- 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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- 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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- Decorated palladium nanoparticles on mesoporous organosilicate as an efficient catalyst for Sonogashira coupling reaction
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Abstract: Reforming mesoporous silica was provided by the reaction of SBA‐15 with (3-aminopropyl)triethoxysilane, the product of which was treated with furfural to give SBA-propyl-imine-furan. In the next step, palladium chloride was attached to the funct
- Mohajer, Fatemeh,Mohammadi Ziarani, Ghodsi,Badiei, Alireza
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p. 589 - 601
(2020/09/17)
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- An unsymmetrical Schiff-base derived recyclable Pd-catalyst for Suzuki–Miyaura and Sonogashira reactions in aqueous media
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Abstract: A water-soluble palladium (II) complex containing an unsymmetrical Schiff-base ligand was synthesized and applied as catalyst Suzuki–Miyaura and Sonogashira cross-coupling reactions in aqueous media. Notably, moderate to excellent yields of biaryls were obtained in Suzuki reaction with usually less reactive aryl and heteroaryl chlorides under relatively mild condition. Moderate-to-high yields of aryl-alkynes were also obtained in Sonogashira reactions using aryl bromides. Apart from hydrophilic nature, the accomplishment of reactions in water, high recyclability, broad functional group tolerance, etc., are other advantages of the system. Graphic abstract: [Figure not available: see fulltext.]
- Das, Pankaj,Gogoi, Achinta,Puzari, Amlan
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- A Waste-Minimized Approach to Cassar-Heck Reaction Based on POLITAG-Pd0 Heterogeneous Catalyst and Recoverable Acetonitrile Azeotrope
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Three different Pd0-based heterogeneous catalysts were developed and tested in the Cassar–Heck reaction (i. e., copper-free Sonogashira reaction) aiming at the definition of a waste minimized protocol. The cross-linked polymeric supports used in this investigation were designed to be adequate for different reaction media and were decorated with different pincer-type ionic ligands having the role of stabilizing the formation and dimension of palladium nanoparticles. Among the ionic tags tested, bis-imidazolium showed the best performances in terms of efficiency and durability of the metal catalytic system. Eventually, aqueous acetonitrile azeotrope was selected as the reaction medium as it allowed the best catalytic efficiency combined with easy recovery and reuse. Finally, the synergy between the selected catalyst and reaction medium allowed to obtain highly satisfactory isolated yields of a variety of substrates while using a low amount of metal catalyst. The high performance of the designed POLymeric Ionic TAG (POLITAG)-Pd0, along with its good selectivity achieved in a copper-free process, also led to a simplified purification procedure allowing the minimization of the waste generated as also proven by the very low E-factor values (1.4–5) associated.
- Valentini, Federica,Ferlin, Francesco,Tomarelli, Elena,Mahmoudi, Hamed,Bagherzadeh, Mojtaba,Calamante, Massimo,Vaccaro, Luigi
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p. 3359 - 3366
(2021/07/28)
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- Glycosyl Triazole Ligand for Temperature-Dependent Competitive Reactions of Cu-Catalyzed Sonogashira Coupling and Glaser Coupling
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Glycosyl triazoles have been introduced as efficient ligands for the Cu-catalyzed Sonogashira reaction to overcome the challenges of sideways homocoupling reactions in Cu catalysis in this reaction. The atmospheric oxygen in a sealed tube did not affect t
- Mishra, Nidhi,Singh, Sumit K.,Singh, Anoop S.,Agrahari, Anand K.,Tiwari, Vinod K.
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p. 17884 - 17895
(2021/12/17)
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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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- Incorporation of Palladium Catalyst Inside Cross-Linked Chitosan Hybrid Nanofibers for the Sonogashira Reaction
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Abstract: Nanofibers are attractive supporting matrices for catalytically active metallic catalysts. Herein, palladium species were successfully incorporated into the modified chitosan/poly(ethylene oxide)/maleic acid nanofibers by electrospinning. Then,
- Zhong, S.
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p. 480 - 485
(2020/07/03)
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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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- 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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- Cu2O Nanocrystals-Catalyzed Photoredox Sonogashira Coupling of Terminal Alkynes and Arylhalides Enhanced by CO2
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Herein the first visible-light-activated Sonogashira C?C coupling reaction at room temperature catalyzed by single-metal heterogeneous Cu2O truncated nanocubes (Cu2O TNCs) was developed. A wide variety of aryl halides and terminal alkynes worked well in this recyclable heterogeneous photochemical process to form the corresponding Sonogashira C?C coupling products in good yields. Mechanistic control studies indicated that CO2 enhances the formation of light-absorbing heterogeneous surface-bound CuI-phenylacetylide (λmax=472 nm), which further undergoes single-electron transfer with aryl iodides/bromides to enable Sonogashira Csp2 ?Csp bond formation. In contrast to literature-reported bimetallic TiO2-containing nanoparticles as photocatalyst, this work avoided the need of cocatalysis by TiO2. Single-metal CuI in Cu2O TNCs was solely responsible for the observed Csp2 ?Csp coupling reactions under CO2 atmosphere.
- Shanmugam, Munusamy,Sagadevan, Arunachalam,Charpe, Vaibhav Pramod,Pampana, V. Kishore Kumar,Hwang, Kuo Chu
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p. 287 - 292
(2019/11/05)
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- One-Pot Conversion of Aldehydes and Aryl Halides to Disubstituted Alkynes via Tandem Seyferth-Gilbert Homologation/Copper-Free Sonogashira Coupling
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A practically convenient protocol has been developed to convert a mixture of an aldehyde, aryl halide, and the Bestmann-Ohira reagent into disubstituted acetylene via a successive addition of base (Cs2CO3) and a Pd(II) catalyst, allowing sufficient time after addition of each of these reagents for the tandem processes (Seyferth-Gilbert homologation and Sonogashira coupling) to occur. Notably, for the latter reaction, no copper catalyst was required.
- Sapegin, Alexander,Krasavin, Mikhail
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p. 8788 - 8795
(2019/07/03)
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- Synthesis and characterization of a new poly(N–heterocyclic carbene Cu complex) immobilized on nano–silica, (CuII–NHCs)n@nSiO2, and its application as an efficient and reusable catalyst in the synthesis of benzimidazoles,
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The present study describes the synthesis and characterization of a new poly(N–heterocyclic carbene Cu complex) immobilized on nano silica, (CuII–NHCs)n@nSiO2. The (CuII–NHCs)n@nSiO2 dendri
- Khajehzadeh, Mostafa,Moghadam, Majid,Jamehbozorgi, Saeed
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p. 173 - 189
(2018/10/21)
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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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- 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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- 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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- Agro waste derived nanosilica supported Pd(ll) complex: A protocol for copper free Sonogashira reaction in water
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A palladium (II) complex immobilized onto nanosilica(Pd-imine@nanoSiO2) has been developed and evaluated as a highly efficient, retrievable catalyst for carbon-carbon triple bond activation reactions between aryl halides and terminal alkynes. Nanosilica has been derived from rice husk by simple and eco-compatible methodology. The catalyst has been extensively characterized by techniques such as FT-IR, UV–vis, powder XRD, XPS, SEM-EDX, thermogravimetric analysis, BET surface area measurement. The catalyst can be reused for five consecutive runs without compromising much with the activity. Easy preparation, its long shelf life, air-stability, wide substrate scope, ‘in water’ reactions, easy separability and good recyclability make it an ideal system for Sonogashira cross-coupling reaction. Moreover, various alkyne substrates were efficiently cross-coupled with a broad range of aryl iodides and aryl bromides to afford diaryl alkynes, providing improved yields with low catalyst loading in water. This protocol is also suitable for aliphatic alkynes.
- Gogoi, Rajjyoti,Saikia, Rituraj,Borah, Geetika
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- Recyclable Pd/CuFe2O4 nanowires: A highly active catalyst for C-C couplings and synthesis of benzofuran derivatives
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Pd/CuFe2O4 nanowire-catalyzed cross coupling transformations are described. Notably, these reactions showed excellent functional group tolerance. Further, the protocol is applied to a one-pot synthesis of benzofurans via a Sonogashira coupling and intramolecular etherification sequence. The catalyst was reused and found to maintain its activity and stability.
- Lakshminarayana, Bhairi,Chakraborty, Jhonti,Satyanarayana,Subrahmanyam, Ch.
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p. 21030 - 21039
(2018/06/13)
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- A novel and highly efficient polyaniline-functionalized multiwall carbon nanotube-supported cu(I) complex for Sonogashira coupling reactions of aryl halides with phenylacetylene
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A polyaniline-functionalized multiwall carbon nanotube-supported Cu(I) complex was developed as an efficient catalyst for the Sonogashira reactions of aryl halides with phenylacetylene in the presence of potassium hydroxide in dimethylformamide at 135?°C under nitrogen atmosphere. The corresponding products were generated in good to excellent yields using this catalytic system. Moreover, the multiwall carbon nanotube-supported Cu(I) catalyst was simply recycled and reused for six consecutive runs.
- Hajipour, Abdol R.,Jajarmi, Saeideh
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- Sonogashira-type cross-coupling reactions catalyzed by copper complexes of pincer N-heterocyclic carbenes
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Copper complexes of N-heterocyclic carbenes (NHC) have recently received great attention in catalysis, however, the application scope has been limited to neutral complexes bearing monodentate ligands. Herein, we report the synthesis and full characterization of a cationic Cu-pincer bis(NHC) complex with bulky tert-butyl wingtips that serves as catalyst for the coupling of aryl iodides and phenylacetylene, alongside its analogs with small alkyl substituents. Unlike other copper catalysts that require an inert atmosphere to prevent alkyne homocoupling, a competing side reaction to Sonogashira reaction, the Cu-pincer bis(NHC) complexes provide good to excellent cross-coupling yields in air. Interestingly, the reaction under argon affords substantially reduced cross-coupling, indicative of the oxygen involvement and its facilitating effect in the mechanism. In our controlled studies, the air-assisted cross-coupling reaction came to a complete stop when using a radical trap, suggesting the presence of a radical in the mechanism. Examining the reaction of Cu-pincer bis(NHC) complexes with oxygen via UV–vis spectroscopy reveals a dark green chromophore formation at ?40 °C with strong absorbance (ε > 400 M?1cm?1) at 460 nm and 500 nm, likely due to a high-valent copper-oxygen adduct.
- Domyati, Doaa,Latifi, Reza,Tahsini, Laleh
-
supporting information
p. 98 - 105
(2018/03/06)
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- Pd(NHC)PEPPSI-diazonium salts: An efficient blend for the decarboxylative Sonogashira cross coupling reaction
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An efficient N-heterocyclic carbene based Pd complex is described for the de-carboxylative Sonogashira coupling reaction with diazonium salts under ligand and co-catalyst free conditions. Pd(NHC)PEPPSI not only offers an air and moisture stable pre-cataly
- Bhojane, Jeevan Manohar,Jadhav, Vilas Gangadhar,Nagarkar, Jayashree Milind
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supporting information
p. 6775 - 6780
(2017/07/17)
-
- Palladium-catalyzed deacetonative coupling of aryl propargylic alcohols with aryl chlorides in water
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A highly efficient and green process for palladium-catalyzed deacetonative coupling of aryl propargylic alcohols with aryl chlorides has been developed. The reaction occurs smoothly in neat water with 2 mol% PdCl2 as catalyst, and various synthetically useful functional groups, including ether, aldehyde, ketone, and heterocyclics, are well tolerated. Moreover, the reaction could proceed through a consecutive Sonogashira/deacetonative process using 2-methyl-3-butyn-2-ol and aryl chlorides as coupling partners, affording the symmetric alkynes in good yields.
- Chang, Feng,Liu, Yanping
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supporting information
p. 961 - 967
(2017/05/04)
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- Ligand- and copper-free Sonogashira and Heck couplings of (Het)aryl chlorides and bromides catalyzed by palladium nanoparticles supported on in situ generated Al(OH)3
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The ligand- and copper-free Sonogashira reaction of (Het)aryl halides (Br and Cl) with various terminal alkynes and the Heck coupling of (Het)aryl halides (Br and Cl) with a series of olefins, catalyzed by palladium nanoparticles supported on newly generated Al(OH)3, were developed. The catalyst can be readily recovered and reused 6 times without significant loss of activity and palladium leaching.
- Li, Xing,Gong, Xiaolei,Li, Zhipeng,Chang, Honghong,Gao, Wenchao,Wei, Wenlong
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p. 2475 - 2479
(2017/02/05)
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- Functionalization of multi-walled carbon nanotubes with pramipexole for immobilization of palladium nanoparticles and investigation of catalytic activity in the Sonogashira coupling reaction
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Pramipexole drug was attached to the surface of multi-walled carbon nanotubes (MWCNTs) by reaction of acylated carbon nanotubes with pramipexole for the first time. The modified MWCNTs were characterized using Fourier transform infrared spectroscopy, tran
- Abbasi, Sahar,Hekmati, Malak
-
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- An ambient temperature Sonogashira cross-coupling protocol using 4-aminobenzoic acid as promoter under copper and amine free conditions
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A new methodology has been developed based on Pd(OAc)2 and 4-aminobenzoic acid catalytic system for the Sonogashira cross-coupling reaction at ambient temperature under copper and amine free conditions. The newly developed catalytic system is conveniently applicable to the aryl iodides and terminal acetylenes. The catalytic system is much efficient because of the use of easily available and low cost additive.
- Das, Sameeran Kumar,Sarmah, Manashi,Bora, Utpal
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p. 2094 - 2097
(2017/05/10)
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- Gallic acid-derived palladium(0) nanoparticles as in situ-formed catalyst for Sonogashira cross-coupling reaction in ethanol under open air
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A simple and eco-friendly protocol using gallic acid-derived palladium(0) nanoparticles as in situ-formed catalyst for Sonogashira reactions in ethanol under optimum thermal conditions have been developed. Excellent yields were obtained with the addition of a small amount of gallic acid (1 mol%) to the reaction mixture. The formation of the PdNPs was confirmed by using UV/Vis spectroscopy, and their size and morphology were determined by TEM and XRD analysis. Both aliphatic and aromatic terminal alkynes displayed efficient reactivity with the catalytic system. Moreover, the reaction condition is highly compatible with less reactive aryl bromides at moderate temperature, and further can be reused repeatedly up to four cycles. Since gallic acid is a non-toxic naturally abundant phytochemical, the present method provides an efficient alternative route for Sonogashira reaction with natural feedstock as additive.
- Sarmah, Manashi,Mondal, Manoj,Gohain, Shivanee Borpatra,Bora, Utpal
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- Palladium stabilized on poly and mono sulfonamide ligands as novel, simple, effective, and recyclable nano catalysts for C-C cross-coupling reactions
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Poly and mono sulfonamide ligands were successfully used for the stabilization of palladium nanoparticles. The prepared nano catalysts that appeared to be heterogeneous and novel were characterized with various analytical tools. To establish the catalytic activity of the prepared catalysts, they were used in the Suzuki-Miyaura and Sonogashira-Hagihara coupling reactions of aryl halides under low palladium loading conditions. The catalysts showed good stability and could be recovered and reused for seven reaction cycles without significant loss of catalytic activity.
- Ghorbani-Vaghei, Ramin,Sarmast, Narges
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p. 1073 - 1080
(2017/10/03)
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- In situ generation of palladium nanoparticles using agro waste and their use as catalyst for copper-, amine- and ligand-free Sonogashira reaction
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The use of water extract of waste papaya bark ash for the in situ generation of palladium nanoparticles (Pd NPs) as an efficient and environmentally friendly basic medium for the Sonogashira reaction at room temperature is reported. This methodology follows green chemistry principles as the reaction is performed using agro waste (natural feedstock) for the generation of the Pd NPs as well as for providing a basic medium for the reaction in the absence of any additional organic or inorganic base, ligand and copper salt, giving excellent yield of cross-coupled product at room temperature. The reaction conditions are compatible with electronically diverse aryl iodides and electronically diverse alkyne derivatives.
- Dewan, Anindita,Sarmah, Manashi,Bora, Utpal,Thakur, Ashim J.
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- Supported palladium nanoparticles-catalyzed decarboxylative coupling approaches to aryl alkynes, indoles and pyrrolines synthesis
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The polystyrene supported palladium (Pd@PS) nanoparticles (NPs) catalyzed decarboxylative coupling (DC) of arylhalides and alkynyl carboxylic acids was developed for the synthesis of diaryl alkynes. Indole and 3-pyrroline heterocycles were also synthesized from 2-iodo anilines/amino benzocycloheptene bromide and alkynyl carboxylic acids, following a domino decarboxylative coupling-cyclization (DCC) approach under the same catalytic conditions. The combined anchoring and catalytic behaviour of Pd@PS makes the process favourable for the product formation.
- Reddy, C. Bal,Bharti, Richa,Kumar, Sandeep,Das, Pralay
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p. 71117 - 71121
(2016/08/05)
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- Palladium NPs supported on novel imino-pyridine-functionalized MWCNTs: Efficient and highly reusable catalysts for the Suzuki-Miyaura and Sonogashira coupling reactions
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In this article a new heterogeneous nanocatalyst based on palladium supported on functionalized multi-walled carbon nanotubes (MWCNTs) has been introduced. The synthetic process of the mentioned nanocatalyst, MWCNT-imino-pyridine/Pd, has been described. The characterization of the MWCNT-imino-pyridine/Pd was afforded by SEM, EDX, TEM, FTIR, ICP, and XRD. The surface structure of the materials was confirmed using Fourier transform infrared (FTIR) spectroscopy. The catalytic activity of MWCNT-imino-pyridine/Pd was tested in Sonogashira and Suzuki-Miyaura cross-coupling reactions affording various derivatives of both aryl alkynes and biaryls. The catalyst can be readily recovered and recycled at least six times without significant loss of catalytic activity.
- Adib, Mehdi,Karimi-Nami, Rahman,Veisi, Hojat
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p. 4945 - 4951
(2016/07/06)
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- Facile preparation of highly stable and active hybrid palladium nanoparticles: effectual, reusable and heterogeneous catalyst for coupling reactions
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Palladium nanoparticles were supported on a bed of Fe3O4@-NH2@Murexide using a simple and efficient method, and characterized using Fourier transform infrared spectroscopy, X-ray diffraction, scanning and transmission elec
- Adib, Mehdi,Yasaei, Zahra,Karimi-Nami, Rahman,Khakyzadeh, Vahid,Veisi, Hojat
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p. 748 - 752
(2016/09/04)
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- Gram-Scale Preparation of Pd@PANI: A Practical Catalyst Reagent for Copper-Free and Ligand-Free Sonogashira Couplings
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Palladium nanoparticles on the polyaniline (Pd@PANI) catalyst are now easily prepared on a gram scale through the oxidative polymerization of aniline in the presence of PdCl2 by using air as a clean oxidant. The material is found to be very stable and can be stored for more than one year without deactivation. Thus, it may become a commercial reagent in organic synthesis, depending on its application scopes. This article reported the first example of Pd@PANI-catalyzed Sonogashira couplings free of copper and ligands.
- Yu, Lei,Han, Zhe,Ding, Yuanhua
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p. 2124 - 2129
(2016/12/24)
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- Scope and limitations of a DMF bio-alternative within Sonogashira cross-coupling and Cacchi-type annulation
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Pd-catalysed C-C bond formation is an essential tool within the pharmaceutical and agrochemical industries. Many of these reactions rely heavily on polar aprotic solvents; however, despite their utility, these solvents are incompatible with the drive towards more sustainable chemical synthesis. Herein, we describe the scope and limitations of an alternative to DMF derived from renewable sources (Cyrene) in Sonogashira cross-coupling and Cacchi-type annulations.
- Wilson, Kirsty L.,Kennedy, Alan R.,Murray, Jane,Greatrex, Ben,Jamieson, Craig,Watson, Allan J. B.
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supporting information
p. 2005 - 2011
(2016/10/05)
-
- Discovery of the 3-Imino-1,2,4-thiadiazinane 1,1-Dioxide Derivative Verubecestat (MK-8931)-A β-Site Amyloid Precursor Protein Cleaving Enzyme 1 Inhibitor for the Treatment of Alzheimer's Disease
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Verubecestat 3 (MK-8931), a diaryl amide-substituted 3-imino-1,2,4-thiadiazinane 1,1-dioxide derivative, is a high-affinity β-site amyloid precursor protein cleaving enzyme 1 (BACE1) inhibitor currently undergoing Phase 3 clinical evaluation for the treat
- Scott, Jack D.,Li, Sarah W.,Brunskill, Andrew P. J.,Chen, Xia,Cox, Kathleen,Cumming, Jared N.,Forman, Mark,Gilbert, Eric J.,Hodgson, Robert A.,Hyde, Lynn A.,Jiang, Qin,Iserloh, Ulrich,Kazakevich, Irina,Kuvelkar, Reshma,Mei, Hong,Meredith, John,Misiaszek, Jeffrey,Orth, Peter,Rossiter, Lana M.,Slater, Meagan,Stone, Julie,Strickland, Corey O.,Voigt, Johannes H.,Wang, Ganfeng,Wang, Hongwu,Wu, Yusheng,Greenlee, William J.,Parker, Eric M.,Kennedy, Matthew E.,Stamford, Andrew W.
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supporting information
p. 10435 - 10450
(2016/12/16)
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- Urea as mild and efficient additive for palladium catalyzed Sonogashira cross coupling reaction
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A catalytic system based on Pd(OAc)2/urea has been developed for Sonogashira cross coupling of aryl halides with terminal alkynes at room temperature. This catalytic system effectively promotes Sonogashira coupling of both aryl iodides and aryl bromides to give polyfunctional alkynes under copper and amine free conditions. The catalytic system is readily accessible, inexpensive and highly flexible for both aromatic and aliphatic alkynes.
- Sarmah, Manashi,Dewan, Anindita,Thakur, Ashim J.,Bora, Utpal
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p. 914 - 916
(2016/02/05)
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- A green protocol for ligand, copper and base free Sonogashira cross-coupling reaction
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A convenient methodology has been developed for palladium catalyzed Sonogashira cross-coupling reaction under mild and green reaction conditions. The reaction is catalyzed by an in situ generated catalytic system based on Pd(OAc)2and WEB (water extract of banana peels ash) in the absence of any organic or inorganic base, ligand and copper salt with excellent yield of cross coupled product. The reaction condition is compatible with electronically diversified aryl iodides and electronically diversified aryl or aliphatic alkyne. The present method developed for the Sonogashira reaction offers many advantages including high conversion, high economy, the involvement of non-toxic green substrates, etc.
- Dewan, Anindita,Sarmah, Manashi,Bora, Utpal,Thakur, Ashim J.
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supporting information
p. 3760 - 3763
(2016/07/26)
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- DABCO-functionalized silica-copper(i) complex: A novel and recyclable heterogeneous nanocatalyst for palladium-free Sonogashira cross-coupling reactions
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A DABCO-functionalized silica supported copper(i)-based nanocatalyst was successfully prepared using a novel and simple route, in which the DABCO as an important functional entity acts as both a stable linker and an excellent chelator. Initially, Cu(ii) i
- Hajipour, Abdol Reza,Hosseini, Seyed Mostafa,Mohammadsaleh, Fatemeh
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p. 6939 - 6945
(2016/08/09)
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- Synthesis and characterization of functionalized titania-supported Pd catalyst deriving from new orthopalladated complex of benzophenone imine: Catalytic activity in the copper-free Sonogashira cross-coupling reactions at low palladium loadings
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The present work describes the preparation of organically modified TiO2-supported Pd catalyst originated from the new benzophenone imine-derived CN-palladacycle. The heterogeneous organic-inorganic hybrid catalyst system has been characterized by FT-IR, XRD, SEM, EDX, TEM and XPS techniques and exhibited good catalytic activity in the Sonogashira cross-coupling reactions of phenylacetylene with aryl halides under copper-, amine- and phosphine-free conditions, in conjunction with the ultra low catalyst Pd-loading. Significantly, the heterogeneous Pd catalyst allowed the reaction of phenylacetylene with aryl iodides to improve in excellent yields under very mild conditions using green solvent. Finally, the reusability of the supported Pd-complex was investigated by multiple reuses of the supported catalyst in subsequent Sonogashira cross-couplings.
- Karami, Kazem,Abedanzadeh, Sedigheh,Hervés, Pablo
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p. 93660 - 93672
(2016/10/18)
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- Palladium-Catalyzed Domino Process: Synthesis of Symmetrical Diarylalkynes, cis- and trans-Alkenes using Lithium Acetylide as a Synthon
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An efficient domino protocol has been developed for the synthesis of symmetrical diarylalkynes. Notably, the method was successful in the presence of a palladium catalyst without the support of a copper co-catalyst. Significantly, the method enabled the use of the commercially available and cheap lithium acetylide ethylenediamine complex as a source of acetylene for the construction of dual C-C bonds, with a wide range of compatibility towards various substituents of the aryl bromides/iodides. Significantly, this protocol was successfully applied to the synthesis of cis- and trans-alkenes in a highly stereoselective manner in a sequential one-pot process.
- Krishna, Jonnada,Krishna Reddy, Alavala Gopi,Satyanarayana, Gedu
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p. 3597 - 3610
(2016/01/25)
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- Application of organoselenides in the Suzuki, Negishi, Sonogashira and Kumada cross-coupling reactions
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We reported herein the regio- and stereoselective palladium-catalyzed cross-coupling reactions of unsaturated organoselenides with Sonogashira, Suzuki, Negishi and Kumada partners. The reactions were in general carried out with Pd(PPh3)4 (10 mol%), in DMF at 80 °C to afford the cross-coupling products in good yields. This strategy tolerated a wide range of substrates, such as alkynyl, vinyl, aryl and heteroaryl selenides with a variety of sensitive functional groups and gave the cross-coupling products in good yields.
- Stein,Bilheri,Zeni
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supporting information
p. 15522 - 15525
(2015/10/28)
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- Substituent effect of diimino-palladium (II) pincer complexes on the catalysis of Sonogashira coupling reaction
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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.
- Zhang, Jin-Hua,Li, Ping,Hu, Wen-Ping,Wang, Hong-Xing
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p. 107 - 112
(2015/06/02)
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- Palladium immobilized on amidoxime-functionalized magnetic Fe3O4 nanoparticles: A highly stable and efficient magnetically recoverable nanocatalyst for sonogashira coupling reaction
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We describe the synthesis of a novel Fe3O4/amidoxime (AO)/Pd nanocatalyst by grafting of AO groups on Fe3O4 nanoparticles and subsequent deposition of Pd nanoparticles. Prior to grafting of AO, the 2-cyanoethyl-
- Veisi, Hojat,Sedrpoushan, Alireza,Maleki, Behrooz,Hekmati, Malak,Heidari, Masoud,Hemmati, Saba
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p. 834 - 839
(2016/01/25)
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- Palladium particles from oxime-derived palladacycle supported on Fe3O4/oleic acid as a catalyst for the copper-free Sonogashira cross-coupling reaction
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An oxime-derived palladacycle was synthesized using 4-bromobenzoxime and pyridine in CHCl3, and characterized by FT-IR and 1H NMR spectroscopy. This Pd complex was supported on Fe3O4/oleic acid and shown to be an efficient catalyst for the copper-free Sonogashira cross-coupling reaction of various aryl halides with phenylacetylene in air and in ethanol or mixed aqueous medium. The oxime-derived palladacycle gave highly active palladium nanoparticles for the organic synthesis. The coupling products were obtained in high yields with low Pd loading and the heterogeneous catalyst can be separated by an external magnet and reused six times without loss of its activity. The characterization of the catalyst was carried out by XRD, SEM and TEM. Both TEM and XRD revealed that the palladium nanoparticles were well dispersed with diameters from 5 to 10 nm and average size 9.97 nm.
- Karami, Kazem,Najvani, Samaneh Dehghani,Naeini, Nasrin Haghighat,Hervés, Pablo
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p. 1047 - 1053
(2015/07/01)
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- Copper(i) catalyzed Sonogashira reactions promoted by monobenzyl nicotinium chloride, a N-donor quaternary ammonium salt
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A novel and effective catalytic system using monobenzylnicotinium chloride combined with copper(i) chloride was employed for the first time in Sonogashira cross-coupling reactions of phenylacetylene with various aryl halides. The goal was to use an efficient green media by using copper instead of palladium in metal-catalyzed coupling reactions. Monobenzyl nicotinium chloride, a quaternary ammonium salt containing a coordinating centre, plays an important role in this catalytic system and increases the efficiency of Cu(i) species during the reaction. A number of internal alkynes were produced in moderate to excellent yields in short reaction times in DMF at 135-140 °C. The efficiency of this catalytic system was compared with the copper-based catalyst obtained from dibenzylnicotinium chloride which has no N-donor active site, wherein lower activity was observed due to lack of a coordination site.
- Hajipour, Abdol Reza,Boostani, Elaheh,Mohammadsaleh, Fatemeh
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p. 94369 - 94374
(2015/11/17)
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- Methionine: A green and efficient promoter for copper-catalyzed Sonogashira cross-coupling reactions
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In the presence of amino acids as environmentally friendly ligands, CuI-catalyzed Sonogashira cross-coupling of various aryl halides with phenylacetylene was conducted to afford the corresponding internal alkynes. l-Methionine was found to be useful for t
- Hajipour, Abdol R.,Mohammadsaleh, Fatemeh
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p. 787 - 792
(2016/01/25)
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- A highly efficient copper and ligand free protocol for the room temperature Sonogashira reaction
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A mild and efficient catalytic system based on PdCl2 and Na2SO4 has been developed for the Sonogashira reaction of aryl iodides at room temperature. The system provides a simple route to obtain polyfunctional alkynes under ligand and copper free conditions. The procedure is equally efficient for aliphatic alkynes and aryl bromides. This journal is
- Gogoi, Ankur,Dewan, Anindita,Bora, Utpal
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- Microwave-assisted Sonogashira cross-coupling reaction catalyzed by CN-ortho-palladated complex of tribenzylamine under copper-free conditions
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Abstract The catalytic activity of [Pd{C6H4(CH2N(CH2Ph)2)} (μ-Br)]2 complex as an efficient, stable and non-sensitive to air and moisture catalyst was investigated in the Sonogashira cross-coupling reaction under microwave irradiation. In the presence of catalytic amount of this homogeneous catalytic system, various aryl halides were efficiently coupled with phenylacetylene under copper-free conditions. The substituted internal alkynes were produced in excellent yields in short reaction times in NMP at 100°. The combination of dimeric complex as homogenous catalyst and microwave irradiation and also NMP as microwave-active polar solvent gave higher yields in shorter reaction times.
- Hajipour, Abdol R.,Rafiee, Fatemeh
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p. 1163 - 1169
(2015/06/02)
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- Synthesis of Multinuclear Copper Complexes Bridged by Diquinolylamidinates and Their Application to Copper-Catalyzed Coupling of Terminal Alkynes and Aryl, Allyl, and Benzyl Halides
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A dinuclear copper complex containing N,N′-diquinolylformamidinate and a tetranuclear copper complex containing N,N′-diquinolylacetamidinate were synthesized. The structure of complexes was confirmed by X-ray analysis, showing that copper atoms were bridg
- Nakane, Takayuki,Tanioka, Yuta,Tsukada, Naofumi
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p. 1191 - 1196
(2015/04/27)
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- Ligand Control of E/Z Selectivity in Nickel-Catalyzed Transfer Hydrogenative Alkyne Semireduction
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A nickel-catalyzed transfer hydrogenative alkyne semireduction protocol that can be applied to both internal and terminal alkynes using formic acid and Zn as the terminal reductants has been developed. In the case of internal alkynes, the (E)- or (Z)-olefin isomer can be accessed selectively under the same reaction conditions by judicious inclusion of a triphos ligand.
- Richmond, Edward,Moran, Joseph
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p. 6922 - 6929
(2015/10/05)
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- Phosphane-ligated ionic palladium complexes: Synthesis, characterization and application as efficient and reusable precatalysts for the homogeneous carbonylative sonogashira reaction under CuI-free conditions
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The stable ionic PdII complexes 1A-4A were synthesized through the complexation of PdCl2(MeCN)2 with the phosphane-functionalized ionic liquids (FILs) 1-4 with π-acceptor character. Single-crystal X-ray diffraction analyses showed that 1A-4A were all composed of PdII-centred square-planar cations and triflate (OTf-, CF3SO3-) counteranions. The complex cations in 1A-3A possessed structural similarity to trans-PdCl2(PPh 3)2. The cation in 4A was a new PdII-centered planar complex ligated by the phosphane-carbon anion-carbene (PCC) pincer in a tripodal manner. The stabilities of 1A-4A were improved due to the intensive π-backbonding interaction between the Pd and P atoms. When complexes 1A-4A were used as precatalysts for homogeneous carbonylative Sonogashira coupling of PhI with phenylacetylene free of CuI, 1A-3A exhibited excellent catalytic behaviour with a TON of up to 1700 at a CO pressure of 0.5 MPa and moderate temperature of 100 °C, whereas 4A exhibited poor activity towards the transformation of PhI due to the high stability of 4A. The recycling experiments of 3A in [Bpy]BF4 (as a solvent) indicated that 3A could be recycled for 5 runs with neither activity loss nor metal leaching into the organic phase. Complex 3A also proved to be a general precatalyst for the carbonylative Sonogashira couplings of a wide range of aryl iodides with phenylacetylene. The selectivity of the desired carbonylation product depended more on electronic effects than the steric effects of the substituents of the aryl iodides. The ionic palladium complexes 1A-4A ligated by imidazolium-based-phosphanes were prepared and shown, by single-crystal X-ray diffraction analyses, to be composed of PdII-centered square-planar cations and OTf- counteranions. The complexes were tested as precatalysts for the homogeneous carbonylative Sonogashira coupling of aryl iodides with phenylacetylene. Copyright
- Zhang, Jing,Wang, Yongyong,Zhao, Xiaoli,Liu, Ye
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p. 975 - 985
(2014/03/21)
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