- Copper-free Sonogashira cross-coupling reactions catalyzed by an efficient dimeric C,N-palladacycle in DMF/H2O
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Very small concentrations of a dimeric C,N-palladacycle were used as an efficient homogeneous catalyst for Sonogashira cross-coupling reactions between various aryl halides and phenylacetylene. The catalytic reactions were performed without the need for copper in DMF/H2O. This catalytic system shows excellent yields for aryl iodides and bromides and even in the case of aryl chlorides.
- Karami, Kazem,Haghighat Naeini, Nasrin
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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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- Phosphine-free copper-mediated Sonogashira coupling reaction
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A new, efficient, and inexpensive system has been developed to catalyze Sonogashira cross-coupling reactions between aryl iodides and terminal alkynes. We have employed CuO as well as a novel polymer-supported Cu-N-heterocyclic carbene complex, synthesize
- Borude, Vasant S.,Shah, Rikhil V.,Shukla, Sanjeev R.
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- Alternating magnetic field mediated micro reaction system for palladium-catalyzed coupling reactions
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A continuous flow reaction system in which a palladium magnetic catalyst was immobilized and vibrated by an alternating induced magnetic field was developed. The alternating electromagnetic field improved the mixing efficiency and catalytic activity for the palladium-catalyzed coupling reactions. This flow reaction system showed good product yields for various reactions such as Sonogashira, Heck, Suzuki, Stille, Hiyama and decarboxylative coupling reactions.
- Kim, Hee Jae,Choi, Jinseop,Choe, Jaehoon,Song, Kwang Ho,Lee, Sunwoo
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- Heterogeneous copper-free Sonogashira coupling reaction catalyzed by a reusable palladium Schiff base complex in water
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Heterogeneous Sonogashira coupling of terminal alkynes with aryl halides was studied over a polymer-supported macrocyclic Schiff base palladium complex. The cross-coupling reaction proceeded smoothly by adding a piperidine in water medium. The catalyst ex
- He, Ying,Cai, Chun
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- A 1D palladium coordination polymer and its catalytic activity in microwave-assisted Sonogashira reactions
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A palladium coordination polymer, [Pd(dppp)(L)](OTf)2·(H2O)] (1) (dppp = 1,3-bis(diphenylphosphino)propane), was prepared from a bipyridine-type ligand (L = (4-py)–CH = N–C10H6–N = CH–(4-py)) and [Pd(dppp)](OTf)
- Lee, Gang Min,Lee, Soon W.
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- Reduced graphene oxide supported Cu2O nanoparticles as an efficient catalyst for Sonogashira coupling reaction
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Reduced graphene oxide supported Cu2O nanoparticles were prepared by a liquid-phase reduction method and employed as an efficient heterogeneous catalyst for Sonogashira cross-coupling reaction. The catalyst exhibits high activity and selectivit
- Wang, Bing,Wang, Yingyong,Guo, Xiaoning,Jiao, Zhifeng,Jin, Guoqiang,Guo, Xiangyun
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- Synthesis of octasubstituted cyclooctatetraenes and their use as electron transporters in organic light emitting diodes
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The synthesis and characterization of octasubstituted cyclooctatetraenes (COTs) as well as their use as electron transporting materials in organic LEDs are reported. Tetraaryl-tetraarylethynyl-cyclooctatetraenes [C8Ar4(C≡CAr)4/
- Lu, Ping,Hong, Haiping,Cai, Guoping,Djurovich, Peter,Weber, William P.,Thompson, Mark E.
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- Photocatalytic Sonogashira reaction over silicon carbide supported Pd-Cu alloy nanoparticles under visible light irradiation
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The Sonogashira reaction is an important reaction for forming carbon-carbon bonds in organic synthesis, which is typically carried out under harsh reaction conditions. We herein report that PdCu alloy nanoparticles supported on SiC can efficiently catalyz
- Wang, Bing,Wang, Yingyong,Li, Jiazhou,Guo, Xiaoning,Bai, Gailing,Tong, Xili,Jin, Guoqiang,Guo, Xiangyun
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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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- 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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- Ligand-free (: Z)-selective transfer semihydrogenation of alkynes catalyzed by in situ generated oxidizable copper nanoparticles
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Herein, we present (Z)-selective transfer semihydrogenation of alkynes based on in situ generated CuNPs in the presence of hydrogen donors, such as ammonia-borane and a green protic solvent. This environmentally friendly method is characterized by operational simplicity combined with high stereo- and chemoselectivity and functional group compatibility. Auto-oxidation of CuNPs after the completion of a semihydrogenation reaction results in the formation of a water-soluble ammonia complex, so that the catalyst may be reused several times by simple phase-separation with no need for any special regeneration processes. Formed NH4B(OR)4 can be easily transformed back into ammonia-borane or into boric acid. In addition, a one-pot tandem sequence involving a Suzuki reaction followed by semihydrogenation was presented, which allows minimization of chemical waste production.
- Grela, Karol,Kusy, Rafa?
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supporting information
p. 5494 - 5502
(2021/08/16)
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- Highly efficient synthesis of 1,2-disubstituted acetylenes derivatives from the cross-coupling reactions of 1-bromoalkynes with organotitanium reagents
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A Highly efficient route for the synthesis of 1,2-disubstituted acetylene derivatives has been developed by nickel catalyzed cross-couplings of alkynyl halides with aryl titanium reagents under mild conditions. This has given corresponding cross-coupling products good to excellent isolated yields of up to 92 %. The aryls bearing electron-donating or electron-withdrawing groups in either alkynylhalides or aryltitanium substrates gave cross-coupling products good yields. This process was simple and easily performed, which provides an efficient method for the synthesis of 1,2-disubstituted acetylenes derivatives.
- Li, Qing-Han,Wu, Chuan
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supporting information
(2021/08/25)
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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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- 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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p. 4701 - 4705
(2021/06/11)
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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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- 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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- Palladium-catalyzed alkynylation of aromatic amines via in situ formed trimethylammonium salts
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A palladium-catalyzed alkynylation of aromatic amines with terminal alkynes via in situ formed trimethylammonium salts is developed. Compared with previous system using ammonium salts as starting materials and high loading of pre-prepared NHC-Pd catalyst (10 mol% Pd), this reaction directly employed amines as the coupling partners and the commercially available Pd2(dba)3/PPh2Cy (1 mol% Pd) as the catalyst, greatly simplifying the manipulation and decreasing the cost.
- Chen, Tieqiao,Huang, Tianzeng,Liu, Long,Yu, Wen-Qing
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supporting information
(2020/02/04)
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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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- 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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- 1-Aryltriazenes in the Suzuki, Heck, and Sonogashira Reactions in Imidazolium-ILs, with [BMIM(SO3H)][OTf] or Sc(OTf)3 as Promoter, and Pd(OAc)2 or NiCl2·glyme as Catalyst
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1-Aryltriazenes, the protected and more stable form of aryl-diazonium species, can be conveniently unmasked with Br?nsted acidic-IL or Sc(OTf)3 and coupled with a host of aryl/heteroaryl boronic acids, styrenes, and aryl/alkyl acetylenes in the Suzuki, Heck and Sonogashira reactions in one-pot and in respectable isolated yields, by using palladium or nickel catalyst in readily available imidazolium ILs as solvent, under mild conditions. The scope of these reactions are explored, and the potential for recovery/reuse of the IL solvent is also addressed.
- Sutar, Suraj M.,Savanur, Hemantkumar M.,Malunavar, Shruti S.,Prabhala, Pavankumar,Kalkhambkar, Rajesh G.,Laali, Kenneth K.
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supporting information
p. 6088 - 6093
(2019/09/17)
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- Preparation method of aryl alkyne catalyzed by visible light
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The invention discloses a simple and convenient method for directly synthesizing an aryl alkyne compound through photoredox catalysis. Aryl fluoroborate diazoate is used as an aryl free radical source, and different types of aryl alkyne are synthesized in situ through a decarboxylation process. A reaction has good functional group tolerability, and a simple domestic visible light source can be used for synthesizing the aryl alkyne of different functional groups under mild, neutral and transition-free metal reaction conditions.
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Paragraph 0046-0049
(2019/11/13)
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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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- 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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- 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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- The CuFe2O4@SiO2@ZrO2/SO42-/Cu nanoparticles: An efficient magnetically recyclable multifunctional Lewis/Br?nsted acid nanocatalyst for the ligand- and Pd-free Sonogashira cross-coupling reaction in water
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Herein, the synthesis and application of copper-incorporated sulfated zirconium oxide supported on CuFe2O4 NPs (CuFe2O4@SiO2@ZrO2/SO42-/Cu NPs) as a novel Lewis/Br?nsted acid nanocatalyst were studied for the Sonogashira C-C cross-coupling reaction. The fabricated CuFe2O4@SiO2@ZrO2/SO42-/Cu catalyst exhibited efficient activity for a large variety of aryl iodides/bromides and, most importantly, aryl chlorides in water and in the presence of NaOH as a base in short reaction times. The catalyst was fully characterized by FTIR, TG-DTG, VSM, XRD, EDX, FE-SEM and TEM analyses. A synergetic effect could be considered to have arisen from the various Lewis acid and Br?nsted acid sites present in the catalyst. The efficient incorporation of copper into zirconia provided a robust highly stable hybrid, which prevented any metal leaching, whether from the magnetite moiety and/or Cu sites in the reaction mixture. Moreover, the catalyst was successfully recovered from the mixture by a simple external magnet and reused for at least 9 consecutive runs. Zero metal leaching, stability, consistency with a variety of substrates, fast performance, cost-effectiveness, environmental friendliness, and preparation with accessible and cheap materials are some of the advantages and highlights of the current protocol.
- Nasseri, Mohammad Ali,Alavi, Seyyedeh Ameneh,Kazemnejadi, Milad,Allahresani, Ali
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p. 20749 - 20759
(2019/07/12)
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- Ligand-free, recyclable palladium-functionalized magnetite nanoparticles as a catalyst in the Suzuki-, Sonogashira, and Stille reaction
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A magnetically reusable ligand-free Fe3O4 palladium functionalized catalyst system was successfully prepared without the use of reducing agents, but by making use of the reduction potential of magnetite. The stabilizer was variated depending on the investigated reaction, whereby poly(ethylene glycol) (PEG) stabilized nanoparticles were used for the Suzuki reaction, as it requires protic conditions, while oleic acid stabilized nanoparticles were used for the Sonogashira and Stille reaction. It was found that it was possible to perform the Suzuki reaction and the Sonogashira reaction resulting in good to excellent conversions under air. Despite the good results for the Suzuki and the Sonogashira reaction it was not possible to perform the Stille reaction using this easily synthesized catalyst system due to the poisoning of the reusable catalyst by the tin-compound. Furthermore, the reusable catalyst system was recycled and reused for five times, resulting in a separable, straightforward and less time-consuming catalyst system.
- De Cattelle, Amaury,Billen, Arne,O'Rourke, Galahad,Brullot, Ward,Verbiest, Thierry,Koeckelberghs, Guy
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- Iron-Catalyzed Cross-Coupling of Alkynyl and Styrenyl Chlorides with Alkyl Grignard Reagents in Batch and Flow
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Transition-metal-catalyzed cross-coupling chemistry can be regarded as one of the most powerful protocols to construct carbon–carbon bonds. While the field is still dominated by palladium catalysis, there is an increasing interest to develop protocols that utilize cheaper and more sustainable metal sources. Herein, we report a selective, practical, and fast iron-based cross-coupling reaction that enables the formation of Csp?Csp3 and Csp2?Csp3 bonds. In a telescoped flow process, the reaction can be combined with the Grignard reagent synthesis. Moreover, flow allows the use of a supporting ligand to be avoided without eroding the reaction selectivity.
- Deng, Yuchao,Wei, Xiao-Jing,Wang, Xiao,Sun, Yuhan,No?l, Timothy
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p. 14532 - 14535
(2019/11/21)
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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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- Cobalt catalyzed stereodivergent semi-hydrogenation of alkynes using H2O as the hydrogen source
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Cobalt-catalyzed stereodivergent semi-hydrogenation of internal alkynes to alkenes is developed. The reaction proceeded through transfer hydrogenation under mild conditions using a base metal CoI2 as the catalyst, and H2O/MeOH as the hydrogen source with Zn as the reductant. The E/Z-selectivity of the product could be switched by changing the solvent and by inclusion/exclusion of a bidentate phosphine ligand (dppe). This method provides a simple and cost effective pathway for the synthesis of 1,2-dideuterioalkenes.
- Li, Kangkui,Khan, Ruhima,Zhang, Xuexin,Gao, Yang,Zhou, Yongyun,Tan, Heng,Chen, Jingchao,Fan, Baomin
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supporting information
p. 5663 - 5666
(2019/05/21)
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- Sonogashira Cross-Coupling of Aryltrimethylammonium Salts
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A protocol for C(sp)-C(sp2) bond formation via the Sonogashira coupling reaction involving C-N bond cleavage with aryltrimethylammonium triflate as an electrophilic coupling partner is described in this work. The reactions proceeded well under mild conditions with a stoichiometric ratio of alkyl, aryl, or heteroaryl acetylenes and provided yields of up to 93%. Numerous useful functional groups were tolerated under the reaction conditions. Direct amine alkynylation can be achieved through a one-pot process without the isolation of ammonium salt. The protocol can be performed on a gram scale. Density functional theory calculations were performed to investigate the reaction mechanism that involved oxidative addition, alkyne coordination, deprotonation, and reductive elimination, which yielded the cross-coupling product.
- Chen, Qianwei,Gao, Fengchen,Tang, Huiling,Yao, Miao,Zhao, Qian,Shi, Yanhui,Dang, Yanfeng,Cao, Changsheng
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p. 3730 - 3736
(2019/04/13)
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- Pd-Catalyzed decarboxylative alkynylation of alkynyl carboxylic acids with arylsulfonyl hydrazides via a desulfinative process
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In the presence of a Pd(ii)/P-ligand catalytic system, decarboxylative alkynylation of alkynyl carboxylic acids and arylsulfonyl hydrazides by desulfinative coupling could provide aryl alkynes in satisfactory yields by either judiciously selecting palladium catalysts or modulating phosphine ligands under mild conditions. The reported coupling reactions are very practical as they do not require the protection of inert gas or oxygen and are tolerant to many functional groups.
- Chang, Sheng,Liu, Ying,Yin, Shu Zhu,Dong, Lin Lin,Wang, Jian Feng
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supporting information
p. 5357 - 5362
(2019/04/04)
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- Highly efficient synthesis of 1,2-disubstituted acetylenes derivatives from the cross-coupling reactions of 1-bromoalkynes with organoalane reagents
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A Highly efficient route for the synthesis of 1,2-disubstituted acetylene derivatives has been developed by palladium catalyzed cross-couplings of alkynyl halides with (hetero)aryl aluminium reagents under mild conditions. This has given corresponding cross-coupling products good to excellent isolated yields of up to 99%. The aryls bearing electron-donating or electron-withdrawing groups in either alkynylhalides or arylaluminum substrates gave cross-coupling products good yields. This process was simple and easily performed, which provides an efficient method for the synthesis of 1,2-disubstituted acetylenes derivatives. On the basis of the experimental results, a possible catalytic cycle has been proposed.
- Shao, Xue-Bei,Jiang, Xin,Li, Qing-Han,Zhao, Zhi-Gang
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p. 6063 - 6070
(2018/09/12)
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- Development of a Palladium-Catalyzed Process for the Synthesis of Z-Alkenes by Sequential Sonogashira–Hydrogenation Reaction
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A novel and selective sequential one-pot protocol for the synthesis of Z-alkenes via Sonogashira–semihydrogenation is reported. The efficiency of the methodology is increased by utilizing PdCl2/BuPAd2 as homogeneous catalyst for the Sonogashira coupling and subsequently transforming the transition metal complex into a heterogeneous Pd hydrogenation catalyst. This methodology represents one of the rare examples directly combining homogeneous and heterogeneous catalysis.
- Hancker, S?ren,Neumann, Helfried,Beller, Matthias
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supporting information
p. 5253 - 5259
(2018/09/14)
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- Palladium nanoparticles immobilized on cyclodextrin-decorated halloysite nanotubes: Efficient heterogeneous catalyst for promoting copper- and ligand-free Sonogashira reaction in water–ethanol mixture
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Combining the excellent features of halloysite nanoclay and cyclodextrin, a novel hybrid system was designed and synthesized based on covalent attachment of tosylated cyclodextrin to thiosemicarbazide-functionalized halloysite nanoclay and used for the im
- Sadjadi, Samahe
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- Heterogenized Cu (II) salen complex grafted on graphene oxide nanosheets as a precursing catalyst for the Pd-free Sonogashira coupling
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Cu (II) salen complex immobilized on graphene oxide nanosheets [Cu (II) salen@GO] was synthesized with 3-chloropropyltrimethoxysilan as a linker and wholly characterized using various techniques like X-ray diffraction, Fourier-transform infrared, scanning electron microscopy/energy-dispersive X-ray spectroscopy, transmission electron microscopy, as well as atomic absorption spectroscopy (AAS). Cu (II) salen@GO as an effective heterogeneous catalyst has been investigated for the Sonogashira coupling reaction in dimethylsulfoxide with good to high yield (98%) in 4?hr at 110°C when the loading of Cu was 0.7?mmol?g?1 based on Cu element analysis by AAS. It was understood that heterogeneous catalyst was as active as its homogeneous analog, and presented good recoverability and no significant loss in activity within successive runs.
- Ghabdian, Mahdieh,Nasseri, Mohammad A.,Allahresani, Ali,Motavallizadehkakhky, Alireza
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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
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supporting information
p. 98 - 105
(2018/03/06)
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- Transition-Metal-Free Highly Chemoselective and Stereoselective Reduction with Se/DMF/H2O System
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A novel metal-free reduction system, in which H2Se (or HSe-) produced in situ from Se/DMF/H2O acts as the active reducing species, has been developed. By using water as an inexpensive, safe, and environmentally friendly surrogate as the hydrogen donor, this new reduction system incorporating Se/DMF/H2O displayed high selectivity and good activity in the reduction of α,β-unsaturated ketones and alkynes. Therefore, this reduction system has great potential to be a general and practical reduction methodology in organic transformation.
- Li, Hong-Chen,An, Cui,Wu, Ge,Li, Guo-Xing,Huang, Xiao-Bo,Gao, Wen-Xia,Ding, Jin-Chang,Zhou, Yun-Bing,Liu, Miao-Chang,Wu, Hua-Yue
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supporting information
p. 5573 - 5577
(2018/09/12)
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- Palladium-Catalyzed Decarboxylative Coupling Reactions of Propiolic Acid Derivatives and Arylsulfonyl Hydrazide
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Arylsulfonyl hydrazides were employed as coupling partners for the decarboxylative coupling reaction of propiolic acid derivatives. When the reaction was conducted using Pd(TFA) 2 (1.0 mol%), dppp (1.0 mol%), and Cu(OAc) 2 (2.4 equiv
- Park, Jaerim,Song, Kwang Ho,Lee, Sunwoo
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p. 3197 - 3204
(2018/08/12)
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- Potassium tert-butoxide-mediated generation of arynes from o-bromoacetophenone derivatives
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o-bromoacetophenone derivatives as new versatile aryne precursors are induced to selectively eliminate the CAr–Br and CAr–C(Ac) bonds in the help of t-BuOK. Furthermore, the active aryne intermediates are successfully appl
- Chang, Denghu,Gao, Fei,Shi, Lei
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p. 2428 - 2434
(2018/04/24)
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- Synthesis of Internal Alkynes through an Effective Tandem Elimination-Hydrodebromination-Cross-Coupling of gem-Dibromoalkenes with Halobenzenes
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Carbon-carbon couplings are among the most important strategies for constructing functional molecules in organic synthetic chemistry, and cheap, diverse, and readily available coupling partners are crucial to these diverse reactions. In this contribution, we report the first palladium-catalyzed C-C cross-coupling reaction of two kinds of organic halide, a gem -dibromoalkene and a halobenzene, as the starting materials. Terminal alkynes were generated in situ through a tandem elimination-hydrodebromination process, and the internal alkyne final products were synthesized in one pot. The reaction proceeded under simple, facile, and classic copper-free Sonogashira coupling reaction conditions in good to excellent yields.
- Ji, Yuan,Zhong, Ning,Kang, Zinan,Yan, Guobing,Zhao, Ming
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supporting information
p. 209 - 214
(2018/03/26)
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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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- Visible-light-enhanced photocatalytic Sonogashira reaction over silicon carbide supported Pd nanoparticles
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Sonogashira reaction of aryl halides with terminal alkynes can be realized by a visible-light-driven heterogeneous catalytic route using silicon carbide supported Pd nanoparticles as the catalyst under copper-, and ligand-free conditions. Under the irradi
- Wang, Bing,Guo, Xiaoning,Jin, Guoqiang,Guo, Xiangyun
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- Method for synergistically catalyzing Sonogashira cross-coupling reaction with carbonyl iron cluster compounds and trace palladium
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The invention discloses a method for synergistically catalyzing a Sonogashira cross-coupling reaction with carbonyl iron cluster compounds and trace palladium. According to the method, palladium chloride and triiron dodecarbonyl are taken as catalysts, acetylenic ketone is taken as a ligand, methanol is taken as a solvent, aryl halide, terminal alkyne and K2CO3 are subjected to a reaction , and arylethynylene compounds are obtained. With the adoption of the method, the use amount of palladium metal is reduced obviously, reaction operation is simple, the condition is mild (the temperature is commonly about 60 DEG C), compatibility of functional groups is good, the yield is high, the use quantity of the catalysts is low, and the productivity is high.
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Paragraph 0024; 0025; 0026; 0027; 0028-0047; 0064; 0065
(2017/07/19)
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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(II) Chloride Complexes of N,N′-Disubstituted Imidazole-2-thiones: Syntheses, Structures, and Catalytic Performances in Suzuki-Miyaura and Sonogashira Coupling Reactions
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Reactions of PdCl2 with 2 equiv of N,N′-disubstituted-imidazole-2-thiones R1R2C3N2S (R1 = R2 = Me (1a), iPr (1b), Cy (1c), C6Me3H2 (1d); R1 = Me, R2 = Ph (1e)) under the different conditions afford five mononuclear complexes trans-[(R1R2C3N2S)2PdCl2] (R1 = R2 = Me (2a), iPr (2b), Cy (2c), C6Me3H2 (2d); R1 = Me, R2 = Ph (2e)) and five binuclear Pd(II) complexes [(PdCl2){μ-(R1R2C3N2S)}]2 (R1 = R2 = Me (3a), iPr (3b), Cy (3c), C6Me3H2 (3d); R1 = Me, R2 = Ph (3e)), respectively. Complexes 2a-2e are easily converted into the corresponding 3a-3e by adding equimolar PdCl2 in refluxing MeOH, while the reverse reaction is achieved at room temperature by addition of 2 equiv of 1a-1e. In 2b, 2d, and 2e, each Pd(II) holds a distorted square planar geometry completed by two trans Cl atoms and two trans S atoms. Complexes 3a-3e have a dimeric [Pd2S2] structure in which two {PdCl2} units are interlinked by two N,N′-disubstituted-imidazole-2-thiones. Each Pd(II) adopts a distorted square planar geometry accomplished by two cis Cl atoms and two cis bridging S atoms. Among them, complex 3d has the two largest C6Me3H2 groups on the 2 and 5 positions of imidazole-2-thione, the longest Pd-μ-S bond, the largest S-Pd-S angle, and displays the highest catalytic activity toward Suzuki-Miyaura and copper-free Sonogashira cross-coupling reactions, which are confirmed by density functional theory calculations. The results provide an interesting insight into the introduction of various substituent groups into the periphery ligands of coordination complex-based catalysts, which could tune their geometric structures to acquire the best catalytic activity toward organic reactions.
- Zhang, Li-Ming,Li, Hai-Yan,Li, Hong-Xi,Young, David James,Wang, Yong,Lang, Jian-Ping
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p. 11230 - 11243
(2017/09/25)
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- Palladium Nanoparticles Immobilized on Individual Calcium Carbonate Plates Derived from Mussel Shell Waste: An Ecofriendly Catalyst for the Copper-Free Sonogashira Coupling Reaction
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The conversion of waste into high-value materials is considered an important sustainability strategy in modern chemical industries. A large volume of shell waste is generated globally from mussel cultivation. In this work, mussel shell waste (Perna viridis) is transformed into individual calcium carbonate plates (ICCPs) and is applied as a support for a heterogeneous catalyst. Palladium nanoparticles (3–6 nm) are deposited with an even dispersion on the ICCP surface, as demonstrated by X-ray diffraction and scanning electron microscopy. Using this system, Sonogashira cross-coupling reactions between aryl iodides and terminal acetylenes were accomplished in high yields with the use of 1 % Pd/ICCP in the presence of potassium carbonate without the use of any copper metal or external ligand. The Pd/ICCP catalyst could also be reused up to three times and activity over 90 % was maintained with negligible Pd-metal leaching. This work demonstrates that mussel shell waste can be used as an inexpensive and effective support for metal catalysts in coupling reactions, as demonstrated by the successful performance of the Pd-catalyzed, copper-free Sonogashira cross-coupling process.
- Saetan, Trin,Lertvachirapaiboon, Chutiparn,Ekgasit, Sanong,Sukwattanasinitt, Mongkol,Wacharasindhu, Sumrit
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p. 2221 - 2230
(2017/09/06)
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- N, N -Dimethylformamide-stabilized copper nanoparticles as a catalyst precursor for Sonogashira-Hagihara cross coupling
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We report the catalysis of a Sonogashira-Hagihara cross-coupling reaction using a DMF-stabilized copper nanoparticle catalyst. The reaction proceeded with low catalyst loadings, and a turnover number of 4.0 × 103 was recorded for 0.01 mol% cata
- Oka, Hideo,Kitai, Katsuya,Suzuki, Takeyuki,Obora, Yasushi
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p. 22869 - 22874
(2017/07/10)
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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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- A phosphine-free, atom-efficient cross-coupling of aryl iodides with triarylindiums or trialkynylindiums catalyzed by immobilization of palladium(0) in MCM-41
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The first phosphine-free heterogeneous atom-efficient cross-coupling reaction of aryl iodides with triarylindiums or trialkynylindiums was achieved in THF at 68 °C by using 1 mol% of MCM-41-immobilized palladium(0)-Schiff base complex [MCM-41-N,N-Pd(0)] as catalyst, yielding a variety of unsymmetrical biaryls and arylalkynes in good to excellent yields. The heterogeneous palladium(0) catalyst could easily be prepared via a simple procedure from commercially readily available reagents, and recovered by filtration of the reaction solution and recycled at least 10 times without significant loss of activity.
- Lei, Zhiwei,Liu, Haiyi,Cai, Mingzhong
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- Three-Component One-Pot Synthesis of Unsymmetrical Diarylalkynes by Thermocontrolled Sequential Sonogashira Reactions Using Potassium Ethynyltrifluoroborate
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Unsymmetrical diarylalkynes were synthesized in moderate to good yields through a three-component one-pot procedure involving thermocontrolled sequential Sonogashira reactions with potassium ethynyltrifluoroborate and two different reactive aryl halides. The one-pot procedure was initiated by the palladium/copper-catalyzed Sonogashira coupling of potassium ethynyltrifluoroborate to an aryl iodide or electron-deficient aryl bromide at 40 °C. Following a subsequent deboronative Sonogashira reaction of the in situ generated potassium (arylethynyl)trifluoroborate, a second coupling to a less-active electron-rich aryl bromide at 80 °C, without any additional palladium/copper catalyst or base, gave rise to unsymmetrical diarylalkynes.
- Kim, Taejung,Jeong, Kyu Hyuk,Kim, Youngseok,Noh, Taesub,Choi, Jaeyoung,Ham, Jungyeob
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p. 2425 - 2431
(2017/05/12)
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- Nickel-catalyzed decarboxylative coupling of an alkynyl carboxylic acid with aryl iodides
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A decarboxylative coupling reaction with an alkynyl carboxylic acid and aryl iodides in the presence of a nickel catalyst was developed. When the reaction was conducted with NiCl2 (10?mol%), Xantphos (15?mol%), Mn (1.0?equiv), and Cs2CO3 (1.5?equiv), the desired diaryl alkynes were formed in moderated to good yields. Furthermore, this method does not produce the diyne, which is formed in the homocoupling of alkynyl carboxylic acids.
- Son, Yujeong,Kim, Han-Sung,Lee, Ju-Hyeon,Jang, Jisun,Lee, Chin-Fa,Lee, Sunwoo
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p. 1413 - 1416
(2017/03/17)
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