- Synthesis and Optoelectronic Properties of Hexa-peri-hexabenzoborazinocoronene
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The first rational synthesis of a BN-doped coronene derivative in which the central benzene ring has been replaced by a borazine core is described. This includes six C?C ring-closure steps that, through intramolecular Friedel–Crafts-type reactions, allow
- Dosso, Jacopo,Tasseroul, Jonathan,Fasano, Francesco,Marinelli, Davide,Biot, Nicolas,Fermi, Andrea,Bonifazi, Davide
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- Pd nanoparticles catalyst supported on TMU-16-NH2 metal-organic framework for Sonogashira cross-coupling reaction
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The current article presented the synthesis and characterization of a novel, unique, and effective heterogeneous catalytic system, based on a metal-organic framework named Pd@TMU-16-NH2 with high catalytic performance. Also, the application of
- Alinezhad, Heshmatollah,Ghasemi, Shahram,Kiani, Ameneh
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- Pd supported on clicked cellulose-modified magnetite-graphene oxide nanocomposite for C-C coupling reactions in deep eutectic solvent
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Cellulose-modified magnetite-graphene oxide nanocomposite was prepared via click reaction and utilized for immobilization of palladium (Pd) nanoparticles without using additional reducing agent. The abundant OH groups of cellulose provided the uniform dispersion and high stability of Pd nanoparticles, while magnetite-graphene oxide as a supporting material offered high specific surface area and easy magnetic separation. The as-prepared nanocomposite served as a heterogeneous catalyst for the Heck and Sonogashira coupling reactions in various hydrophilic and hydrophobic deep eutectic solvents (DESs) as sustainable and environmentally benign reaction media. Among the fifteen DESs evaluated for coupling reactions, the hydrophilic DES composed of dimethyl ammonium chloride and glycerol exhibited the best results. Due to the low miscibility of catalyst and DES in organic solvents, the separated aqueous phase containing both of the catalyst and DES can be readily recovered by evaporating water and retrieved eight times with negligible loss of catalytic performance.
- Karimi, Sabah,Masteri-Farahani, Majid,Niakan, Mahsa,Shekaari, Hemayat
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- Introduction of a Recyclable Basic Ionic Solvent with Bis-(NHC) Ligand Property and The Possibility of Immobilization on Magnetite for Ligand- and Base-Free Pd-Catalyzed Heck, Suzuki and Sonogashira Cross-Coupling Reactions in Water
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A new versatile and recyclable NHC ligand precursor has been developed with ligand, base, and solvent functionalities for the efficient Pd-catalyzed Heck, Suzuki and Sonogashira cross-coupling reactions under mild conditions. Furthermore, NHC ligand precursor was immobilized on magnetite and its catalytic activity was also evaluated towards the coupling reactions as a heterogeneous catalyst. The NHC ligand precursor was prepared with imidazolium functionalization of TCT followed by a simple ion exchange by hydroxide ions. However, the results revealed an excellent catalytic activity for the both homogeneous and heterogeneous catalytic systems. 1.52?g.cm?3 and 1194 cP was obtained for the density and viscosity of the NHC ligand precursor respectively. On the other hand, the heterogeneous type could be readily recovered from the reaction mixture and reused for several times while preserving its properties. Heterogeneous nature of the magnetic catalyst was studied by hot filtration, mercury poisoning, and three-phase tests. High to excellent yields were obtained for all entries for the both homogeneous and heterogeneous catalysts, which reflects the high consistency of the catalyst. Graphic Abstract: [Figure not available: see fulltext.]
- Min, Qingwang,Miao, Penghua,Chu, Deyu,Liu, Jinghan,Qi, Meijuan,Kazemnejadi, Milad
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p. 3030 - 3047
(2021/02/16)
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- Versatile and an efficient Sonogashira coupling reaction catalyzed with modified Pd-functionalized TMU-16 as a novel and reusable nanocatalyst
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This research paper, reports the preparation of palladium impregnated [Zn2(BDC)2(4-bpdh)]3DMF (Pd@TMU-16) with a simple liquid impregnation-reduction method as a novel and efficient catalyst with the high catalytic performance for co
- Alinezhad, Heshmatollah,Ghasemi, Shahram,Kiani, Ameneh
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- Simple and efficient diaryl alkyne synthesis method
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The embodiment of the invention discloses a simple and efficient diaryl alkyne synthesis method. The method comprises the steps of by taking arylmethylbenzotriazole and aromatic aldehyde as raw materials, carrying out addition and double-beta-elimination reaction under the action of bis (trimethylsilyl) amino salt MN (SiMe3) 2 to synthesize diaryl alkyne by a one-pot method. The raw materials and chemical reagents used in the method are easy to obtain, the reaction conditions are mild, the operation is simple, the substrate universality is good, the product yield is high, and the method is a simple and efficient diaryl alkyne synthesis method.
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Paragraph 0026; 0029-0031
(2021/04/14)
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- Aerobic Cu and amine free Sonogashira and Stille couplings of aryl bromides/chlorides with a magnetically recoverable Fe3O4@SiO2 immobilized Pd(II)-thioether containing NHC
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Two value added C–C cross coupling reactions; Sonogashira and Stille couplings were achieved at milder conditions in the catalytic presence of a magnetically recoverable heterogeneous catalyst Fe3O4@SiO2@NHC^SPh-Pd(II). The catalyst was earlier reported for Suzuki-Miyaura reaction, and as an extension of its catalytic efficiency, the Stille and Sonogashira cross coupling reactions under aerobic condition has been explored in present report. The Sonogashira coupling of aryl bromides and terminal alkynes produced an excellent yield (~96% at 0.25 mol% Pd) of the desired coupling product under copper and amines free conditions. Moreover, an excellent Stille coupling of readily available and more latent aryl chlorides and trialkylstannane was obtained (yields up to 95% at 0.25 mol% Pd) in absence of toxic fluorides additives. The broad substrate scope of the catalyst for both the coupling reactions and the magnetically recoverable feature of catalyst make this reaction highly desirable for industrial applications of present heterogeneous catalysis.
- Khandaka, Himanshu,Sharma, Kamal Nayan,Joshi, Raj Kumar
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supporting information
(2021/02/20)
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- Immobilized Pd on a NHC-functionalized metal-organic FrameworkMIL-101(Cr): An efficient heterogeneous catalyst in the heck and copper-free Sonogashira coupling reactions
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A heterogeneous palladium catalyst system based on immobilization of palladium moieties on a N-heterocyclic carbene (NHC) modified metal organic framework (MOF) was developed for the Heck and copper-free Sonogashira coupling reactions. In order to prepare this catalyst system, first, MIL-101(Cr) was functionalized with NHC moieties through a post synthetic modification (PSM) approach, and then Pd metal was stabilized on the prepered MIL-101(Cr)-NHC substrate. This material was characterized using various microscopic and spectroscopic techniques and then was used as an efficient heterogeneous Pd catalyst system in the Heck and copper-free Sonogashira reactions. Results of the heterogeneity tests showed that the Pd-NHC-MIL-101(Cr) catalyst can efficiently catalyzed these coupling reactions heterogeneously and no remarkable changes observed in the morphology and structure of MIL-101(Cr) template during the reaction progress. Also, existence of palladium nanoparticles immobilized on the MOF structure affirmed by the TEM and XPS analysis confirmed the oxidation state of Pd. A variety of alkene and alkyne derivatives were synthesized in good to excellent yields using this heterogeneous Pd catalyst system under normal conditions. More importantly Pd-NHC-MIL-101(Cr) catalyst was simply recovered from the reaction medium without remarkable decreasing in its catalytic activities after five times of reusability. The ICP analysis showed the very low Pd and Cr metals leaching, representing high stability and applicability of this catalyst in Pd coupling reactions.
- Niknam, Esmaeil,Panahi, Farhad,Khalafi-Nezhad, Ali
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supporting information
(2021/01/12)
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- Synthesis of N-Heterocyclic Carbine Silver(I) and Palladium(II) Complexes with Acylated Piperazine Linker and Catalytic Activity in Three Types of C—C Coupling Reactions
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Two bis-imidazolium salts LH2·Cl2 and LH2·(PF6)2 with acylated piperazine linker and two N-heterocyclic carbene (NHC) silver(I) and palladium(II) complexes [L2Ag2](PF6)2 (1) and [L2Pd2Cl4] (2) were prepared. The crystal structures of LH2·Cl2 and 1 were confirmed by X-ray analysis. In 1, one 26-membered macrometallocycle was generated through two silver(I) ions and two bidentate ligands L. The catalytic activity of 2 was investigated in Sonogashira, Heck-Mizoroki and Suzuki-Miyaura reactions. The results displayed that these C—C coupling reactions can be smoothly carried out under the catalysis of 2.
- Liu, Qingxiang,Zhang, Xiantao,Zhao, Zhixiang,Li, Xinying,Zhang, Wei
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supporting information
p. 605 - 613
(2021/02/01)
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- Bimetal Cooperatively Catalyzed Arylalkynylation of Alkynylsilanes
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An unprecedented Pd/Rh cooperatively catalyzed arylalkynylation of alkynylsilanes was developed to merge an alkynylidene moiety with benzosilacycle. These silaarenes possess a particular aggregation-induced emission behavior. Mechanistic investigations demonstrate that the relay trimetallic transmetalation plays a pivotal role in governing this transformation.
- Chen, Xing,Li, Mengke,Liu, Zhipeng,Yang, Can,Xie, Haisheng,Hu, Xinwei,Su, Shi-Jian,Jiang, Huanfeng,Zeng, Wei
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p. 6724 - 6728
(2021/09/08)
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- Systematic studies on the effect of fluorine atoms in fluorinated tolanes on their photophysical properties
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In this study, we synthesized a series of fluorinated and non-fluorinated tolanes, in which one or more fluorine atoms were systematically introduced into one aromatic ring of a tolane scaffold, and systematically evaluated their photophysical properties. All the tolanes with or without fluorine substituents were found to have poor photoluminescence (PL) in tetrahydrofuran (THF) solutions. On the other hand, in the crystalline state, non-fluorinated and fluorinated tolanes with one or four fluorine atoms were less emissive, whereas fluorinated tolanes with three or five fluorine atoms exhibited high PL efficiencies (φPL) up to 0.51. X-ray crystallographic analyses of the emissive fluorinated tolanes revealed that the position of the fluorine substituent played a key role in achieving a high φPL. Fluorine substituents at the ortho (2/6) and para (4) positions led to tight and rigid packing due to plural π–π stacking and/or hydrogen bonding interactions, resulting in enhanced φPL caused by the suppression of non-radiative deactivation. Additionally, fluorinated tolanes with three fluorine atoms exhibited notable aggregation-induced PL emission enhancement in THF/water mixed solvents. This demonstrates that the PL characteristics of small PL materials can be tuned depending on the usage requirements.
- Konno, Tsutomu,Morita, Masato,Yamada, Shigeyuki
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supporting information
(2021/05/25)
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- Co3O4 nanoparticles embedded in triple-shelled graphitic carbon nitride (Co3O4/TSCN): a new sustainable and high-performance hierarchical catalyst for the Pd/Cu-free Sonogashira–Hagihara cross-coupling reaction
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Inspired by the synthesis of triple-shelled periodic mesoporous organosilica hollow spheres, a straightforward and controllable approach for the preparation of Co3O4 NPs embedded in triple-shelled graphitic carbon nitride has been es
- Ghodsinia, Sara S. E.,Akhlaghinia, Batool,Jahanshahi, Roya
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p. 3217 - 3244
(2021/05/17)
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- Xantphos-coordinated palladium dithiolates: Highly efficient catalyst for decarboxylative Sonogashira reaction into corresponding alkynes
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This work reports Xantphos-coordinated palladium dithiolate complexes as catalysts for decarboxylative Sonogashira coupling reaction of phenyl propiolic acid and 2-butynoic acid with various iodoarenes. These palladium aryl dithiolate complexes were synthesized and characterized by 1H and 31P nuclear magnetic resonance (NMR) spectroscopy, melting point, and elemental analysis (CHNS). Synthetic utility for the reported protocol is explored for the effect of various functional groups on the yield of corresponding heteroaryl alkynes. The current protocol showed excellent catalytic activity towards decarboxylative alkynylation reaction with high turn-over number (TON) up to 105 and turn-over frequency (TOF) up to 104 h?1. The catalyst could be recycled up to six recycles without losing its catalytic activity. The in situ generation of palladium nanoparticles (PdNPs) was observed after the third recycle, and the amount was significant after the sixth recycle, which were confirmed and characterized by powder X-ray diffraction (XRD), scanning electron microscope (SEM), and energy-dispersive X-ray (EDX) analysis and high-resolution transmission electron microscopy (HR-TEM). The catalytic activity of the reaction is attributed to the formation of PdNPs.
- Lokolkar, Manjunath S.,Mane, Pravin A.,Dey, Sandip,Bhanage, Bhalchandra M.
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- Synthesis of Unprotected and Highly Substituted Indoles by the Ruthenium(II)-Catalyzed Reaction of Phenyl Isocyanates with Diaryl/Diheteroaryl Alkynes/Ethyl-3-phenyl Propiolates
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A one-pot transformation has been developed for the synthesis of unprotected and highly substituted indoles by an in situ installed carbamide-directed Ru(II)-catalyzed intermolecular oxidative annulation of phenyl isocyanates with diaryl/diheteroaryl alkynes/ethyl phenyl propiolates in the presence of Cu(OAc)2·H2O as an oxidant and AgSbF6 as an additive at 120 °C within 3 h.
- Kumar, Amrendra,Tadigoppula, Narender
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supporting information
p. 8 - 12
(2021/01/13)
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- Ligand-Promoted Alkynylation of Aryl Ketones: A Practical Tool for Structural Diversity in Drugs and Natural Products
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Conversion of the numerous aryl ketones into aryl electrophiles via Ar-C(O) cleavage remains a challenging yet highly desirable transformation in Sonogashira-type coupling. Herein, we report a palladium-catalyzed ligand-promoted alkynylation of unstrained aryl ketones. The protocol allows the alkynylation to be carried out in a one-pot procedure with broad functional-group tolerance and substrate scope. The potential applications of this protocol in drug discovery and chemical biology are further demonstrated by late-stage diversification of a number of pharmaceuticals and natural products. More importantly, two different biologically important fragments derived from a pharmaceutical and natural product could be connected by the consecutive alkynylation of ketones. Distinct from aryl halides in conventional Sonogashira reactions, the protocol provides a practical tool for the 1,2-bifunctionalization of aryl ketone by merging ketone-directed ortho-C-H activation with ligand-promoted ipso-Ar-C(O) alkynylation.
- Xu, Hui,Ma, Biao,Fu, Zunyun,Li, Han-Yuan,Wang, Xing,Wang, Zhen-Yu,Li, Ling-Jun,Cheng, Tai-Jin,Zheng, Mingyue,Dai, Hui-Xiong
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p. 1758 - 1764
(2021/02/09)
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- 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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- Decarbonylative Sonogashira Cross-Coupling of Carboxylic Acids
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Decarbonylative Sonogashira cross-coupling of carboxylic acids by palladium catalysis is presented. The carboxylic acid is activated in situ by the formation of a mixed anhydride and further decarbonylates using the Pd(OAc)2/Xantphos system to provide an aryl-Pd intermediate, which is intercepted by alkynes to access the traditional Pd(0)/(II) cycle using carboxylic acids as ubiquitous and orthogonal electrophilic cross-coupling partners. The methodology efficiently constructs new C(sp2)-C(sp) bonds and can be applied to the derivatization of pharmaceuticals. Mechanistic studies give support to decarbonylation preceding transmetalation in this process.
- Liu, Chengwei,Szostak, Michal
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supporting information
p. 4726 - 4730
(2021/06/28)
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- Palladium-catalyzed decarbonylative sonogashira coupling of terminal alkynes with carboxylic acids
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A direct decarbonylative Sonogashira coupling of terminal alkynes with carboxylic acids was achieved through palladium catalysis. This reaction did not use overstoichiometric oxidants, thus overcoming the homocoupling issue of terminal alkynes. Under the reaction conditions, a wide range of carboxylic acids including those bioactive ones could couple readily with various terminal alkynes, thus providing a relative general method for preparing internal alkynes.
- Chen, Tieqiao,Huang, Tianzeng,Li, Chunya,Li, Wenhui,Li, Xinyi,Li, Zhaohui,Liu, Long,Tang, Zhi,Zhang, Tao
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supporting information
p. 3304 - 3309
(2021/05/31)
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- Facile one-pot synthesis of diarylacetylenes from arylaldehydes: Via an addition-double elimination process
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A practical one-pot protocol has been developed to synthesize diarylacetylenes from arylaldehydes by treatment with 1-(arylmethyl)benzotriazoles and LiN(SiMe3)2. The reaction proceeded through imine formation, Mannich-type addition and double elimination to deliver products in up to 99% yields with broad substrate scope. In addition, gram-scale synthesis of 1-bromo-4-(phenylethynyl)benzene has been demonstrated.
- Chen, Jianyang,Zhang, Xuan,Wu, Jiajun,Wang, Rui,Lei, Chunlin,An, Yanan
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supporting information
p. 4701 - 4705
(2021/06/11)
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- Palladium-catalyzed relay C–H functionalization to construct novel hybrid-arylcyclophosphorus ligand precursors
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A new relay C–H functionalization of di([1,1′-biphenyl]-2-yl)phosphine oxide to obtain esterified and hydroxylated products with different hypervalent iodines as oxidants under palladium catalysis is disclosed. This reaction provides a more effective and concise strategy for the synthesis of novel structural hybrid-arylcyclophosphorus ligand precursors with a wide range of substrates and good functional group tolerance.
- Bai, Peng-Bo,Wang, Juan,Yang, Shang-Dong
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supporting information
(2021/11/17)
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- Anthracen-9-ylmethylene-(4-methoxyphenyl)amine: efficient promoter for silver-free palladium-catalyzed aerobic oxidative Sonogashira reactions
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An efficient protocol for the synthesis of unsymmetrical substituted diarylacetylenes by the C(sp2)–C(sp) cross-coupling reactions of substituted phenylacetylenes and electronically different arylboronic acids has been developed. Anthracen-9-ylmethylene-(4-methoxyphenyl)amine was employed as an efficient promoter in this Pd(OAc)2-catalyzed oxidative Sonogashira reaction in air in the absence of silver salt under optimized reaction conditions. The impact of reaction parameters such as solvent, base, reaction temperature and time in this silver-free aerobic oxidative Sonogashira cross-coupling reaction was also evaluated. Electron-deficient phenylacetylenes, which are sluggish coupling partners in the traditional Sonogashira reaction, underwent coupling in this protocol. The catalytic system is inexpensive, effortlessly attainable and highly flexible for functionalized phenylacetylenes and arylboronic acids. Graphic abstract: [Figure not available: see fulltext.].
- Lakshmipraba, Jagadeesan,Prabhu, Rupesh Narayana,Dhayabaran, Victor Violet
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p. 325 - 331
(2020/04/15)
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- (E)-N-(pyren-1-ylmethylene)benzenamine: efficient promoter for additive-free palladium catalyzed aerobic oxidative coupling of arylboronic acids and terminal alkynes
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Abstract: A highly productive protocol for the synthesis of internal alkynes by the carbon–carbon cross-coupling reactions of electronically different arylboronic acids with substituted phenylacetylenes was described by employing (E)-N-(pyren-1-ylmethylene)benzenamine with Pd(OAc)2. The influence of reaction parameters such as solvent, base and reaction temperature in this carbon–carbon cross-coupling reaction was also investigated. The substrate scope could be expanded to electron-poor alkynes, for which the conventional Sonogashira reaction gives poor yields. Moderate to excellent yield was obtained in the oxidative Sonogashira-type coupling reaction. Graphic abstract: [Figure not available: see fulltext.]
- Lakshmipraba, Jagadeesan,Prabhu, Rupesh Narayana,Dhayabaran, Victor Violet
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p. 3661 - 3669
(2020/04/21)
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- Shuttling Catalyst: Facilitating C?C Bond Formation via Cross-Couplings with a Thermoresponsive Polymeric Ligand
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A poly(ethylene glycol) (PEG) linked ortho-MeO-phenyldicyclohexylphosphine (MeO-WePhos) ligand has been synthesized to promote Pd-catalyzed carbon-carbon bond formation by cross-couplings including Sonogashira, Heck, Hiyama and Stille reactions, providing corresponding (hetero)aryl substituted alkynes, alkenes and bi(hetero)aryls in good to excellent isolated yields with low Pd loadings. Facilitated by the lower critical solution temperature behaviour of the polymeric monophosphine ligand, the metal-complex could rapidly shuttle between organic and water phases as regulated by temperature, enabling highly efficient catalyst recycling via a simple phase separation. The chemical structure of ligand was determined by matrix-assisted laser desorption/ionization-time of flight mass spectrometry, nuclear magnetic resonance spectrometry and size-exclusion chromatography measurements. Notably, as demonstrated by the inductively coupled plasma-atomic emission spectrometry measurement, 98% Pd was kept in the water phase after 6 cycles of catalyst recycling experiments. Given the profound impact of transition-metal-catalyzed covalent bond formation and the increasing demand of sustainable chemistry, this work provides an alternative method to conduct cross-couplings with a polymeric shuttling catalyst.
- Wang, Erfei,Zhang, Jiawei,Zhong, Zhuoran,Chen, Kaixuan,Chen, Mao
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p. 419 - 423
(2020/01/08)
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- Palladium(II) phthalocyanines efficiently promote phosphine-free Sonogashira cross-coupling reaction at room temperature
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Herein we report that exceptionally simple and inexpensive Pd(II) complexes of phthalocyanines efficiently catalyze direct formation of diphenylacetylenes at ambient conditions with low loading of catalyst (0.5 mol%). Results of this study demonstrate that terminal alkynes reacted mildly with p-substituted aryl bromides at room temperature under Pd and Cu-cocatalysis to give the corresponding phenylacetylenes in yields up to 98%. Also we have examined this catalyst in Sonogashira cross-coupling with aryl chlorides and it was very effective and this reaction at room temperature that there is no examples in recent articles. This protocol represents the first use of palladium phthalocyanine as homogeneous catalyst in the Pd/Cu-promoted Sonogashira reaction. The palladium(II) phthalocyanine complex is significantly more active in Sonogashira cross-coupling between aryl halides and terminal alkynes as compared with traditional catalysts because of absence of palladium black formation through agglomeration of metal particles and deactivation of catalyst.
- Platonova, Yana B.,Tomilova, Larisa G.,Volov, Alexander N.
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p. 224 - 228
(2020/09/17)
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- A new approach to large scale production of dimethyl sulfone: A promising and strong recyclable solvent for ligand-free Cu-catalyzed C-C cross-coupling reactions
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Dimethyl sulfone (DMSN) was easily prepared through efficient oxidation of dimethyl sulfoxide (DMSO) and used as a strong and green solvent for organic reactions. A mixture of HNO3/NaOCl was used as an oxidizing agent for efficient oxidation of DMSO to DMSN. The effect of DMSN was evaluated for copper-catalyzed coupling reactions. It is worth noting that DMSN could play the role of a ligand for copper ions. A general survey was accomplished for various types of C-C cross-coupling reactions catalyzed by CuI in DMSN in the absence of any ligand. Moderate to good yields were achieved for Sonogashira, Heck, and Suzuki cross-coupling reactions. Finally, DMSN was recovered and reused for several consecutive runs without any loss of its activity.
- Cheng, Shen,Wei, Wei,Zhang, Xingyu,Yu, Hewei,Huang, Mingming,Kazemnejadi, Milad
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p. 2069 - 2076
(2020/04/07)
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- Ni(acac)2/2,6-bis(diphenylphosphino)pyridine/CuI: A highly efficient palladium-free homogeneous catalyst for the Sonogashira cross-coupling reaction
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A highly efficient palladium-free homogeneous catalyst involving Ni(acac)2/2,6-bis(diphenylphosphino)pyridine ((Ph2P)2py)/CuI components was used for the Sonogashira cross-coupling reaction. The Sonogashira reaction was in
- Ataei, Ali,Daryanavard, Marzieh,Joshaghani, Mohammad,Rafiee, Ezzat
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- Sustainable Ligand-Free Heterogeneous Palladium-Catalyzed Sonogashira Cross-Coupling Reaction in Deep Eutectic Solvents
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The commercially available and cheap Pd/C was found to promote Sonogashira couplings in the environmentally friendly choline chloride/glycerol eutectic mixture in the absence of external ligands. Under heterogeneous conditions, (hetero)aryl iodides were successfully coupled with both aromatic and aliphatic alkynes in yields ranging from 50 to 99 % within 3 h at 60 °C. The aforementioned catalytic system proved to be effective also towards electron-rich iodides, which are notoriously known to be poorly reactive in Pd-catalyzed Sonogashira coupling reactions. The eutectic mixture and the catalyst could easily and successfully be recycled up to four times with an E-factor as low as 24.4.
- Messa, Francesco,Dilauro, Giuseppe,Perna, Filippo M.,Vitale, Paola,Capriati, Vito,Salomone, Antonio
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p. 1979 - 1984
(2020/02/20)
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- Fast heck-cassar-sonogashira (hcs) reactions in green solvents
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The replacement of toxic solvents with greener alternatives in Heck-Cassar-Sonogashira (HCS) cross-couplings was investigated. The fine-tuning of the HCS protocol allowed to achieve complete conversions and high speed under mild conditions. N-Hydroxyethylpyrrolidone (HEP) gave the best results. Moreover, the methodology was successfully applied to the synthesis of an intermediate of the anticancer drug Erlotinib, demonstrating the versatility of the new green protocol.
- Cabri, W.,Corbisiero, D.,Daka, A.,Fantoni, T.,Ferrazzano, L.,Martelli, G.,Ricci, A.,Tolomelli, A.,Viola, A.
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supporting information
p. 3969 - 3973
(2020/06/08)
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- Ruthenium-Catalyzed E-Selective Alkyne Semihydrogenation with Alcohols as Hydrogen Donors
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Selective direct ruthenium-catalyzed semihydrogenation of diaryl alkynes to the corresponding E-alkenes has been achieved using alcohols as the hydrogen source. The method employs a simple ruthenium catalyst, does not require external ligands, and affords the desired products in > 99% NMR yield in most cases (up to 93% isolated yield). Best results were obtained using benzyl alcohol as the hydrogen donor, although biorenewable alcohols such as furfuryl alcohol could also be applied. In addition, tandem semihydrogenation-alkylation reactions were demonstrated, with potential applications in the synthesis of resveratrol derivatives.
- Ekebergh, Andreas,Begon, Romain,Kann, Nina
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p. 2966 - 2975
(2020/03/04)
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- Palladium(II) complexes containing sterically bulky O, N donor ligands: Synthesis, characterization and catalytic activity in the Suzuki-Miyaura and Sonogashira coupling reactions
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A new class of palladium(II)1-(arylazo)naphtholate complexes of the type [Pd(L1-4)2] containing sterically bulky O, N donor functionalized arylazo ligands has been synthesized. These palladium(II) complexes were characterized by elemental analysis and spectral (FT-IR, UV–Vis, 1H NMR and 13C NMR) studies. The molecular structure of the Palladium(II) complexes [Pd(L1)2] and [Pd(L2)2] were established by X-ray crystallography. These complexes were found to efficiently catalyze the Suzuki-Miyaura coupling of arylboronic acids and aryl halides, and the Sonogashira reaction of aryl halides and phenylacetylene in DMF and i-PrOH media to afford the corresponding C–C coupling products in high yields.
- Nandhini, Raja,Vijayan, Paranthaman,Venkatachalam, Galmari
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- Palladium anchored on guanidine-terminated magnetic dendrimer (G3-Gu-Pd): An efficient nano-sized catalyst for phosphorous-free Mizoroki-Heck and copper-free Sonogashira couplings in water
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In this research, a novel type of Fe3O4&at;silica-supported dendrimer capped by guanidine groups for immobilization of palladium was reported. This novel nano-sized catalyst was characterized by FTIR, TGA, XRD, FESEM, EDX, VSM, XPS and HRTEM methods. Enhanced catalytic activity of the prepared catalyst in Mizoroki-Heck and copper-free Sonogashira coupling reactions were evaluated in water as a green solvent. The influence of the various reaction parameters such as catalyst dosage, time and temperature on two mentioned C–C coupling reactions were studied. Results showed that the catalyst could be easily recovered by simple separation by an external magnet and reused for five cycles of recovery without considerable losing of its activity.
- Khalafi-Nezhad, Ali,Moaddeli, Ali,Niknam, Esmaeil
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- Gold(I)-Catalyzed Cross-Coupling Reactions of Arenediazonium Salts with Alkynoic Acids
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Abstract: The reaction of simple alkynoate salts with isolated arenediazonium tetrafluoroborate salts that had been pre-conditioned with the gold(I) catalyst AuCl(Me2S) led to the formation of cross-coupled products via a decarboxylative Sonogashira reaction process in modest yield and under mild conditions. The major by-product is a defunctionalized aryl moiety stemming from the diazonium salt, which competitively forms via hydrodediazonation. Good functional group tolerance and reaction site selectivity were attained in this limited investigation.
- Abrams, J. N.,Chi, B. K.
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p. 1236 - 1244
(2020/09/17)
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- Ligand-Free and Recyclable Palladium(II) Acetate Catalyzes the Decarboxylative Cross-Coupling of Alkynyl Carboxylic Acids with Arylboronic Acids in Aqueous PEG-400
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A novel and ligand-free method was developed for the decarboxylative cross-coupling of alkynylcarboxylic acids with arylboronic acids. By using an environmentally friendly H 2 O-poly(ethylene glycol) (PEG-400) system as the reaction medium, a series of internal alkynes were synthesized in good yields and with remarkable selectivity. The Pd(OAc) 2-H 2 O-PEG-400 catalytic system could be used for up to three cycles without any loss of activity, demonstrating the robustness of the approach.
- Chen, Ying,Hu, Min,Tang, Bo-Xiao,Wang, Yi-Hua,Wen, Qi-Qi,Xie, Bao-Xing,Yang, Shi-Yao,Zhong, Hai-Qing,Zou, Hong
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supporting information
p. 793 - 796
(2020/05/19)
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- Synthesis of a Cellulosic Pd(salen)-Type Catalytic Complex as a Green and Recyclable Catalyst for Cross-Coupling Reactions
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Abstract: A green recyclable cellulose-supported Pd(salen)-type catalyst was synthesized through sequential three steps: chlorination with thionyl chloride, modification by ethylenediamine, and the formation of Schiff base with salicylaldehyde to immobilize palladium chloride through multiple binding sites. This novel heterogeneous cellulosic Pd(salen)-type catalytic complex was fully characterized by FT-IR, SEM, TEM, XPS, ICP-AES and TG. The traditional cross-coupling chemistry, such as Suzuki, Heck, Sonogashira, Buchwald–Hartwig amination and etherification, was then investigated in the presence of the above cellulose-palladium nanoparticle. Studies have shown that the synthesized catalyst shows high activity and efficiency for all types of transformations, providing the corresponding carbon–carbon or carbon–heteroatom coupling products in a general and mild manner. Furthermore, the catalyst demonstrates high to excellent yields and is easily recycled by simple filtration for up to twelve cycles without any significant loss of catalytic activity. Graphic Abstract: [Figure not available: see fulltext.]
- Sun, Peng,Yang, Jiaojiao,Chen, Chunxia,Xie, Kaijun,Peng, Jinsong
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p. 2900 - 2910
(2020/03/31)
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- Green synthesis of graphene oxide (GO)-anchored Pd/Cu bimetallic nanoparticles using: Ocimum sanctum as bio-reductant: An efficient heterogeneous catalyst for the Sonogashira cross-coupling reaction
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To explore the synergism between two metal centers we have synthesized graphene oxide (GO) supported Pd/Cu?GO, Pd?GO and Cu?GO nanoparticles through bio-reduction of Pd(NO3)2 and CuSO4·5H2O using Tulsi (Ocimum sanctum) leaf extract as the reducing and stabilizing agent. The graphene oxide (GO) was obtained by oxidation of graphite following a simplified Hummer's method. The as-prepared nanomaterials have been extensively characterized by FTIR, powder X-ray diffraction (PXRD), HRTEM, TEM-EDS, XPS, ICP-AES and BET surface area measurement techniques. The morphological study of Pd/Cu?GO revealed that crystalline bimetallic alloy type particles were dispersed on the GO layer. The activity of Pd?GO, Cu?GO and Pd/Cu?GO as catalysts for the Sonogashira cross-coupling reaction have been investigated and it was found that the Pd/Cu?GO nanostructure showed highly superior catalytic activity over its monometallic counterparts, substantiating the cooperative influence of the two metals. The inter-atom Pd/Cu transmetalation between surfaces was thought to be responsible for its synergistic activity. The catalyst showed higher selectivity towards coupling of aryl iodides with both aliphatic and aryl alkynes resulting in moderate to excellent isolated yield of the desired products (45-99%). The products have been characterized by GC-MS and 1H-NMR spectroscopic techniques and compared with authentic samples. The Pd/Cu?GO catalyst could be easily isolated from the reaction products and reused for up to at least ten successive runs effectively.
- Borah, Geetika,Gogoi, Pradip K.,Hussain, Farhaz Liaquat,Mech, Swapna Devi,Pahari, Pallab,Sultana, Samim
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p. 23108 - 23120
(2020/07/03)
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- Ultrafine Pd nanoparticles loaded benzothiazole-linked covalent organic framework for efficient photocatalytic C-C cross-coupling reactions
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We proposed a strategy that a benzothiazole-linked covalent organic framework (TTT-COF) was used as a substrate to prepare metal composite photocatalyst Pd NPs?TTT-COF. Firstly, benzothiazole linked TTT-COF exhibited superior chemical stability and photoresponse. Moreover, a finer particle size (2.01 nm) and more uniform distribution of Pd NPs were observed in Pd NPs?TTT-COF owing to the binding interaction between Pd NPs and S in benzothiazole groups. Pd NPs?TTT-COF exhibited superior efficiency and reusability in photocatalytic C-C cross-coupling reactions. Mechanism study suggested that photogenerated electrons and holes on TTT-COF played important roles in these reactions. This journal is
- Cai, Yaqi,Niu, Hongyun,Xu, Lin,Yang, Yongliang,Zhang, Hui,Zhao, Weijia
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p. 29402 - 29407
(2020/10/02)
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- Diorganyl tellurides as substrates in Sonogashira coupling reactions under mild conditions
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A new method of Sonogashira coupling reactions between diorganyl tellurides and terminal alkynes is reported. The coupling reactions are performed using Pd(dppf)Cl2 as a catalyst, CuI as a co-catalyst in the presence of K2CO3 in DMSO. The reactions are carried out at room temperature and completed within 2 h when phenyl acetylene is used as a terminal alkyne. For aliphatic terminal alkynes, such as 1-hexyne and 1-octyne, an elevated temperature and longer reaction time are needed for the completion of the reactions. This process results in good yields of Sonogashira coupling products which is applicable for diaryl, divinyl and dialkynyl tellurides but not applicable for dialkyl tellurides.
- Zhang, Shaozhong,Ailneni, Chandra,Al-Mohammed Baqer, Osamah,Lolla, Mahati,Mannava, Bala Bharathi,Siraswal, Parvinlal,Yen, Changchi,Jin, Jin
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supporting information
p. 217 - 225
(2019/11/22)
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- A series of (NHC)Pd(N?O)(OAc) complexes: synthesis, characterization and catalytic activities towards desulfinative Sonogashira coupling of arylsulfonyl hydrazides with arylalkynes
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A series of well-defined N-heterocyclic carbene palladium (II) complexes with general formula (NHC)Pd(N?O)(OAc) were prepared through reaction of Pd (NHC)(OAc)2(H2O) with 1-methyl-1H-pyrazole-3-carboxylic acid or 1-methyl-1H-indazole-3-carboxylic acid in the presence of K2CO3. These complexes were then used for desulfinative Sonogashira coupling of arylsulfonyl hydrazides with terminal alkynes. With low catalyst loading, all synthesized palladium compounds exhibited moderate to high catalytic activities for the reactions.
- Lu, Jian-Zhong,Wang, Tian,Yang, Jin,Zhao, Ya-Yu,Zhu, Guang-Hao
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- Palladium/copper-cocatalyzed decarbonylative alkynylation of acyl fluorides with alkynylsilanes: Synthesis of unsymmetrical diarylethynes
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Palladium/copper-cocatalyzed decarbonylative alkynylation of acyl fluorides with alkynylsilanes is described. This reaction not only effectively inhibits the formation of undesired homocoupled products by avoiding the addition of a base, but also exhibits a wide substrate scope to provide a general access to diverse unsymmetrical diarylethynes.
- Chen, Qiang,Fu, Liyan,Nishihara, Yasushi
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supporting information
p. 7977 - 7980
(2020/09/09)
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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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- Bis-salophen palladium complex immobilized on Fe3O4@SiO2 nanoparticles as a highly active and durable phosphine-free catalyst for Heck and copper-free Sonogashira coupling reactions
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New Fe3O4@SiO2 core-shell superparamagnetic nanoparticles functionalized by a bis-salophen Schiff base Pd complex were synthesized and employed as an efficient magnetic nanocatalyst in the Heck and Sonogashira cross coupling reactions. The synthesized nanostructures were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), dynamic light scattering (DLS), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), elemental analysis (CHN), cyclic voltammetry (CV), Brunauer-Emmett-Teller analysis (BET), and UV-vis spectroscopy. The morphology and size of the nanoparticles were investigated by FE-SEM and TEM analyses. Furthermore, the magnetic properties of the catalyst were investigated by VSM analysis. The loading content and leaching amounts of palladium on the catalyst were measured by inductively coupled plasma (ICP) analysis. Also, the thermal behavior of this magnetic heterogeneous catalyst was studied using a TGA instrument. This heterogeneous catalytic system showed a good performance in the coupling of aryl halides with alkynes (Sonogashira reaction) as well as aryl halides with alkene derivatives (Heck reaction). High to excellent yields were achieved for these C-C coupling reactions. The catalyst can be simply separated from the reaction media by an external magnet and reused for eight consecutive runs without any significant loss of activity. Finally, the kinetics of the reactions were studied in this work.
- Sardarian, Ali Reza,Kazemnejadi, Milad,Esmaeilpour, Mohsen
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p. 3132 - 3145
(2019/03/06)
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- Green, cost-effective and efficient procedure for Heck and Sonogashira coupling reactions using palladium nanoparticles supported on functionalized Fe3O4@SiO2 by polyvinyl alcohol as a highly active, durable and reusable catalyst
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A novel heterogenized organometallic catalyst was synthesized by coordinating palladium with polyvinyl alcohol-functionalized Fe3O4@SiO2 nanospheres. This novel catalyst was characterized using Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscope, field emission scanning electron microscope, dynamic light scattering, UV–vis spectroscopy, X-ray photoelectron spectroscopy, energy dispersive X-ray analysis, thermogravimetric analysis and inductively coupled plasma analysis. The prepared palladium nanoparticles supported on polyvinyl alcohol functionalized Fe3O4@SiO2 nanoparticles were successfully applied as a magnetically recyclable catalyst in Heck and Sonogashira coupling reactions in water. They showed remarkable activity toward aryl halides (I, Br, Cl) using very low palladium loading in excellent yields and demonstrated high TONs (mmol of product per mmol of catalyst). Also, the catalyst could be magnetically separated and reused seven times without any appreciable loss of catalytic activity.
- Sardarian, Ali Reza,Eslahi, Hassan,Esmaeilpour, Mohsen
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- Functionalized graphene oxide anchored to Ni complex as an effective recyclable heterogeneous catalyst for Sonogashira coupling reactions
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The Sonogashira cross coupling reaction is an applied method for preparation of diarylethyne compounds from readily available aryl halide derivatives and phenyl acetylene. The coupling reaction using nickel complex of N,N′-Bis(2-hydroxyethyl)ethylenediami
- Naeimi, Hossein,Kiani, Fatemeh
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- A palladium catalyzed aryl alkyne preparation method
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The invention discloses a palladium catalyzed aryl alkyne of the preparation method, comprises the following steps: in the catalyst, under the action of the ligand and alkali, substituted with aryl sulfonyl chloride alkynoic occurs in the organic solvent escapes suosuo the coupling reaction, after the reaction is finished after treatment to obtain the aryl alkyne. Used in the preparation method of the cheap raw material, the reaction and simple post treatment operation, at the same time, the reaction less side reaction, high yield of the product.
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Paragraph 0037; 0038; 0039
(2019/05/21)
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- Rate Enhancement in CAN-Promoted Pd(PPh3)2Cl2-Catalyzed Oxidative Cyclization: Synthesis of 2-Ketofuran-4-carboxylate Esters
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Stoichiometric ceric ammonium nitrate (CAN) and a catalytic amount of Pd(PPh3)2Cl2 (5 mol %) can rapidly produce multisubstituted 2-ketofuran-4-carboxylate esters from 2-propargylic 1,3-ketoesters via oxidative O-cyclization reaction. Pd(PPh3)2Cl2 was found to be the crucial catalyst as its inclusion greatly enhanced the rate of the reaction and cleanly afforded the products within minutes. Over 30 substrates were successfully converted to the desired compounds in mostly moderate to good yields.
- Ruengsangtongkul, Sureeporn,Chaisan, Nattawadee,Thongsornkleeb, Charnsak,Tummatorn, Jumreang,Ruchirawat, Somsak
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supporting information
p. 2514 - 2517
(2019/04/30)
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- Conjugated mesoporous polyazobenzene–Pd(II) composite: A potential catalyst for visible-light-induced Sonogashira coupling
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We herein report the direct harnessing of visible light energy by a novel semiconducting azobenzene-based colloidal porous organic polymer, B3-Azo4 amenable to post-synthetic Pd(II)-complexation for photo-induced Sonogashira coupling using polymer → metal energy transfer process. Completely mesoporous nano-sized particles of the obtained organic network manifested excellent Pd(II) coordinating ability and afforded desired catalytic products at room temperature under aerobic condition in aqueous medium. The protocol remained valid for different aromatic and aliphatic substrates as well. A possible reaction mechanism for photo-mediated Sonogashira coupling catalyzed by Pd-B3-Azo4 is also proposed.
- Nath, Ipsita,Chakraborty, Jeet,Khan, Anish,Arshad, Muhammad N.,Azum, Naved,Rab, Malik A.,Asiri, Abdullah M.,Alamry, Khalid A.,Verpoort, Francis
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p. 183 - 189
(2019/08/07)
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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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- Aqueous phase catalyzed Sonogashira cross-coupling reaction and separation and purification method
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The invention discloses an aqueous phase catalyzed Sonogashira cross-coupling reaction and separation and purification method. The method includes adopting molecular sieve-supported palladium as a catalyst, water as a solvent and quaternary ammonium base
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Paragraph 0016-0019
(2019/02/10)
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- Porous organic polymer with: In situ generated palladium nanoparticles as a phase-transfer catalyst for Sonogashira cross-coupling reaction in water
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A new Pd nanoparticle loaded and imidazolium-ionic liquid decorated organic polymer of Pd@PTC-POP was readily fabricated via a Pd(PPh3)4 catalysed in situ one-pot Suzuki cross-coupling reaction between imidazolium attached dibromoben
- Dong, Ying,Chen, Yun-Qi,Jv, Jing-Jing,Li, Yue,Li, Wen-Han,Dong, Yu-Bin
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p. 21671 - 21678
(2019/07/30)
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- Functionalization of multi-walled carbon nanotubes by the baclofen drug to immobilize palladium nanoparticles and catalyze Sonogashira coupling reactions
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The baclofen-MWCNTs-Pd nanocatalyst was synthesized through covalent grafting of baclofen molecules onto surface-modified carbon nanotubes and immobilizing Pd nanoparticles by the baclofen ligands. The chemical structure of the produced nanocatalyst was s
- Nazari, Pooneh,Hekmati, Malak
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- Synthesis and characterization of γ-Fe2O3@SiO2-(CH2)3-PDTC-Pd magnetic nanoparticles: A new and highly active catalyst for the Heck/Sonogashira coupling reactions
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In this research, the synthesis and characterization of a novel catalyst is reported based on the preparation of the Pd complex of (pyridin-2-ylmethyl)dithiocarbamate (PDTC) supported on γ-Fe2O3@SiO2 magnetic nanoparticles (γ-Fe2O3@SiO2-(CH2)3-PDTC-Pd). The catalyst is characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, inductively coupled plasma analysis, X-ray powder diffraction, X-ray photoelectron spectroscopy, and vibrating-sample magnetometer measurements. The catalytic performance of γ-Fe2O3@SiO2-(CH2)3-PDTC-Pd was evaluated in the Heck/Sonogashira coupling reactions of various aryl halides with various alkenes/phenylacetylene in water. The synthesized nanocatalyst showed a high catalytic activity even in very small amounts (5 mg, less than 0.1 mol%), was easily separated using magnetic decantation and was reused for ten cycles without any appreciable loss of its reactivity.
- Tashrifi, Zahra,Bahadorikhalili, Saeed,Lijan, Hossein,Ansari, Samira,Hamedifar, Haleh,Mahdavi, Mohammad
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p. 8930 - 8938
(2019/06/17)
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