycles.
A novel silver iodide catalyzed sonogashira coupling reaction
Li, Pinhua,Wang, Lei
, p. 2261 - 2265 (2006)
A novel and efficient Ag-catalyzed Sonogashira coupling reaction has been developed. Terminal alkynes couple with aryl iodides and aryl bromides in the presence of silver iodide, tri-phenylphosphine and potassium carbonate to afford the corresponding cross-coupling products in high yields. Georg Thieme Verlag Stuttgart.
A facile protocol for copper-free palladium-catalyzed Sonogashira coupling in aqueous media
Jung, Da-Young,Kim, Seung-Hoi,Park, Soo Youl
supporting information, (2021/11/09)
The combination of a readily available palladium catalyst and an eco-friendly basic aqueous solution of room-temperature ionic liquid, choline hydroxide (ChOH), was used in a facile protocol alternative to the Sonogashira coupling reaction, alkynylation of aryl halides in the absence of a copper cocatalyst and an external base. The dual nature of ChOH to act as a base and a green solvent played a crucial role in the catalytic cycle. The coupling reaction progressed efficiently to form a Csp-Csp2 bond under the identified conditions although the reaction outcome depended significantly on the substrates.
Copper(0) nanoparticle catalyzed Z-Selective Transfer Semihydrogenation of Internal Alkynes
Moran, Maria Jesus,Martina, Katia,Bieliunas, Vidmantas,Baricco, Francesca,Tagliapietra, Silvia,Berlier, Gloria,De Borggraeve, Wim M.,Cravotto, Giancarlo
supporting information, p. 2850 - 2860 (2021/05/06)
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.).
A conjugated microporous polymer as a recyclable heterogeneous ligand for highly efficient regioselective hydrosilylation of allenes
Jiang, Ya-Nan,Zeng, Jia-Hao,Yang, Ying,Liu, Zhi-Kai,Chen, Jun-Jia,Li, Ding-Chang,Chen, Li,Zhan, Zhuang-Ping
supporting information, p. 1597 - 1600 (2020/02/13)
Pyridines containing adjacent CC bonds were utilized as ligand units and integrated into the skeleton of conjugated microporous polymers. The resultant Pd-CMP-1 was first applied as a highly efficient heterogeneous catalytic system for Pd-catalyzed allene hydrosilylation towards a wide range of allenes to produce branched allylsilanes with high regioselectivity. The ligand units of the polymer, along with the confinement effect of the porous structure, jointly regulated the regioselectivity. The parts-per-million (ppm) levels of Pd, coordinated with the recyclable heterogeneous ligand, show promise for industrial applications. This work opens a new front of using CMP as an intriguing platform for developing highly efficient catalysts to control the regioselectivities in allene hydrosilylation.
