- Palladium-catalyzed direct arylation of polyfluoroarenes with organosilicon reagents
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The palladium-catalyzed direct arylation of polyfluoroarenes with organosilicon reagents was achieved by establishing general reaction conditions. This protocol was compatible with a broad range of functional groups and offered the desired products in moderate to good yields. Copyright
- Fan, Huixin,Shang, Yaping,Su, Weiping
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- Suzuki-Miyaura coupling reaction using pentafluorophenylboronic acid
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(Chemical Equation Presented) We have found new conditions for the Suzuki-Miyaura coupling reaction applicable to pentafluorophenylboronic acid (C6F5B(OH)2) (1), which is an inactive substrate under normal conditions. The
- Korenaga, Toshinobu,Kosaki, Takahiro,Fukumura, Rokki,Ema, Tadashi,Sakai, Takashi
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- Palladium nanocrystals stabilized by cucurbit[6]uril as efficient heterogeneous catalyst for direct C-H functionalization of polyfluoroarenes
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Palladium nanocrystals (Pd NCs) featuring abundant surface defects are successfully synthesized by using cucurbit[6]uril as a stabilizer. Employing the as-prepared Pd NCs as catalyst, an efficient approach to the direct C-H functionalization of electron-d
- Cao, Minna,Wu, Dongshuang,Su, Weiping,Cao, Rong
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- Synthesis and phase-transition of 4-alkoxycarbonylphenyl 4′-n-alkoxy-2, 3, 5, 6-tetrafluorobiphenyl-4-carboxylates
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Two new homologous series of compounds containing symmetrically tetrafluorinated phenyl units, 4-[(s)-2-methylbutoxycarbonyl]phenyl and 4-n-pentyloxyphenyl 4′-n-alkoxy-2, 3, 5, 6-tetrafluorobiphenyl-4-carboxylates (n = 5-10) have been synthesized from 1-p
- Wen,Tian,Guo,Chen
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- The effect of N-heterocyclic carbene ligands in the palladium-catalyzed cross-coupling reaction of K[C6F5BF3] with aryl iodides and aryl bromides
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The effect of N-heterocyclic carbene (NHC) ligands on the catalytic activity of in situ generated palladium complexes in the model cross-coupling reaction of K[C6F5BF3] with 4-FC6H4I was studied. Based on the obtained results, a series of pentafluorobiphenyls C6F5C6H4X were prepared from K[C6F5BF3] and XC6H4I or 4-CF3C6H4Br in high yields under aerobic conditions.
- Adonin, Nicolay Yu.,Babushkin, Dmitrii E.,Parmon, Valentin N.,Bardin, Vadim V.,Kostin, Gennadiy A.,Mashukov, Vasiliy I.,Frohn, Hermann-Josef
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- Evaluating the electronic properties of ditopic and hetero-ditopic ligands derived from benzimidazole and pyrazole by 13C NMR spectroscopy
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Huynh's electronic parameter (HEP) was applied to distinguish the electronic properties of benzimidazole and pyrazole donors in N^N ditopic and N^N′ hetero-ditopic, dinucleating ligands by 13C NMR spectroscopy of their dipalladium complexes bea
- Huynh, Han Vinh,Lu, Yuchen,Meng, Qi,Teng, Qiaoqiao,Zhu, Rongmei
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- TBu3P-coordinated 2-phenylaniline-based palladacycle complexes as precatalyst for Pd-catalyzed coupling reactions of aryl halides with polyfluoroarenes by a C-H activation strategy
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A tBu3P-coordinated 2-phenylaniline-based palladacycle complex was demonstrated to be an efficient precatalyst for Pd-catalyzed coupling reactions of aryl halides with polyfluoroarenes that operates through a C-H activation strategy. The ready
- Zhang, Hong-Hai,Dong, Jie,Hu, Qiao-Sheng
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- Direct palladium-catalyzed desulfitative CC coupling of polyfluoroarenes with arylsulfinate salts: Water-accelerated reactions
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A new approach to the synthesis of fluorinated biaryl compounds from easily available starting materials is described. This protocol is based on the direct palladium-catalyzed desulfitative cross-coupling of polyfluoroarenes with various arylsulfinate salts via CH bond activation, accelerated by trace amount of water. The method allows the synthesis of various fluorinated biaryl products in moderate to good yields, and tolerated a variety of functional groups, including alkyl, phenyl, methoxy, fluoro, and chloro groups.
- Lin, Xiaoxi,You, Yi,Weng, Zhiqiang
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- Highly efficient heterogeneous copper-catalyzed decarboxylative cross-coupling of potassium polyfluorobenzoates with aryl halides leading to polyfluorobiaryls
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The heterogeneous decarboxylative cross-coupling reaction of potassium polyfluorobenzoates with aryl iodides and bromides was achieved in diglyme or DMAc at 130 or 160 °C in the presence of 10-20 mol% of a 1,10-phenanthroline-functionalized MCM-41-immobilized copper(i) complex, [MCM-41-Phen-CuI], yielding a variety of polyfluorobiaryls in good to excellent yields. This heterogeneous copper(i) complex could easily be prepared via a simple procedure from commercially readily available and inexpensive reagents, exhibited the same catalytic activity as the homogeneous CuI/Phen system, and was recovered by filtration of the reaction solution and recycled at least 8 times without significant loss of catalytic activity.
- Lin, Yang,Cai, Mingzhong,Fang, Zhiqiang,Zhao, Hong
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- Catalytic intermolecular direct arylation of perfluorobenzenes
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Penta-, tetra-, tri-, and difluorobenzenes undergo direct arylation with a wide range of arylhalides in high yield. Inverse reactivity is observed compared to the common electrophilic aromatic substitution pathway since electron-deficient, C-H acidic aren
- Lafrance, Marc,Rowley, Christopher N.,Woo, Tom K.,Fagnou, Keith
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- Copper-catalyzed cross-coupling of arenediazonium tetrafluoroborates with polyfluoroarenes
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A novel cross-coupling reaction of arenediazonium tetrafluoroborates with polyfluoroarenes is briefly described. It has advantages of high reaction efficiency, excellent functional group compatibility, mild reaction conditions, short reaction time, and inexpensive ligand. This reaction also can be performed as a one-pot process from anilines omitting isolation of arenediazonium tetrafluoroborates. It has been extended to the preparation of biaryls containing polyfluoroarene structural moiety.
- Zhu, Xingyi,Li, Feng,Su, Weike
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- Palladium-Catalyzed Carbon–Fluorine and Carbon–Hydrogen Bond Alumination of Fluoroarenes and Heteroarenes
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Through serendipitous discovery, a palladium bis(phosphine) complex was identified as a catalyst for the selective transformation of sp2C?F and sp2C?H bonds of fluoroarenes and heteroarenes to sp2C?Al bonds (19 examples, 1
- Chen, Wenyi,Hooper, Thomas N.,Ng, Jamues,White, Andrew J. P.,Crimmin, Mark R.
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- Palladium-catalyzed decarbonylative and decarboxylative cross-coupling of acyl chlorides with potassium perfluorobenzoates affording unsymmetrical biaryls
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This paper describes the synthesis of unsymmetrical biaryls by the palladium-catalyzed cross-coupling reaction of acyl chlorides with potassium perfluorobenzoates. This transformation is unique in that it involves simultaneous decarbonylation and decarbox
- Fu, Liyan,You, Jingwen,Nishihara, Yasushi
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- Copper-Catalysed Suzuki-Miyaura Cross-Coupling of Highly Fluorinated Aryl Boronate Esters with Aryl Iodides and Bromides and Fluoroarene?Arene π-Stacking Interactions in the Products
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A combination of copper iodide and phenanthroline as the ligand is an efficient catalyst for Suzuki-Miyaura cross-coupling of highly fluorinated boronate esters (aryl?Bpin) with aryl iodides and bromides to generate fluorinated biaryls in good to excellent yields. This method represents a nice alternative to traditional cross-coupling methods which require palladium catalysts and stoichiometric amounts of silver oxide. We note that π???π stacking interactions dominate the molecular packing in the partly fluorinated biaryl crystals investigated herein. They are present either between the arene and perfluoroarene, or solely between arenes or perfluoroarenes, respectively.
- Budiman, Yudha P.,Friedrich, Alexandra,Radius, Udo,Marder, Todd B.
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- A new application of (polyfluoroorgano)trifluoroborate salts: The palladium-catalysed cross-coupling reaction with substituted benzenediazonium tetrafluoroborates
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For the first time (polyfluoroorgano)trifluoroborate salts, namely K[C6F5BF3], K[C6HF4BF3] (all three isomers), K[3,4,5-C6H2F3BF3], and K[CF2=CFBF3] were principally applied as reagents to Pd-catalysed cross-coupling reactions. A series of polyfluorinated biphenyls (polyfluorophenyl)trifluoroborate salts on the reactivity in the coupling reaction was elucidated. In addition to (polyfluorophenyl)trifluoroborate salts, the cross-coupling was expanded to a first example of a perfluoroalkenyl reagent. K[CF2=CFBF3] reacted with [4-FC6H4N2][BF4] and formed CF2=CF-C6H4F-4.
- Frohn, Hermann-Josef,Adonin, Nicolay Yu.,Bardin, Vadim V.,Starichenko, Vladimir F.
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- The influence of the nature of phosphine ligand on palladium catalysts for cross-coupling of weakly nucleophilic potassium pentafluorophenyltrifluoroborate with ArHal and PhCH2Hal (Hal=Br, Cl)
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The influence of the ligand nature on catalytic activity of palladium catalysts for cross-coupling of weakly nucleophilic potassium pentafluorophenyltrifluoroborate, which imitates the behavior of electron-deficient organoboron reagents, with aryl halides, ArHal (Hal=Br, Cl) was studied. The activity of the catalysts generated in situ from Pd(OAc) 2 and appropriate phosphorous containing ligands and the reaction selectivity was found to depend on the nature of bulky phosphines used as ligands. As a result, conditions for involving the electron-deficient organoboron reagent - potassium pentafluorophenyltrifluoroborate - in the palladium-catalyzed cross-coupling with aryl bromides and aryl chlorides were identified. It was demonstrated that the chosen conditions are appropriate for the reaction of K[C6F5BF3] with benzyl chloride and benzyl bromide deriving pentafluorophenylarylmethanes, C6F 5CH2Ar.
- Shabalin, Anton Yu.,Adonin, Nicolay Y.,Bardin, Vadim V.,Parmon, Valentin N.
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- Highly efficient cross-coupling reactions with the perfluoroorganotrifluoroborate salts K [RFBF3] (RF=C6F5, CF2=CF)
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Potassium pentafluorophenyl- and trifluorovinyltrifluoroborates, both containing electron-poor organo groups, reacted with iodobenzene and p-substituted iodobenzenes in the presence of palladium compounds and stoichiometric amounts of silveroxide to the f
- Frohn,Adonin,Bardin,Starichenko
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- Ligand-free palladium/copper co-catalyzed direct arylation of polyfluoroarenes with aryl iodides
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New reaction conditions for the direct arylation of polyfluoroarenes with aryl iodides have been developed. This reaction can be co-catalyzed by palladium/copper without ligands and exhibits excellent functional group compatibility.
- Zhang, Xinyan,Yu, Jian,Yan, Guobing
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- Copper-catalyzed arylation and alkenylation of polyfluoroarene C-H bonds
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An efficient, copper-catalyzed method for the arylation, alkenylation, and benzylation of polyfluoroarenes has been developed. Arenes containing two or more fluorine substituents on the aromatic ring can be efficiently functionalized. The best results are
- Do, Hien-Quang,Daugulis, Olafs
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- Palladium-Catalyzed Solid-State Polyfluoroarylation of Aryl Halides Using Mechanochemistry
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The Suzuki–Miyaura cross-coupling between polyfluorinated arylboron nucleophiles and aryl halides enables the efficient construction of polyfluorinated structural motifs frequently found in organic materials and catalysts. A key challenge associated with
- Takahashi, Rikuro,Seo, Tamae,Kubota, Koji,Ito, Hajime
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p. 14803 - 14810
(2021/12/09)
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- Transition-Metal-Free Coupling of Polyfluorinated Arenes and Functionalized, Masked Aryl Nucleophiles
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A chemoselective C(sp2)?C(sp2) coupling of sufficiently electron-deficient fluorinated arenes and functionalized N-aryl-N’-silyldiazenes as masked aryl nucleophiles is reported. The fluoride-promoted transformation involves the in situ generation of the aryl nucleophile decorated with various sensitive functional groups followed by a stepwise nucleophilic aromatic substitution (SNAr). These reactions typically proceed at room temperature within minutes. This catalytic process allows for the functionalization of both coupling partners, furnishing highly fluorinated biaryls in good yields.
- Finck, Lucie,Oestreich, Martin
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p. 11061 - 11064
(2021/06/12)
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- Selective synthesis of fluorinated biaryls by [MCl2(PhPEWO-F)] (M = Ni, Pd) catalysed Negishi cross-coupling
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Highly selective cross-couplings to polyfluorinated assymmetric biaryls, including the symmetric biaryl C6F5-C6F5, are achieved at relatively low temperature (80 °C) and in short times using [MCl2(PhP
- Espinet, Pablo,Ponce-De-León, Jaime
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supporting information
p. 10875 - 10878
(2021/10/22)
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- Room-temperature Pd/Ag direct arylation enabled by a radical pathway
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Direct arylation is an appealing method for preparing π-conjugated materials, avoiding the prefunctionalization required for traditional cross-coupling methods. A major effort in organic electronic materials development is improving the environmental and economic impact of production; direct arylation polymerization (DArP) is an effective method to achieve these goals. Room-temperature polymerization would further improve the cost and energy efficiencies required to prepare these materials. Reported herein is new mechanistic work studying the underlying mechanism of room temperature direct arylation between iodobenzene and indole. Results indicate that room-temperature, Pd/Ag-catalyzed direct arylation systems are radical-mediated. This is in contrast to the commonly proposed two-electron mechanisms for direct arylation and appears to extend to other substrates such as benzo[b]thiophene and pentafluorobenzene.
- Luscombe, Christine K.,Mayhugh, Amy L.
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supporting information
p. 384 - 390
(2020/03/27)
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- Preparation method of para-substituted aryl compound
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The invention discloses a preparation method of a para-substituted aryl compound shown as a formula (I) which is described in the specfication. The preparation method is characterized by comprising the following step of: subjecting an aryl sulfonium salt shown as a formula (II) which is described in the specfication and boride to a coupling reaction in a solvent in an inert atmosphere under the action of alkali and a palladium catalyst to obtain the para-substituted aryl compound. According to the method, mono-substituted aromatic hydrocarbon is taken as a substrate, the aryl sulfonium salt isconstructed in situ, and the palladium catalyst catalyzes the aryl sulfonium salt constructed in situ to undergo the Suzuki-Miyaura coupling reaction, so a mono-substituted aromatic hydrocarbon para-arylation or alkenylation product is constructed quickly and efficiently. The method is mild in conditions, high in substrate universality and wide in tolerance of a heterocyclic coupling substrate.
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Paragraph 0265-0268
(2020/06/09)
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- Gold-Catalyzed Chemoselective Couplings of Polyfluoroarenes with Aryl Germanes and Downstream Diversification
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This report describes the chemoselective coupling of polyfluoroarenes with aryl germanes in the presence of aromatic C-I, C-Br, C-Cl, C-OTf, and C-SiMe3 groups, as well as demonstrates the further downstream diversification to give richly functionalized and highly fluorinated polyarenes. The strategy relies on an in situ Umpolung of the FnArH, followed by selective Au(I)/Au(III)-catalyzed coupling with electron-poor or-rich aryl germanes, even in the presence of challenging ortho-substituents, and widens the currently available coupling space in oxidative gold catalysis to previously inaccessible electron-poor/electron-poor biaryls.
- Dahiya, Amit,Fricke, Christoph,Schoenebeck, Franziska
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p. 7754 - 7759
(2020/04/30)
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- para-Selective arylation and alkenylation of monosubstituted arenes using thianthreneS-oxide as a transient mediator
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Using thianthreneS-oxide (TTSO) as a transient mediator,para-arylation and alkenylation of mono-substituted arenes have been demonstratedviaapara-selective thianthrenation/Pd-catalyzed thio-Suzuki-Miyaura coupling sequence under mild conditions. This reaction features a broad substrate scope, and functional group and heterocycle tolerance. The versatility of this approach was further demonstrated by late-stage functionalization of complex bioactive scaffolds, and direct synthesis of some pharmaceuticals, including Tetriprofen, Ibuprofen, Bifonazole, and LJ570.
- Chen, Xiao-Yue,Nie, Xiao-Xue,Wu, Yichen,Wang, Peng
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p. 5058 - 5061
(2020/05/18)
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- Light-Induced Tetrazole-Quinone 1,3-Dipolar Cycloadditions
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Quinones were firstly used as dipolarophiles in a photoclick 1,3-cycloaddition with 2,5-diaryltetrazoles, as photoactivatable predipoles, providing a novel and efficient access to three types of pyrazole-fused quinones (indazoledione derivatives). Distinc
- Ortiz-Rojano, Laura,Rojas-Martín, Jaime,Rodríguez-Diaz, Ciro,Carre?o, M. Carmen,Ribagorda, Maria
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supporting information
p. 15050 - 15054
(2019/11/13)
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- Pd/C as Heterogeneous Catalyst for the Direct Arylation of (Poly)fluorobenzenes
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The potential of the heterogeneous catalyst 10 % Pd/C in the direct arylation of (poly)fluorobenzene derivatives with aryl bromides has been investigated. In general, high yields of biaryl derivatives were obtained by using tri-, tetra-, and pentafluorobe
- Mao, Shuxin,Shi, Xinzhe,Soulé, Jean-Fran?ois,Doucet, Henri
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- Gold-Catalyzed Direct Oxidative Arylation with Boron Coupling Partners
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An efficient synthesis of biaryls through a gold-catalyzed oxidative cross-coupling of arenes with strong electron-deprived aryl boronates is presented herein. Regio- and chemocontrol are achieved by the selective activation of these coupling partners by gold at different oxidation states. Under reaction conditions devoid of basic additives or directing groups, the role of acetato ligand as an internal base has been revealed as a key parameter for expanding the reaction scope in these transformations.
- Hofer, Manuel,Genoux, Alexandre,Kumar, Roopender,Nevado, Cristina
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supporting information
p. 1021 - 1025
(2017/01/18)
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- Metal-Free Perfluoroarylation by Visible Light Photoredox Catalysis
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Visible light and eosin Y catalyze the direct arylation of simple arenes with fluorinated aryl bromides by a photoredox process. The reaction scope is broad in fluorinated compounds and arenes and the general and simple procedure provides a metal-free alt
- Meyer, Andreas U.,Slanina, Tomá?,Yao, Chang-Jiang,K?nig, Burkhard
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p. 369 - 375
(2016/01/12)
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- NHC Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions of Aryl Boronate Esters with Perfluorobenzenes
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An efficient Suzuki-Miyaura cross-coupling reaction of perfluorinated arenes with aryl boronate esters using NHC nickel complexes as catalysts is described. The efficiencies of different boronate esters (p-tolyl-Beg, p-tolyl-Bneop, p-tolyl-Bpin, p-tolyl-B
- Zhou, Jing,Berthel, Johannes H. J.,Kuntze-Fechner, Maximilian W.,Friedrich, Alexandra,Marder, Todd B.,Radius, Udo
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p. 5789 - 5794
(2016/07/14)
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- Weakly nucleophilic potassium aryltrifluoroborates in palladium-catalyzed Suzuki-Miyaura reactions? Relative reactivity of K[4-RC6F4BF3] and the role of silver-assistance in acceleration of transmetallation
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Small differences in the reactivity of weakly nucleophilic potassium aryltrifluoroborates are revealed in the silver-assisted Pd-catalyzed cross-coupling of K[4-RC6F4BF3] (R = H, Bu, MeO, EtO, PrO, iPrO, BuO, t-BuO, CH2=CHCH2O, PhCH2O, PhCH2CH2O, PhO, F, pyrazol-1-yl, pyrrol-1-yl, and indol-1-yl) with ArX (4-BrC6H4CH3, 4-IC6H4F and 3-IC6H4F). An assumed role of silver(I) compounds AgmY (Y = O, NO3, SO4, BF4, F) consists in polarization of the Pd-X bond in neutral complex ArPdLnX with the generation of the related transition state or formation of [ArPdLn][XAgmY] with a highly electrophilic cation and subsequent transmetallation with the weakly nucleophilic borate. Efficiency of AgmY as a polarizing agent decreases in order Ag2O > AgNO3 ≈ Ag2SO4 > Ag[BF4] > AgF. No clear correlation between the reactivity of K[4-RC6F4BF3] and substituent electron parameters, σI and σR °, of the aryl group 4-RC6F4 was found.
- Bardin, Vadim V.,Shabalin, Anton Yu,Adonin, Nicolay Yu
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supporting information
p. 608 - 616
(2015/06/08)
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- Palladium-Catalyzed Olefination and Arylation of Polyfluoroarenes Using Molecular Oxygen as the Sole Oxidant
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The palladium-catalyzed cross-dehydrogenative-coupling of polyfluoroarenes with alkenes or simple arenes has been developed. The approach is characterized by using atmospheric pressure of molecular oxygen as the sole oxidant, and provides a straightforward and environmentally benign route to functionalized polyfluoroarenes.
- Huang, Qiufeng,Zhang, Xinyu,Qiu, Lin,Wu, Jiajun,Xiao, Hanbing,Zhang, Xiaofeng,Lin, Shen
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p. 3753 - 3757
(2016/01/25)
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- A general direct arylation of polyfluoroarenes with heteroaryl and aryl chlorides catalyzed by palladium indolylphosphine complexes
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The first general examples of direct coupling of heteroaryl chlorides, especially substituted 2-pyridyl chlorides which were previously found to be problematic, with electron-deficient polyfluoroarenes are reported. Pd(OAc)2 associated with 3-(
- Yuen, On Ying,Charoensak, Mueangkaew,So, Chau Ming,Kuhakarn, Chutima,Kwong, Fuk Yee
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supporting information
p. 857 - 861
(2015/03/31)
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- Palladium-Catalyzed Zinc-Amide-Mediated C-H Arylation of Fluoroarenes and Heteroarenes with Aryl Sulfides
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C-H arylation of polyfluoroarenes and heteroarenes with aryl sulfides proceeds smoothly with the aid of a palladium-N-heterocyclic carbene catalyst. A bulky zinc amide, TMPZnCl an effective base to generate the corresponding arylzinc species in situ. This arylation protocol is practically much easier to perform than our previous method, which necessitates preparation of the arylzinc reagents in advance from the corresponding aryl halides. Aryl sulfides that are prepared through sulfur-specific reactions, such as SNAr sulfanylation and extended Pummerer reactions, undergo this direct arylation, offering interesting transformations that are otherwise difficult to achieve with conventional halogen-based organic synthesis.
- Otsuka, Shinya,Yorimitsu, Hideki,Osuka, Atsuhiro
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supporting information
p. 14703 - 14707
(2015/10/20)
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- Pd-catalyzed direct arylation of electron-deficient polyfluoroarenes with aryliodine(III) diacetates
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A Pd-catalyzed direct arylation of electron-deficient polyfluoroarenes with readily available aryliodine(III) diacetates was developed with moderate to good yields. The process exhibited good functional tolerance with respect to methyl, methoxy, bromo, chloro, trifluoromethyl, cyano, and aldehyde groups. Mechanistic studies revealed this coupling involved in situ generation of aryl iodide from heating-promoted decomposition of aryliodine(III) diacetate, followed by coupling with polyfluoroarenes substrates to afford the desired products.
- Fu, Zhengjiang,Xiong, Qiheng,Zhang, Wenbiao,Li, Zhaojie,Cai, Hu
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supporting information
p. 123 - 126
(2015/02/05)
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- Palladium-catalyzed coupling reaction of perfluoroarenes with diarylzinc compounds
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This report describes the first Pd0-catalyzed cross-coupling of hexafluorobenzene (C6F6) with diarylzinc compounds to give a variety of pentafluorophenyl arenes. This reaction could be applied to other perfluoroarenes, such as octafluorotoluene, pentafluoropyridine, and perfluoronaphthalene, to give the corresponding polyfluorinated coupling products. The optimal ligand in this catalytic reaction was PCy3, and lithium iodide was indispensable as an additive for the coupling reaction. One of the roles of lithium iodide in this catalytic reaction was to promote the oxidative addition of one Ci£F bond of C6F 6 to palladium. Stoichiometric reactions revealed that an expected oxidative-addition product, trans-[Pd(C6F5)I(PCy 3)2], generated from the reaction of [Pd(PCy 3)2] with C6F6 in the presence of lithium iodide, was not involved in the catalytic cycle. Instead, a transient three-coordinate, monophosphine-ligated species, [Pd(C6F 5)I(PCy3)], emerged as a potential intermediate in the catalytic cycle. Therefore, we isolated a novel PdII complex, [Pd(C6F5)I(PCy3)(py)], in which pyridine (py) acted as a labile ligand to generate the transient species. In fact, in the presence of lithium iodide, this PdII complex was found to react smoothly with diphenylzinc to give the desired pentafluorophenyl benzene, whereas the same reaction conducted in the absence of lithium iodide resulted in a decreased yield of pentafluorophenyl benzene, which indicated that the other role of lithium iodide was to enhance the reactivity of the organozinc species during the transmetalation step.
- Ohashi, Masato,Doi, Ryohei,Ogoshi, Sensuke
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supporting information
p. 2040 - 2048
(2014/03/21)
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- Transition-metal-free synthesis of fluorinated arenes from perfluorinated arenes coupled with grignard reagents
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A simple method to obtain organofluorine compounds from perfluorinated arenes coupled with Grignard reagents in the absence of a transition-metal catalyst was reported. In particular, the perfluorinated arenes could react not only with aryl Grignard reagents but also with alkyl Grignard reagents in moderate to good yields.
- Sun, Yunqiang,Sun, Hongjian,Jia, Jiong,Du, Aiqin,Li, Xiaoyan
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supporting information
p. 1079 - 1081
(2014/03/21)
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- Palladium-catalyzed direct arylation of polyfluoroarene and facile synthesis of liquid crystal compounds
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A convenient approach has been developed to prepare polyfluorobiphenyl by Pd(OAc)2/PCy3-catalyzed direct arylation of polyfluoroarenes with aromatic halides in the presence of Cs2CO 3 as base and toluene as solvent. In most cases, the desired arylated products of aromatic bromides were obtained in good to excellent yield at 80°C, and aryl chlorides also gave modest to good yields of arylated products at 110°C. According to this efficient C - C bondforming method, polyfluorobiphenyl liquid crystal compounds were prepared by Pd-catalyzed direct arylation reactions of polyfluoroarenes with long alkyl chain substituted aryl bromides in 62-96% yield. Copyright
- Ma, Xiaowei,Liu, Yan,Liu, Ping,Xie, Jianwei,Dai, Bin,Liu, Zhiyong
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p. 180 - 185
(2014/03/21)
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- An organic cation as a silver(i) analogue for the arylation of sp 2 and sp3 C-H bonds with iodoarenes
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Reactions promoted by stoichiometric amounts of silver salts suffer from high cost, limited availability and raise environmental concerns. This manuscript describes studies leading to the discovery of a general replacement for silver with an inexpensive and convenient organic salt in palladium catalyzed direct C(sp2)-H and C(sp3)-H arylation reactions.
- Arroniz, Carlos,Denis, J. Gabriel,Ironmonger, Alan,Rassias, Gerasimos,Larrosa, Igor
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p. 3509 - 3514
(2014/08/18)
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- TBu3P-Coordinated 2-Phenylaniline-Based Palladacycle Complexes as Precatalyst for Pd-Catalyzed Coupling Reactions of Aryl Halides with Polyfluoroarenes by a C-H Activation Strategy
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A tBu3P-coordinated 2-phenylaniline-based palladacycle complex was demonstrated to be an efficient precatalyst for Pd-catalyzed coupling reactions of aryl halides with polyfluoroarenes that operates through a C-H activation strategy. The ready
- Zhang, Hong-Hai,Dong, Jie,Hu, Qiao-Sheng
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p. 1327 - 1332
(2015/10/05)
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- A cooperative Pd-Cu system for direct C-H bond arylation
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A novel and efficient method for C-H arylation using well-defined Pd- and Cu-NHC systems has been developed. This process promotes the challenging construction of C-C bonds from arenes or heteroarenes using aryl bromides and chlorides. Mechanistic studies
- Lesieur, Mathieu,Lazreg, Fa?ma,Cazin, Catherine S. J.
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supporting information
p. 8927 - 8929
(2014/08/05)
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- A General Suzuki-Miyaura Coupling of Aryl Chlorides with Potassium Aryltrifluoroborates in Water Catalyzed by an Efficient CPCy Phendole-phos-Palladium Complex
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General examples of the palladium-catalyzed Suzuki-Miyaura cross-coupling of aryl or heteroaryl chlorides with potassium aryl- or heteroaryltrifluoroborates in water are presented. The palladium complex comprising of palladium(II) acetate and 'CPCy Phendole-phos' is found to be a highly effective catalyst system for this coupling reaction with low catalyst loading (down to 0.005 mol% Pd).
- Yuen, On Ying,Wong, Shun Man,Chan, Kin Fai,So, Chau Ming,Kwong, Fuk Yee
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supporting information
p. 2826 - 2832
(2015/10/21)
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- Palladium-catalyzed desulfitative direct C-H arylation of electron-deficient polyfluoroarenes with sodium arenesulfinates
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The palladium-catalyzed direct arylation of electron-deficient polyfluorobenzenes was developed in the presence of silver carbonate and trisodium phosphate. This protocol allowed use of both electron- deficient and electron-rich aromatic sulfinic acid sodium salts as arylating reagents for the direct arylation of a variety of polyfluoroarenes to produce fluorobiaryls in good to excellent yields, providing a complement to the existing methods for the direct arylation of polyfluoroarenes.
- Miao, Tao,Wang, Lei
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p. 429 - 436
(2014/05/20)
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- Preparation of fluorinated biaryls through direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates
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The direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates gave the desired products of fluorinated biaryls in good to excellent yields. A diverse set of important functional groups including methoxy, aldehyde, ester, nitro and halide can be well tolerated in the protocol.
- Fang, Xin,Huang, Yuanyuan,Chen, Xiaoqing,Lin, Xiaoxi,Bai, Zhengshuai,Huang, Kuo-Wei,Yuan, Yaofeng,Weng, Zhiqiang
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- Pd-catalyzed decarboxylative cross-coupling of perfluorobenzoic acids with simple arenes
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Using a Pd/Ag bimetallic system, arylations of simple arenes with perfluorobenzoic acids have been achieved by decarboxylative C-H bond functionalization, providing the desired cross-coupling products in moderate to good yields. These straightforward protocols provide new and efficient methods for the synthesis of fluorobiphenyl scaffolds under simple and mild conditions.
- Luo, Hai-Qing,Dong, Wen,Loh, Teck-Peng
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supporting information
p. 2833 - 2836
(2013/06/05)
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- Scope of direct arylation of fluorinated aromatics with aryl sulfonates
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The scope and limitations of direct arylation of fluorinated aromatics with aryl sulfonates was examined. Pd(OAc)2, in the presence of MePhos and KOAc in THF, efficiently catalyzed the direct arylation of fluoro aromatics with aryl triflates un
- Chang, Joyce Wei Wei,Chia, Eugene Yurong,Chai, Christina Li Lin,Seayad, Jayasree
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p. 2289 - 2299
(2012/04/10)
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- Pd-catalyzed direct arylation of polyfluoroarenes on water under mild conditions using PPh3 ligand
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We report a Pd-catalyzed direct arylation of polyfluoroarenes with aryl iodides. The advantages of this reaction are its high reaction efficiency, excellent functional group compatibility, mild reaction conditions (70 °C), inexpensive PPh3 ligand, and use of pure water as reaction medium. The usefulness of this reaction has also been demonstrated by rapid preparation of highly functionalized polyfluoroarenes via iterative Pd-catalyzed C-H bond functionalization.
- Chen, Fei,Min, Qiao-Qiao,Zhang, Xingang
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experimental part
p. 2992 - 2998
(2012/05/04)
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- 1,2,3-triazolin-5-ylidenes: Synthesis of hetero-bis(carbene) Pd(II) complexes, determination of donor strengths, and catalysis
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A series of hetero-bis(carbene) complexes trans-[PdBr2( iPr2-bimy)(trz)] 1-4 (iPr2-bimy = 1,3-diisopropylbenzimidazolin-2-ylidene; trz = 1,2,3-triazolin-5-ylidene) bearing the constant iPr2-bimy and varying mesoionic 1,2,3-triazolin-5-ylidenes with different N-substituents has been synthesized as complex probes. Their 13C NMR spectroscopic evaluation shows that mesoionic 1,2,3-triazolin-5-ylidenes are, in general, stronger donors than classical NHCs, while weaker than some nonclassical NHCs, such as pyrazolin-3-ylidenes and mesoionic imidazolin-4-ylidenes. More importantly and for the first time, this methodology proves useful in establishing substituent effects in the donating abilities of 1,2,3-triazolin-5-ylidenes on a finer level. In addition, the trifluoroacetato analogues [Pd(O2CCF 3)2(iPr2-bimy)(trz)] 5-7 have been synthesized through salt metathesis of 1, 2, and 4 with AgO2CCF 3. The catalytic activities of complexes 1, 2, and 4-7 were examined in the direct arylation of pentafluorobenzene. Complexes bearing less donating trz ligands perform better in this catalysis, and trifluoroacetato complexes outperformed their bromido analogues.
- Yuan, Dan,Huynh, Han Vinh
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experimental part
p. 405 - 412
(2012/04/23)
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- Pyrazolin-5-ylidene palladium(II) complexes: Synthesis, characterization, and application in the direct arylation of pentafluorobenzene
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Ten palladium(II) complexes bearing a pyrazolin-5-ylidene ligand have been synthesized by oxidative addition and silver carbene transfer pathways. The weakly bound acetonitrile ligand in the initially obtained trans-[PdBr 2(MeCN)(Pyry)] complex (6, Pyry = 1-phenyl-2,3-dimethylpyrazolin-5- ylidene) could be replaced by other donor ligands, and additional NHC ligands were introduced either by silver carbene transfer reactions or via reaction with in situ generated free carbenes. Using our previously reported 13C NMR-based electronic parameter, the pyrazolin-5-ylidene ligand is estimated to be among the most strongly donating ligands on our scale so far. The complexes obtained were employed as catalysts for the direct arylation of pentafluorobenzene with moderate to good yields under optimized conditions.
- Bernhammer, Jan C.,Huynh, Han Vinh
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experimental part
p. 5121 - 5130
(2012/09/05)
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- Discovery of a full-color-tunable fluorescent core framework through direct C-H (hetero)arylation of N-heterocycles
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All the colors of the rainbow! A full coverage of emission wavelengths in the visible region (405-616 nm) with large Stokes shifts in C3-Indo-Fluor may be straightforwardly and succinctly achieved by the palladium-catalyzed direct C-H arylation of indolizines at the C3 position of the pyrrole ring (see figure). The fluorophores have successfully marked A375 cells. Copyright
- Liu, Bo,Wang, Zhi,Wu, Ningjie,Li, Mingliang,You, Jingsong,Lan, Jingbo
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supporting information; experimental part
p. 1599 - 1603
(2012/03/10)
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- Decarboxylative biaryl synthesis in a continuous flow reactor
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A practical protocol was developed that allows performing decarboxylative cross-coupling reactions in continuous flow reactors. Various biaryls were thus synthesized from aromatic carboxylic acids and aryl triflates using a Cu/Pd-catalyst system.
- Lange, Paul P.,Goossen, Lukas J.,Podmore, Philip,Underwood, Toby,Sciammetta, Nunzio
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supporting information; experimental part
p. 3628 - 3630
(2011/05/02)
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- Palladium-catalyzed cross-coupling of polyfluoroarenes with simple arenes
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The most efficient method to construct biaryls is the direct dehydrogenative cross-coupling of two different aromatic rings. Such an ideal cross arylation starting from distinct polyfluoroarenes and simple arenes was presented. The selectivity of the cross-coupling was controlled by both of the electronic property of fluoroarenes and steric hindrance of simple arenes. Diisopropyl sulfide was essential to promote the efficacy.
- Li, Hu,Liu, Jia,Sun, Chang-Liang,Li, Bi-Jie,Shi, Zhang-Jie
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supporting information; experimental part
p. 276 - 279
(2011/04/17)
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- Pd(OAc)2-catalyzed oxidative C-H/C-H cross-coupling of electron-deficient polyfluoroarenes with simple arenes
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Pd(OAc)2-catalyzed intermolecular C-H/C-H cross-coupling reactions between electron-deficient polyfluoroarenes and simple arenes for the synthesis of fluorinated biaryls have been developed. Deuterium-labeling experiments suggested that C-H bon
- Wei, Ye,Su, Weiping
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supporting information; experimental part
p. 16377 - 16379
(2011/02/22)
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- Pd-catalyzed decarboxylative cross coupling of potassium polyfluorobenzoates with aryl bromides, chlorides, and triflates
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Chemical Equetion Presentation Pd-catalyzed decarboxylative cross coupling of potassium polyfluorobenzoates with aryl bromides, chlorides, and triflates is achieved by using diglyme as the solvent. The reaction is useful for synthesis of polyfluorobiaryls
- Shang, Rui,Xu, Qing,Jiang, Yuan-Ye,Wang, Yan,Liu, Lei
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supporting information; experimental part
p. 1000 - 1003
(2010/06/16)
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- Room-temperature direct arylation of polyfluorinated arenes under biphasic conditions
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Figure presented New biphasic conditions for the palladium-catalyzed direct arylation of electron-poor fluorinated arenes have been developed. Taking advantage of biphasic chemistry, the use of an immiscible mixture of water and an organic solvent allows
- Rene, Olivier,Fagnou, Keith
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supporting information; experimental part
p. 2116 - 2119
(2010/06/20)
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- Copper-catalyzed decarboxylase cross-coupling of potassium polyfluorobenzoates with aryl iodides and bromides
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Chemical Equitation Presentation For copper only: The decarboxylative cross-coupling of readily accessible and nonvolatile potassium polyfluorobenzoates with aryl iodides and bromides using a copper catalyst provides poly-fluorobiaryls and polyfluorostilb
- Shang, Rui,Fu, Yao,Wang, Yan,Xu, Qing,Yu, Hai-Zhu,Liu, Lei
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supporting information; experimental part
p. 9350 - 9354
(2010/03/04)
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