- Palladium phosphine complex catalysts immobilized on silica via a tripodal linker unit for the Suzuki-Miyaura coupling reactions of aryl chlorides
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Silica-immobilized palladium phosphine complex catalysts bearing a tripodal linker unit were tested for their ability to facilitate the Suzuki-Miyaura coupling reactions of aryl chlorides. The catalyst containing the tripodal linker with a trimethylsilyl capping group on the residual surface silanol groups displayed better catalytic activities and lower palladium and phosphorus leaching levels than the catalysts bearing a conventional trialkoxy-type linker.
- Fukaya, Norihisa,Onozawa, Syun-Ya,Ueda, Masae,Miyaji, Takayuki,Takagi, Yukio,Sakakura, Toshiyasu,Yasuda, Hiroyuki
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- Synthesis of alkyl biphenyl-4-carboxylates by reaction of biphenyl with carbon tetrachloride and alcohols in the presence of Fe2(CO)9
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Alkyl biphenyl-4-carboxylates have been synthesized with high selectivity by multicomponent reaction of biphenyl with carbon tetrachloride and aliphatic alcohols in the presence of iron-containing catalysts.
- Bayguzina,Erokhina,Khusnutdinov
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- Synthesis of Pd/SiO2 nanobeads for use in suzuki coupling reactions by reverse micelle sol-gel process
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Pd/SiO2 nanobeads containing tiny Pd clusters with a diameter of about 2 nm were prepared via a sol-gel process for SiO2 by using a water-in-oil microemulsion with Pd complexes and subsequent hydrogen reduction by heat treatment. The Pd/SiO2 nanostructures were employed in Suzuki coupling reactions with various substrates, and they served as good catalysts in these reactions.
- Kim, Mijong,Heo, Eunjung,Kim, Aram,Park, Ji Chan,Song, Hyunjoon,Park, Kang Hyun
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- PEG modification effect of silica on the Suzuki-Miyaura coupling reaction using silica-immobilized palladium catalysts
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The Pd phosphine complex catalysts immobilized onto polyethylene glycol (PEG)-modified silica were prepared in order to clarify the effect of the PEG modification on the Suzuki-Miyaura coupling reaction in organic solvents. For the reaction of ethyl p-bro
- Onozawa, Shun-Ya,Fukaya, Norihisa,Saitou, Kaori,Sakakura, Toshiyasu,Yasuda, Hiroyuki
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- Heterogeneous High-Loading Hyperbranched Polyglycidol with Peripheral NHC–Pd Complex: Synthesis and Application as Catalyst in Suzuki Coupling Reaction
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Abstract: A new polymer-supported highly functionalized dendritic polyether with peripheral NHC–Pd complex was developed by the simple anionic ring opening polymerization of glycidol on bis(3-hydroxypropyl) amine grafted Merrifield resin and its subsequent functional modification of hydroxyl group to NHC–Pd complex. The polymeric material had high stability and swelling capacity in a wide range of solvents, even in water. Similar to supported higher generation dendrimer, the newly developed system showed high palladium content with uniformly distributed and well isolated metal nanocentres. The palladium content was found to be 2.02?mmol/g which was comparatively higher than other heterogeneous NHC–Pd based catalysts and the polymer was used as heterogeneous palladium catalyst for Suzuki coupling reaction. Various factors affecting the catalyst’s performance were studied. The high availability and increased accessibility of catalytic sites, stability and dendrimer like property of the polymeric support, reusability, better resistance to metal leaching, easy synthesis etc. are the important features of this newly synthesized catalytic system. Graphical Abstract: [Figure not available: see fulltext.]
- Anjali,Sreekumar
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- Aminomethylpyridinequinones as new ligands for PEPPSI-type complexes
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A set of six new catalysts possessing quinone moieties in a pyridine ligand was synthesized and fully characterized by standard analytical techniques, including X-Ray crystallography. The results obtained in Suzuki and Mizoroki–Heck cross-coupling reactions catalyzed by quinone-based compounds were comparable to these obtained in the presence of the original PEPPSI complex designed by Organ. DFT calculations allow to see the structural and electronic factors to describe their similarity. On the other hand, steric maps and NCI plots were the tools to have a more global view of the systems studied, leaving the sphere of reactivity around the metal.
- Gajda, Roman,Poater, Albert,Brotons-Rufes, Artur,Planer, Sebastian,Wo?niak, Krzysztof,Grela, Karol,Kajetanowicz, Anna
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p. 138 - 156
(2021/03/22)
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- Charge Neutral [Cu2L2] and [Pd2L2] Metallocycles: Self-Assembly, Aggregation, and Catalysis
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A range of morphologically distinct metallosupramolecular Cu(II) and Pd(II) complexes has been constructed, based on the tritopic ligand 1,1′,1″-(benzene-1,3,5-triyl)tris(4,4-dimethylpentane-1,3-dione) (H3L). By control of the reaction conditions, it is possible to generate distinct coordination assemblies possessing either macrocyclic or polymeric structures and more importantly distinct activity in catalysis of the Suzuki-Miyaura cross-coupling.
- Ko?odziejski, Micha?,Brock, Aidan J.,Kurpik, Gracjan,Walczak, Anna,Li, Feng,Clegg, Jack K.,Stefankiewicz, Artur R.
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supporting information
p. 9673 - 9679
(2021/06/30)
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- 1,2,4-Triazole-3-thione compounds with a 4-ethyl alkyl/aryl sulfide substituent are broad-spectrum metallo-β-lactamase inhibitors with re-sensitization activity
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Metallo-β-lactamases (MBLs) are important contributors of Gram-negative bacteria resistance to β-lactam antibiotics. MBLs are highly worrying because of their carbapenemase activity, their rapid spread in major human opportunistic pathogens while no clinically useful inhibitor is available yet. In this context, we are exploring the potential of compounds based on the 1,2,4-triazole-3-thione scaffold as an original ligand of the di-zinc active sites of MBLs, and diversely substituted at its positions 4 and 5. Here, we present a new series of compounds substituted at the 4-position by a thioether-containing alkyl chain with a carboxylic and/or an aryl group at its extremity. Several compounds showed broad-spectrum inhibition with Ki values in the μM to sub-μM range against VIM-type enzymes, NDM-1 and IMP-1. The presence of the sulfur and of the aryl group was important for the inhibitory activity and the binding mode of a few compounds in VIM-2 was revealed by X-ray crystallography. Importantly, in vitro antibacterial susceptibility assays showed that several inhibitors were able to potentiate the activity of meropenem on Klebsiella pneumoniae clinical isolates producing VIM-1 or VIM-4, with a potentiation effect of up to 16-fold. Finally, a selected compound was found to only moderately inhibit the di-zinc human glyoxalase II, and several showed no or only moderate toxicity toward several human cells, thus favourably completing a promising behaviour.
- Becker, Katja,Benvenuti, Manuela,Bossis, Guillaume,Conde, Pierre-Alexis,Crowder, Michael W.,Dillenberger, Melissa,Docquier, Jean-Denis,Gavara, Laurent,Hernandez, Jean-Fran?ois,Legru, Alice,Mangani, Stefano,Pozzi, Cecilia,Sannio, Filomena,Tassone, Giusy,Thomas, Caitlyn A.,Verdirosa, Federica
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supporting information
(2021/10/12)
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- Synthesis of arylboronates via the Pd-catalyzed desulfitative coupling reaction of sodium arylsulfinates with bis(pinacolato)diboron
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The desulfitative borylation reaction of sodium arylsulfinates with bis(pinacolato)diboron or bis(neopentylglycolato)diboron under palladium catalysis has been developed, allowing selective C-B bond formation to give arylboronates with a range of functional groups in moderate to good yields under mild reaction conditions. A gram-scale preparation as well as the cascade Suzuki-Miyaura cross-coupling of arylboronates demonstrated the potential practical utility in organic synthesis.
- Qiu, Di,Li, Songyi,Yue, Guanglu,Mao, Jinshan,Xu, Bei,Yuan, Xinyu,Ye, Fei
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- Valorisation of urban waste to access low-cost heterogeneous palladium catalysts for cross-coupling reactions in biomass-derived γ-valerolactone
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Herein we report a simple protocol for the valorisation of a common urban biowaste. The lignocellulosic biomass obtained after the pre-treatment of pine needle urban waste is efficiently transformed into a low-cost support (PiNe) for the immobilization of Pd nanoparticles. The final Pd/PiNe heterogeneous catalyst features a small particle size (4.5 nm) and a metal loading (9.9 wt%) comparable with most commercially available and generally used counterparts. In this contribution, we tested the catalytic efficiency of the Pd/PiNe system in two representative cross-couplings, Heck and Hiyama reactions, and compared the results obtained with commercial Pd/C catalyst. The good reactivity in the biomass-derived solvent (GVL) confirms that the Pd/PiNe heterogeneous catalyst is a valid system that can be integrated into a waste valorization chain within a circular economy approach. In addition, the efficiency of the catalyst has also been extended to perform the challenging consecutive Hiyama-Heck reaction to afford differently substituted (E)-1,2-diarylethenes.
- Valentini, Federica,Ferlin, Francesco,Lilli, Simone,Marrocchi, Assunta,Ping, Liu,Gu, Yanlong,Vaccaro, Luigi
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supporting information
p. 5887 - 5895
(2021/08/23)
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- Scalable Negishi Coupling between Organozinc Compounds and (Hetero)Aryl Bromides under Aerobic Conditions when using Bulk Water or Deep Eutectic Solvents with no Additional Ligands
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Pd-catalyzed Negishi cross-coupling reactions between organozinc compounds and (hetero)aryl bromides have been reported when using bulk water as the reaction medium in the presence of NaCl or the biodegradable choline chloride/urea eutectic mixture. Both C(sp3)-C(sp2) and C(sp2)-C(sp2) couplings have been found to proceed smoothly, with high chemoselectivity, under mild conditions (room temperature or 60 °C) in air, and in competition with protonolysis. Additional benefits include very short reaction times (20 s), good to excellent yields (up to 98 %), wide substrate scope, and the tolerance of a variety of functional groups. The proposed novel protocol is scalable, and the practicability of the method is further highlighted by an easy recycling of both the catalyst and the eutectic mixture or water.
- Dilauro, Giuseppe,Azzollini, Claudia S.,Vitale, Paola,Salomone, Antonio,Perna, Filippo M.,Capriati, Vito
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supporting information
p. 10632 - 10636
(2021/04/09)
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- Pd-NHCs Enabled Suzuki-Miyaura Cross-Coupling of Arylhydrazines via C–N Bond Cleavage
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We describe a highly efficient protocol for cross-coupling of phenylhydrazines with arylboronic acids by Pd-NHCs under aerobic reaction condition. A series of well-defined Pd-NHCs complexes were evaluated and the relationship between the structure and the catalytic properties was investigated. It was disclosed that the Pd-PEPPSI-IPr proved to be the robust precatalyst, providing access to a range of (hetero)biaryls in good to excellent yields.
- Zeng, Xiao-Xiao,Li, Dong-Hui,Zhou, Zhen,Xu, Chang,Liu, Feng-Shou
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supporting information
(2021/03/01)
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- New Nickel-Based Catalytic System with Pincer Pyrrole-Functionalized N-Heterocyclic Carbene as Ligand for Suzuki-Miyaura Cross-Coupling Reactions
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A new catalytic system with Ni(NO3)2·6H2O as the catalyst and a pincer pyrrole-functionalized N-heterocyclic carbene as the ligand was employed in the Suzuki-Miyaura cross-coupling reactions of aryl iodides with arylboronic acids. With 5 mol% catalyst, the catalytic reactions proceeded at 160 °C, giving coupling products in isolated yields of up to 94% in short reaction times (1-4 h). The system worked efficiently with aryl iodides bearing electron-donating or electron-withdrawing groups and arylboronic acids with electron-donating groups. Steric effects were observed for both aryl iodides and arylboronic acids. It is proposed that the reactions underwent a Ni(I)/Ni(III) catalytic cycle.
- Guo, Zhifo,Lei, Xiangyang
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supporting information
(2021/09/11)
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- [Pd(4-R3Si-IPr)(allyl)Cl]/K2CO3/EtOH: A highly effective catalytic system for the Suzuki-Miyaura cross-coupling reaction
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A series of R3Si-NHC-Pd complexes 1Pd-7Pd was successfully tested as a pre-catalyst for the Suzuki-Miyaura cross-coupling reaction of aryl chlorides and arylboronic acid derivatives to form a wide range of valuable biphenyl products. Use of the readily available weakly basic potassium carbonate as a base and the highly polar protic ethanol as the reaction solvent gave the target coupling products in good-to-excellent yields. The experimental data pointed to the crucial importance of the preliminary pre-catalyst activation step [i.e., the conversion of Pd(II) to Pd(0)], which is remarkably facilitated by the electron-donating trialkylsilyl groups on the NHC ligands of 1Pd–7Pd, thereby rendering them superior compared to the commercially available IPr-Pd complexes. Computational analysis revealed the mechanism of the Pd(II)→Pd(0) activation step, demonstrating the critical role of the reaction solvent and the base in the preference of our 1Pd–7Pd pre-catalysts, for which this step is both thermodynamically and kinetically more feasible.
- Choe, Yoong-Kee,Choi, Jun-Chul,Faried, Miftah,Fukaya, Norihisa,Lee, Vladimir Ya.,Matsumoto, Kazuhiro,Mizusaki, Tomoteru,Putro, Wahyu S.,Seo, Yuto,Takagi, Yukio
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- 4-Amino-1,2,4-triazole-3-thione-derived Schiff bases as metallo-β-lactamase inhibitors
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Resistance to β-lactam antibiotics in Gram-negatives producing metallo-β-lactamases (MBLs) represents a major medical threat and there is an extremely urgent need to develop clinically useful inhibitors. We previously reported the original binding mode of 5-substituted-4-amino/H-1,2,4-triazole-3-thione compounds in the catalytic site of an MBL. Moreover, we showed that, although moderately potent, they represented a promising basis for the development of broad-spectrum MBL inhibitors. Here, we synthesized and characterized a large number of 4-amino-1,2,4-triazole-3-thione-derived Schiff bases. Compared to the previous series, the presence of an aryl moiety at position 4 afforded an average 10-fold increase in potency. Among 90 synthetic compounds, more than half inhibited at least one of the six tested MBLs (L1, VIM-4, VIM-2, NDM-1, IMP-1, CphA) with Ki values in the μM to sub-μM range. Several were broad-spectrum inhibitors, also inhibiting the most clinically relevant VIM-2 and NDM-1. Active compounds generally contained halogenated, bicyclic aryl or phenolic moieties at position 5, and one substituent among o-benzoic, 2,4-dihydroxyphenyl, p-benzyloxyphenyl or 3-(m-benzoyl)-phenyl at position 4. The crystallographic structure of VIM-2 in complex with an inhibitor showed the expected binding between the triazole-thione moiety and the dinuclear centre and also revealed a network of interactions involving Phe61, Tyr67, Trp87 and the conserved Asn233. Microbiological analysis suggested that the potentiation activity of the compounds was limited by poor outer membrane penetration or efflux. This was supported by the ability of one compound to restore the susceptibility of an NDM-1-producing E. coli clinical strain toward several β-lactams in the presence only of a sub-inhibitory concentration of colistin, a permeabilizing agent. Finally, some compounds were tested against the structurally similar di-zinc human glyoxalase II and found weaker inhibitors of the latter enzyme, thus showing a promising selectivity towards MBLs.
- Baud, Damien,Bebrone, Carine,Becker, Katja,Benvenuti, Manuela,Cerboni, Giulia,Chelini, Giulia,Cutolo, Giuliano,De Luca, Filomena,Docquier, Jean-Denis,Feller, Georges,Fischer, Marina,Galleni, Moreno,Gavara, Laurent,Gresh, Nohad,Kwapien, Karolina,Legru, Alice,Mangani, Stefano,Mercuri, Paola,Pozzi, Cecilia,Sannio, Filomena,Sevaille, Laurent,Tanfoni, Silvia,Verdirosa, Federica,Berthomieu, Dorothée,Bestgen, Beno?t,Frère, Jean-Marie,Hernandez, Jean-Fran?ois
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supporting information
(2020/09/16)
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- Facile Synthesis of Pd Nanoparticles Incorporated into Ultrathin Crystalline g-C3N4with Enhanced Photocatalytic Performance
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Driving chemical reactions by use of sunlight is of great importance for a sustainable future. Pd-based catalysts are commonly employed in thermal catalysis for various chemical reactions such as hydrogenation and coupling reactions. However, very few reports were related to Pd for photocatalytic coupling reactions. In this work, a facile method was developed to synthesize ultra-small Pd nanoparticles anchored on ultrathin crystalline graphitic carbon nitride (g-C3N4) for photocatalysis. Monodisperse Pd nanoparticles with a diameter of about 3 nm were dispersed on ultrathin crystalline g-C3N4 uniformly. The prepared Pd/g-C3N4 catalyst could take the advantages of the unique properties of ultra-small Pd nanoparticles and ultrathin crystalline g-C3N4 and thus exhibited markedly enhanced photocatalytic performance toward Suzuki-Miyaura coupling reaction under visible light irradiation. The preparing method could also be extended to the synthesis of Ru/g-C3N4, Pt/g-C3N4, and Ag/g-C3N4.
- Cao, Changyan,Huang, Yan,Jiang, Mengying,Li, Jun,Peng, Li,Song, Weiguo,Yang, Shuliang
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p. 7526 - 7532
(2020/11/18)
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- Palladium-Catalyzed Three-Component Coupling of Ynamides
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A palladium-catalyzed regioselective three-component coupling of ynamides was developed. The reaction proceeded smoothly to furnish the desired products when carried out at 70 °C in acetonitrile/water with potassium carbonate in the presence of 2.5 mol percent Pd2(dba)3·CHCl3 without a ligand. Various iodides and boronic acids were used in this reaction, and a carbon-carbon bond was formed with satisfactory regioselectivity from the ynamides.
- Wakamatsu, Hideaki,Takahashi, Ayano,Ishii, Ayaka,Kikuchi, Youhei,Sasaki, Madoka,Saito, Yukako,Natori, Yoshihiro,Yoshimura, Yuichi
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supporting information
p. 5299 - 5303
(2020/07/08)
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- Metal-Free Oxidative Esterification of Ketones and Potassium Xanthates: Selective Synthesis of α-Ketoesters and Esters
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A novel and efficient oxidative esterification for the selective synthesis of α-ketoesters and esters has been developed under metal-free conditions. In the protocol, various α-ketoesters and esters are available in high yields from commercially available ketones and potassium xanthates. Mechanistic studies have proven that potassium xanthate not only promotes oxidative esterification but also provides an alkoxy moiety for the reaction, which involves the cleavage and reconstruction of C-O bonds.
- Luo, Xianglin,He, Runfa,Liu, Qiang,Gao, Yanping,Li, Jingqing,Chen, Xiuwen,Zhu, Zhongzhi,Huang, Yubing,Li, Yibiao
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p. 5220 - 5230
(2020/05/18)
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- Stille coupling method for catalyzing aromatic nitro compound by transition metal
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The invention provides a Stille coupling method for catalyzing aromatic nitro compound by transition metal. According to the method, in a nitrogen protection atmosphere, an aromatic nitro compound andan organic tin compound are used as substrates in an organic solvent, a cross coupling reaction is carried out under the action of an alkali under the action of a transition metal catalyst and a ligand, and the aromatic compound is obtained through a column chromatography or recrystallization method. The method is easy to operate, low in price, high in product conversion rate and good in substrate applicability; the method can be used for synthesizing a series of aromatic compounds, and the compounds have wide application values in the fields of pesticides, medicines, materials and the like.
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Paragraph 0025; 0028; 0032-0036
(2020/08/02)
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- One-pot Negishi cross-coupling reaction of aryldiazonium salts via Ni catalysis induced by visible-light
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Visible-light induced catalysis is of high interest for its mild and environmentally benign properties. Herein, a general Ni catalysis accelerated by visible-light was successfully developed for one-pot Negishi coupling reactions at room temperature in a short reaction time (2Zn generated in situ from Grignard reagents and ZnBr2. This protocol provides a convenient access to C–C bond formation for important biaryl components. It tolerates various functional groups, and Hammett study illuminates the possiblility of Ni(III)/Ni(I) redox catalytic cycle.
- Wang, Lianjun,Liu, Gao
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- REAGENTS FOR FLUOROSULFATING ALCOHOLS OR AMINES
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Disclosed herein are compounds of formula Ar—N(SO2F)2, wherein Ar is selected from an optionally substituted aryl, an optionally substituted five-membered heteroaryl, or an optionally substituted six-membered heteroaryl. Also disclosed are methods of synthesizing the above compounds by reacting a compound of formula Ar—NH—R9 with MN(SO2F)2.
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Paragraph 0173-0174
(2019/02/24)
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- Perylenequinonoid-catalyzed photoredox activation for the direct arylation of (het)arenes with sunlight
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Naturally occurring perylenequinonoid pigments (PQPs) have attracted considerable attention owing to their excellent properties of photosensitization. They have been widely investigated as an aspect of photophysics and photobiology. However, their applications in photocatalysis are yet to be explored. We report here that sunlight along with 1 mol% cercosporin, which is one of the perylenequinonoid pigments, catalyzes the direct C-H bond arylation of (het)arenes by a photoredox process with good regioselectivity and broad functional group compatibility. Furthermore, a gram-scale reaction with great conversions of substrates was achieved even by a cercosporin-containing supernatant without organic solvent extraction and purification after liquid fermentation. Thus we set up a bridge between microbial fermentation and organic photocatalysis for chemical reactions in a sustainable, environmentally friendly manner.
- Zhang, Shiwei,Tang, Zhaocheng,Bao, Wenhao,Li, Jia,Guo, Baodang,Huang, Shuping,Zhang, Yan,Rao, Yijian
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supporting information
p. 4364 - 4369
(2019/05/10)
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- Mesoporous carbon supported ultrasmall palladium particles as highly active catalyst for Suzuki-Miyaura reaction
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A fast and efficient eco-friendly two-step preparation of a palladium-containing mesoporous carbon catalyst (C1) from green and readily available carbon precursors (phloroglucinol and glyoxal), a porogen template (pluronic F-127) and PdCl2 is described. Catalyst C1 contains ultra-small Pd nanoparticles (1.2 nm) uniformly dispersed in the carbon network and shows an outstanding activity for Suzuki-Miyaura reactions in pure water: extremely low amounts of palladium (10 μequiv. in most cases) are sufficient to afford almost palladium-free products (containing 0.25 ppm of precious metal without further purification steps).
- Enneiymy, Mohamed,Le Drian, Claude,Ghimbeu, Camelia Matei,Becht, Jean-Michel
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- Construction of Esters through Sulfuryl Fluoride (SO 2 F 2) Mediated Dehydrative Coupling of Carboxylic Acids with Alcohols at Room Temperature
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A facile method for the construction of esters through dehydrative coupling of carboxylic acids with alcohols is developed. The reactions are mediated by sulfuryl fluoride (SO 2 F 2) at room temperature and proceed with high efficiency. The method has several advantages including broad substrate scope, mild conditions, excellent functional group compatibility and affords high yields, even on gram scale.
- Qin, Hua-Li,S Alharbi, Njud,Wang, Shi-Meng
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p. 3901 - 3907
(2019/10/11)
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- Preparation method of Sacubitril intermediate
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The invention discloses a preparation method of an intermediate compound (R)-tert-butyl (1-((1,1'-diphenyl)-4-yl)-3-hydroxypropane-2-yl) carbamate. The preparation method is represented as the formulashown in the description. According to the preparation method, the steps are simple and short, the reaction yield is increased, reaction conditions are mild, most of the intermediates obtained in thereaction process are not required to be purified and can be subjected to the next reaction directly, large-batch synthesis is facilitated, chiral amine with stereospecificity is efficiently synthesized with aminotransferase, and the preparation method is more suitable for industrial production.
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Paragraph 0091-0093
(2019/10/01)
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- Sterically hindered N-heterocyclic carbene/palladium(ii) catalyzed Suzuki-Miyaura coupling of nitrobenzenes
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Palladium-catalyzed denitrative Suzuki coupling of nitroarenes using 2-aryl-5-(2,4,6-triisopropylphenyl)-2,3-imidazolylidene[1,5-a]pyridines as the ligands is described. The key to success is the use of the NHC ligands which show strong donating ability and suitable steric hindrance allowing the successful oxidative addition of Ar-NO2 bonds. Both aromatic and aliphatic boronic acids are tolerated, and a variety of biphenyls and alkylarenes were obtained in good to excellent yields.
- Chen, Kai,Chen, Wei,Yi, Xiaofei,Chen, Wanzhi,Liu, Miaochang,Wu, Huayue
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supporting information
p. 9287 - 9290
(2019/08/08)
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- Method for synthesizing aromatic compound by coupling palladium/imidazole salt with nitroaromatic hydrocarbon and boric acid compound (by machine translation)
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The invention discloses a method, for coupling a palladium/imidazole salt with a nitroaromatic hydrocarbon and a boric acid compound to synthesize an aromatic compound. The method comprises: in organic solvent, taking nitroaromatic hydrocarbon and boric acid compound as substrate, palladium/imidazole salt as a catalyst, carrying out coupling reaction under the action of alkali, and carrying out post-treatment to obtain the aromatic compound. The method is simple, easy to store, low in price, relatively low in ligand consumption, high in product yield, good in substrate applicability, and suitable for alkyl boronic acid. The process of the invention can be used to synthesize a series of aromatic compounds, for example. The compound has wide application value in the fields of pesticides, medicines, materials and the like. (by machine translation)
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Paragraph 0119-0123
(2019/10/01)
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- Visible-Light-Driven Synthesis of Arylstannanes from Arylazo Sulfones
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The visible-light-driven preparation of (hetero)aryl stannanes was carried out under both photocatalyst- and metal-free conditions via irradiation of arylazo sulfones in the presence of hexaalkyldistannanes. The reaction shows a high efficiency and a wide substrates scope. The resulting crude organotin derivatives can be directly employed in a Stille protocol.
- Lian, Chang,Yue, Guanglu,Mao, Jinshan,Liu, Danyang,Ding, Yi,Liu, Zerong,Qiu, Di,Zhao, Xia,Lu, Kui,Fagnoni, Maurizio,Protti, Stefano
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p. 5187 - 5191
(2019/07/03)
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- Unified Protocol for Fe-Based Catalyzed Biaryl Cross-Couplings between Various Aryl Electrophiles and Aryl Grignard Reagents
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The combination of commonly used FeCl3/SIPr with Ti(OEt)4/PhOM enabled a highly general iron-based catalyst system, which could efficiently catalyze the biaryl coupling reaction between various electrophiles (I, Br, Cl, OTs, OCONMe2, OSO2NMe2) and common or functionalized aryl Grignard reagents with high functional group tolerance. Selective couplings of aryl iodides and bromides over the corresponding oxygen-based electrophiles have been achieved, and thus a terphenyl acid intermediate for anidulafungin was conveniently synthesized via an orthogonal coupling strategy.
- Wang, Lei,Wei, Yi-Ming,Zhao, Yan,Duan, Xin-Fang
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p. 5176 - 5186
(2019/05/10)
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- Dihalogen-bridged NHC-palladium(i) dimers: Synthesis, characterisation and applications in cross-coupling reactions
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A di-iodo-bridged PdI dimer bearing an N-heterocyclic carbene ligand was made accessible via the reduction of [(IPr)PdI2]2 in basic methanol solution. The structural features of [(IPr)PdI]2 were explored by single-crystal X-ray analysis. It was found to be a convenient one-component precatalyst with high activity in Suzuki-Miyaura, Buchwald-Hartwig, and Sonogashira reactions.
- Pirkl, Nico,Del Grosso, Alessandro,Mallick, Bert,Doppiu, Angelino,Goo?en, Lukas J.
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supporting information
p. 5275 - 5278
(2019/05/08)
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- Introduction of a Crystalline, Shelf-Stable Reagent for the Synthesis of Sulfur(VI) Fluorides
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The design, synthesis, and application of [4-(acetylamino)phenyl]imidodisulfuryl difluoride (AISF), a shelf-stable, crystalline reagent for the synthesis of sulfur(VI) fluorides, is described. The utility of AISF is demonstrated in the synthesis of a diverse array of aryl fluorosulfates and sulfamoyl fluorides under mild conditions. Additionally, a single-step preparation of AISF was developed that installed the bis(fluorosulfonyl)imide group on acetanilide utilizing an oxidative C-H functionalization protocol.
- Zhou, Hua,Mukherjee, Paramita,Liu, Rongqiang,Evrard, Edelweiss,Wang, Dianpeng,Humphrey, John M.,Butler, Todd W.,Hoth, Lise R.,Sperry, Jeffrey B.,Sakata, Sylvie K.,Helal, Christopher J.,Am Ende, Christopher W.
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supporting information
p. 812 - 815
(2018/02/10)
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- Continuous Visible-Light Photoflow Approach for a Manganese-Catalyzed (Het)Arene C?H Arylation
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Manganese photocatalysts enabled versatile room-temperature C?H arylation reactions by means of continuous visible-light photoflow, thus allowing for efficient C?H arylations in 30 minutes with ample scope. The robustness of the manganese-catalyzed photoflow strategy was shown by visible light-induced gram-scale synthesis, clearly outperforming the batch performance.
- Liang, Yu-Feng,Steinbock, Ralf,Yang, Long,Ackermann, Lutz
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supporting information
p. 10625 - 10629
(2018/08/01)
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- Ligand-Free Bioinspired Suzuki–Miyaura Coupling Reactions using Aryltrifluoroborates as Effective Partners in Deep Eutectic Solvents
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Pd-catalyzed Suzuki–Miyaura cross-coupling between (hetero)aryl halides (Cl, Br, I) and versatile, moisture-stable mono- and bifunctional potassium aryltrifluoroborates proceeded efficiently and chemoselectively in air and under generally mild conditions; a catalyst loading as low as 1 mol % combined with Na2CO3 as a base in choline chloride/glycerol (1:2) deep eutectic solvent (DES) was used as a sustainable and environmentally responsible medium. The catalyst, base, and DES were easily and successfully recycled up to six times with an E-factor as low as 8.74. Valuable biaryls and terphenyl derivatives were furnished in yields of up to 98 %; over 50 reactions were compared and discussed. The methodology was applied for the synthesis of the nonsteroidal anti-inflammatory drugs Felbinac and Diflunisal.
- Dilauro, Giuseppe,García, Sergio Mata,Tagarelli, Donato,Vitale, Paola,Perna, Filippo M.,Capriati, Vito
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p. 3495 - 3501
(2018/09/21)
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- PH-Induced Linkage Isomerism of Pd(II) Complexes: A Pathway to Air- and Water-Stable Suzuki-Miyaura-Reaction Catalysts
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The Pd(II) complexes of the ambidentate pyridyldiketones 2,2-dimethyl-5-(3- or 4-pyridyl)pentane-3,5-dione are readily prepared in their linkage isomeric forms by the appropriate pH control during syntheses. The isolated diketonate- or pyridine-bound species can be interconverted with essentially 100% efficiency by treatment with an acid or base, respectively. Under the normal basic conditions for a Suzuki-Miyaura coupling, only the diketonate forms are present and act as very efficient catalysts for this reaction. The dynamic nature of the presented complexes allows the catalytic process to be quenched and reactivated at any stage without the risk of losing the catalyst's activity.
- Walczak, Anna,Stefankiewicz, Artur R.
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supporting information
p. 471 - 477
(2018/01/10)
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- Development of highly electron-deficient and less sterically-hindered phosphine ligands possessing 1,3,5-triazinyl groups
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Highly electron-deficient and less sterically-hindered phosphine ligands with two or three 1,3,5-triazinyl groups on the phosphorus atoms have been synthesized and examined in transition metal-catalyzed reactions for the first time. Due to the lack of any hydrogens or substituents at ortho-positions of the 1,3,5-triazine towards the phosphorous atom, it is considered that the steric hindrance of the tris(triazinyl)phosphine ligand to a metal center is least among triarylphosphine ligands. In the Stille coupling of aryl iodides, these electron-poor phosphine ligands provided good product yields compared to hitherto well-known phosphine ligands.
- Abe, Kazumi,Kitamura, Masanori,Fujita, Hikaru,Kunishima, Munetaka
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- Synthesis of arylstannanes by palladium-catalyzed desulfitative coupling reaction of sodium arylsulfinates with distannanes
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A novel Pd-catalyzed desulfitative cross-coupling reaction of sodium arylsulfinates with hexaalkyl distannanes is realized, allowing the facile synthesis of functionalized arylstannanes with moderate to excellent yields. The successful implement of gram-scale synthesis and tandem Stille coupling reaction demonstrates the potential applications of this method in organic synthesis.
- Lian, Chang,Yue, Guanglu,Zhang, Haonan,Wei, Liyan,Liu, Danyang,Liu, Sichen,Fang, Huayi,Qiu, Di
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p. 4019 - 4023
(2018/10/04)
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- Electron-Catalyzed Cross-Coupling of Arylboron Compounds with Aryl Iodides
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Arylboroxines in combination with zinc chloride and potassium tert-butoxide were found to undergo the electron-catalyzed cross-coupling with aryl iodides to give the corresponding biaryls without the aid of transition-metal catalysis.
- Okura, Keisho,Teranishi, Tsuyoshi,Yoshida, Yuto,Shirakawa, Eiji
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supporting information
p. 7186 - 7190
(2018/06/15)
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- Gold(i)-catalyzed cross-coupling reactions of aryldiazonium salts with organostannanes
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Gold(i)-catalyzed cross-coupling reactions of aryldiazonium salts with organostannanes are described. This redox neutral strategy offers an efficient approach to diverse biaryls, vinyl arenes and arylacetylenes. Monitoring the reaction with NMR and ESI-MS provided strong evidence for the in situ formation of Ph3PAuIR (R = aryl, vinyl and alkynyl) species which is crucial for the activation of aryldiazonium salts.
- Akram, Manjur O.,Shinde, Popat S.,Chintawar, Chetan C.,Patil, Nitin T.
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supporting information
p. 2865 - 2869
(2018/05/03)
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- Visible-Light-Enabled Preparation of Palladium Nanoparticles and Application as Catalysts for Suzuki-Miyaura Coupling
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Silyl ketones were used for the preparation of palladium nanoparticles (PdNPs) starting with Pd(OAc)2 in dimethylformamide under irradiation with a visible light-emitting diode (LED). Variation of the silyl ketone structure allowed adjustment of the PdNP diameter (1.9 or 5.2 nm). The in situ-formed PdNPs were further stabilized with polyvinylpyrrolidone and then applied as recyclable catalysts in the Suzuki-Miyaura coupling of arylboronic acids with aryl iodides to obtain substituted biphenyls in excellent yields.
- M?sing, Florian,Nüsse, Harald,Klingauf, Jürgen,Studer, Armido
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supporting information
p. 752 - 755
(2018/02/09)
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- Mechanochemical Activation of Zinc and Application to Negishi Cross-Coupling
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A form independent activation of zinc, concomitant generation of organozinc species and engagement in a Negishi cross-coupling reaction via mechanochemical methods is reported. The reported method exhibits a broad substrate scope for both C(sp3)–C(sp2) and C(sp2)–C(sp2) couplings and is tolerant to many important functional groups. The method may offer broad reaching opportunities for the in situ generation organometallic compounds from base metals and their concomitant engagement in synthetic reactions via mechanochemical methods.
- Cao, Qun,Howard, Joseph L.,Wheatley, Emilie,Browne, Duncan L.
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p. 11339 - 11343
(2018/08/28)
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- Dual gold and photoredox catalysed C-H activation of arenes for aryl-aryl cross couplings
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A mild and fully catalytic aryl-aryl cross coupling via gold-catalysed C-H activation has been achieved by merging gold and photoredox catalysis. The procedure is free of stoichiometric oxidants and additives, which were previously required in gold-catalysed C-H activation reactions. Exploiting dual gold and photoredox catalysis confers regioselectivity via the crucial gold-catalysed C-H activation step, which is not present in the unselective photocatalysis-only counterpart.
- Gauchot,Sutherland,Lee
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p. 2885 - 2889
(2017/04/04)
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- Amphipathic monolith-supported palladium catalysts for chemoselective hydrogenation and cross-coupling reactions
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A palladium catalyst immobilized on an amphipathic and monolithic polystyrene-divinylbenzene polymer bearing strongly acidic cation exchange functions (sulfonic acid moieties) (Pd/CM) was developed. It was used as a catalyst for hydrogenation and ligand-free cross-coupling reactions, such as the Suzuki-Miyaura, Mizoroki-Heck, and copper- and amine-free Sonogashira-type reactions, together with a palladium catalyst supported on monolithic polymer (Pd/AM) bearing basic anion exchange functions (ammonium salt moieties), which has been in practical use for the decomposition of hydrogen peroxide produced as a byproduct during the manufacture of ultrapure water. While the Pd/CM was highly active as a catalyst for the hydrogenation and a variety of reducible functional groups could be reduced, the use of Pd/AM led to a unique chemoselective hydrogenation. Aromatic carbonyl groups were tolerant under the Pd/AM-catalyzed hydrogenation conditions, although benzyl esters, benzyl ethers, and N-Cbz groups could be smoothly hydrocracked. The cross-coupling reactions readily proceeded using either catalyst. The palladium leaching from the Pd/CM into the reaction media was never observed during the Sonogashira-type reaction, which was hardly achieved by other palladium-supported heterogeneous catalysts due to the good affinity of the palladium species with alkynes.
- Monguchi, Yasunari,Wakayama, Fumika,Ueda, Shun,Ito, Ryo,Takada, Hitoshi,Inoue, Hiroshi,Nakamura, Akira,Sawama, Yoshinari,Sajiki, Hironao
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p. 1833 - 1840
(2017/01/21)
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- Palladium nanoparticles stabilized by phosphine ligand for aqueous phase room temperature suzuki-Miyaura coupling
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Water soluble phosphine ligand triphenylphosphine-3,3′,3″-trisulfonic acid trisodium salt (TPPTS) was used as the stabilizer as well as the activator to the palladium nanoparticles, which showed a high catalytic performance for aqueous phase Suzuki-Miyaura coupling reaction at room temperature.
- Ge, Jiyuan,Jiang, Jian,Yuan, Chenhuan,Zhang, Chaozhi,Liu, Minghua
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supporting information
p. 1142 - 1145
(2017/03/02)
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- Palladium-catalyzed cross-coupling of aryl chlorides with arylsilatranes
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The cross-coupling reactions of arylsilatranes with readily available and inexpensive aryl chlorides were carried out in toluene/THF at 100 °C for 3 h in the presence of tetrabutylammonium fluoride as an activator for smooth transmetalation and catalytic amounts of palladium(II) acetate and XPhos.
- Yamamoto, Yutaro,Baralle, Alexandre,Godefroy, Ana?s,Murakami, Kei,Yorimitsu, Hideki,Osuka, Atsuhiro
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p. 568 - 574
(2019/05/21)
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- Cobalt-Catalyzed Suzuki Biaryl Coupling of Aryl Halides
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Readily accessed cobalt pre-catalysts with N-heterocyclic carbene ligands catalyze the Suzuki cross-coupling of aryl chlorides and bromides with alkyllithium-activated arylboronic pinacolate esters. Preliminary mechanistic studies indicate that the cobalt
- Asghar, Soneela,Tailor, Sanita B.,Elorriaga, David,Bedford, Robin B.
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p. 16367 - 16370
(2017/12/07)
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- Organozinc-Mediated Direct C?C Bond Formation via C?N Bond Cleavage of Ammonium Salts
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We report a direct cross-coupling reaction between diarylzinc (Ar2Zn) and aryltrimethylammonium salts (ArNMe3 +??OTf) in the presence of LiCl, via C?N bond cleavage. The reaction takes place smoothly upon heating in THF without any external catalyst, enabling an efficient and chemoselective formation of biaryl products. Mechanistic studies indicate that the reaction proceeds through a single electron transfer route.
- Wang, Dong-Yu,Morimoto, Koki,Yang, Ze-Kun,Wang, Chao,Uchiyama, Masanobu
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p. 2554 - 2557
(2017/09/25)
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- SO2F2-Mediated One-Pot Synthesis of Aryl Carboxylic Acids and Esters from Phenols through a Pd-Catalyzed Insertion of Carbon Monoxide
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A one-pot Pd-catalyzed carbonylation of phenols into their corresponding aryl carboxylic acids and esters through the insertion of carbon monoxide has been developed. This procedure offers a direct synthesis of aryl carboxylic acids and esters from inexpensive and abundant starting materials (phenols, SO2F2 and CO) under mild conditions. This method tolerates a broad range of functional groups and is also applicable for the modification of complicated natural products.
- Fang, Wan-Yin,Leng, Jing,Qin, Hua-Li
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supporting information
p. 2323 - 2331
(2017/09/06)
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- Diethyloxalate as “CO” Source for Palladium-Catalyzed Ethoxycarbonylation of Bromo- and Chloroarene Derivatives
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Palladium(II)-catalyzed ethoxycarbonylation of aryl bromides with diethyloxalate oxalate is described. Functionalized aromatic esters can be efficiently synthesized with only 0.65 mol % PdCl2(PPh3)2 catalyst under microwav
- Monrose, Amandine,Salembier, Helori,Bousquet, Till,Pellegrini, Sylvain,Pélinski, Lydie
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supporting information
p. 2699 - 2704
(2017/08/16)
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- Arenediazonium Tosylates (ADTs) as Efficient Reagents for Suzuki-Miyaura Cross-Coupling in Neat Water
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A simple, convenient, and environment-friendly procedure for the preparation of substituted biaryls via Suzuki-Miyaura cross-coupling- was developed. The use of arenediazonium tosylates and corresponding boron compounds allows a conversion in neat water in the presence of commercially available Pd(OAc)2 under mild conditions with tolerance to a wide range of functional groups. A procedure particularly useful for the synthesis of di-ortho-substituted biaryls was developed.
- Kutonova, Ksenia V.,Jung, Nicole,Trusova, Marina E.,Filimonov, Victor D.,Postnikov, Pavel S.,Br?se, Stefan
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p. 1680 - 1688
(2017/03/21)
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- Cobalt-Catalyzed Biaryl Couplings via C-F Bond Activation in the Absence of Phosphine or NHC Ligands
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A highly general and selective Co-catalyzed biaryl coupling through C-F cleavage under phosphine or NHC-free conditions was described. A broad range of aryl fluorides including unactivated fluorides as well as those with sensitive functionalities could couple with various Ti(OEt)4-mediated aryl Grignard reagents with high selectivity under the catalysis of CoCl2/DMPU. Importantly, selective C-F bond activation couplings between two types of fluorines (difluorinated aromatics and on two different coupling partners) and in the presence of C-Cl or C-Br bonds could also be achieved.
- Wei, Juan,Liu, Kun-Ming,Duan, Xin-Fang
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p. 1291 - 1300
(2017/02/10)
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- A metal/zinc oxide nano-heterogeneous array preparation method and application of (by machine translation)
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The invention provides a metal/zinc oxide nano-heterogeneous array of preparation method and application. In the surface of the zinc ZnO nanorod array of preparing, Cu, Ag, Au, Pd, Pt and a plurality of metal nano-particles can be in-situ load to the array in the top end of the stick. Compared with the prior art, the present invention preparation of metal/zinc oxide nano-heterogeneous array has the advantages of: (1) used in the organic catalytic easy recovery; (2) the load of the nano-particle size and distribution is easy to control; (3) does not use the reducing agent and surface active agent, the surface of the nano-particles in the clean, should have good catalytic activity; (4) the metal ion precursor effective utilization rate is high, there will not be any nano-particle-phase nucleation; (5) through the subsequent oxidation method, transition metal nano-particles can be further converted into metal oxide nano-particles, can expand nano-heterogeneous array type. (by machine translation)
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Paragraph 0070-0073
(2017/10/28)
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- Pd-ZnO nanowire arrays as recyclable catalysts for 4-nitrophenol reduction and Suzuki coupling reactions
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In this work, we report a facile approach for the preparation of Pd nanoparticle-ZnO nanowire arrays followed by demonstrating their use as recyclable catalyst for reactions under different conditions. The facile synthesis largely relies on a spontaneous reduction of PdCl42? at the surface of oriented ZnO nanowires grown on a Zn foil. This is due to a combination of the strongly reducing ability of Zn foil and the semiconducting nature of ZnO nanowires. At room temperature and under a weak alkaline condition, the as-prepared Pd nanoparticle-ZnO nanowire arrays show a catalytic activity factor up to 76.6 s?1 g?1 in the reduction of 4-nitrophenol and no obvious decreases in the catalytic activity even after use of 10 times. Meanwhile, the as-prepared Pd nanoparticle-ZnO nanowire arrays exhibit extraordinary catalytic activity toward Suzuki and carbonylative Suzuki reactions at a higher temperature under a stronger alkaline condition. The outstanding performance of the hybrid nanowire arrays is mainly originated from the small size of the Pd nanoparticles (~2-4 nm) with clean surfaces, as well as a strong affinity between the Pd nanoparticles and ZnO nanowires, leading to marginable catalyst loss and aggregation. Considering the multiple choices of both noble metal nanocatalyst and transition metal oxide nanowire array, we expect noble metal nanoparticle-transition metal oxide nanowire arrays to be emerged as a new class of recyclable catalysts attractive for diverse organic reactions to develop pharmaceuticals, natural products and advanced functional materials.
- Hu, Qiyan,Liu, Xiaowang,Tang, Lin,Min, Dewen,Shi, Tianchao,Zhang, Wu
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p. 7964 - 7972
(2017/02/05)
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- Development of a Unique Heterogeneous Palladium Catalyst for the Suzuki–Miyaura Reaction using (Hetero)aryl Chlorides and Chemoselective Hydrogenation
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A unique heterogeneous palladium catalyst (7% Pd/WA30) supported on an anion exchange resin, which contains N,N-dimethylaminoalkyl functionalities on the polymer backbone, was developed. 7% Pd/WA30 could smoothly catalyze Suzuki–Miyaura reactions of even less reactive heteroaryl chlorides and heteroarylboronic acids to afford various (hetero)biaryls due to the electron-donating effect of the tert-amines on WA30 to Pd species. It was also applicable as a chemoselective hydrogenation catalyst, showing inactivity for the hydrogenolysis of tert-butyldimethylsilyl (TBS) ethers, alkyl benzyl ethers, and benzyl alcohols. The tert-amines on WA30 acted as moderate catalyst poisons for Pd, resulting in chemoselective hydrogenation. 7% Pd/WA30 was reused for at least five times without any loss of the hydrogenation catalytic activity. (Figure presented.).
- Ichikawa, Tomohiro,Netsu, Moeko,Mizuno, Masahiro,Mizusaki, Tomoteru,Takagi, Yukio,Sawama, Yoshinari,Monguchi, Yasunari,Sajiki, Hironao
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supporting information
p. 2269 - 2279
(2017/07/07)
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