- Palladium-catalyzed ortho-C-H arylation of acetophenone oxime ethers with aryl pinacol boronic esters
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We report an efficient palladium-catalyzed ortho-C-H arylation of acetophenone oxime ethers with aryl pinacol boronic esters, leading to the synthesis of biaryl derivatives in good yields. Sequential process of iridiumcatalyzed C-H borylation and palladiu
- Reddy, Daggula Mallikarjuna,Wang, Shao-Chien,Du, Kai,Lee, Chin-Fa
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- Photochemical and electrochemical C-N borylation of arylhydrazines
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The C-N borylation of arylhydrazine hydrochlorides with bis(pinacolato)diboron was achieved under photochemical and electrochemical conditions, respectively. This novel and scalable transformation provides two efficient and mild transition-metal-free synt
- Du, Linlin,Sun, Li,Zhang, Hua
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supporting information
p. 1716 - 1719
(2022/02/21)
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- Cu-mediated: vs. Cu-free selective borylation of aryl alkyl sulfones
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A Cu-catalysed borylation of aryl alkyl sulfones was developed for the high yield synthesis of versatile arylboronic esters using a readily prepared NHC-Cu catalyst. In addition, the selective cleavage of either alkyl(C)-sulfonyl or aryl(C)-sulfonyl bonds
- Hu, Jiefeng,Huang, Mingming,Marder, Todd B.,Radius, Udo,Tang, Man,Westcott, Stephen A.
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supporting information
p. 395 - 398
(2022/01/19)
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- Mono-Phosphine Metal-Organic Framework-Supported Cobalt Catalyst for Efficient Borylation Reactions
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We report a metal-organic framework (MOF) supported monoligated phosphine-cobalt complex, which is an active heterogeneous catalyst for aromatic C?H borylation and alkene hydroboration. The mono(phosphine)-Co catalyst (MOF?P?Co) was prepared by metalation of a porous triarylphosphine-functionalized MOF (MOF?P) with CoCl2 followed by activation with NaEt3BH. The MOF catalyst has a broad substrate scope with excellent functional group tolerance to afford arene- and alkyl-boronate esters in excellent yields and selectivity. MOF?P?Co gave a turnover number (TON) of 30,000 and could be recycled and reused at least 13 times in arene C?H borylation. Importantly, the attempt to prepare the homogeneous control (Ph3P?Co) using triphenylphosphine was unsuccessful due to the facile disproportionation reactions or intermolecular ligand exchanges in the solution. In contrast, the site isolation of the active mono(phosphine)-Co species within the MOF affords the robust and coordinatively unsaturated metal complexes, allowing to explore their catalytic properties and the reaction mechanism.
- Akhtar, Naved,Antil, Neha,Balendra,Begum, Wahida,Chauhan, Manav,Gupta, Poorvi,Kumar, Ajay,Malik, Jaideep,Manna, Kuntal,Newar, Rajashree
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supporting information
(2022/03/15)
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- Merging Iridium-Catalyzed C-H Borylations with Palladium-Catalyzed Cross-Couplings Using Triorganoindium Reagents
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A versatile and efficient method to prepare borylated arenes furnished with alkyl, alkenyl, alkynyl, aryl, and heteroaryl functional groups is developed by merging Ir-catalyzed C-H borylations (CHB) with a chemoselective palladium-catalyzed cross-coupling of triorganoindium reagents (Sarandeses-Sestelo coupling) with aryl halides bearing a boronic ester substituent. Using triorganoindium cross-coupling reactions to introduce unsaturated moieties enables the synthesis of borylated arenes that would be difficult to access through the direct application of the CHB methodology. The sequential double catalyzed procedure can be also performed in one vessel.
- Jayasundara, Chathurika R. K.,Gil-Negrete, José M.,Montero Bastidas, Jose R.,Chhabra, Arzoo,Martínez, M. Montserrat,Pérez Sestelo, José,Smith, Milton R.,Maleczka, Robert E.
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p. 751 - 759
(2021/12/27)
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- Unreactive C-N Bond Activation of Anilines via Photoinduced Aerobic Borylation
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Unreactive C-N bond activation of anilines was achieved by photoinduced aerobic borylation. A diverse range of tertiary and secondary anilines were converted to aryl boronate esters in moderate to good yields with wide functional group tolerance under simple and ambient photochemical conditions. This transformation achieved the direct and facile C-N bond activation of unreactive anilines, providing a convenient and practical route transforming widely available anilines into useful aryl boronate esters.
- Ji, Shuohan,Qin, Shengxiang,Yin, Chunyu,Luo, Lu,Zhang, Hua
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supporting information
p. 64 - 68
(2021/12/27)
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- Base-Free Pd-Catalyzed C?Cl Borylation of Fluorinated Aryl Chlorides
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Catalytic C?X borylation of aryl halides containing two ortho-fluorines has been found to be challenging, as most previous methods require stoichiometric amounts of base and the polyfluorinated aryl boronates suffer from protodeboronation, which is accele
- Budiman, Yudha P.,Lorenzen, Sabine,Liu, Zhiqiang,Radius, Udo,Marder, Todd B.
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supporting information
p. 3869 - 3874
(2021/02/03)
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- Engaging Ag(0) single atoms in silver(I) salts-mediated C-B and C-S coupling under visible light irradiation
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Silver(I) salts were found active in the borylation and sulfenylation of aryl iodides under visible light irradiation. The optimized borylation protocol using AgF did not need any additive, operated under very mild conditions, and well tolerated a broad scope of substrates and boron sources. Formation of Ag(0) single atoms (AgSAs) during the borylation reactions was examined using high-angle annular dark field aberration-corrected scanning transmission electron microscope (HAADF AC-STEM) and electron paramagnetic resonance (EPR). The activities of the silver(I) salts were affected by the anions and could be associated with their abilities in formation of AgSAs during the reactions. Kinetic studies showed that the deiodination rate was linearly correlated with the loading of AgSAs, and hence AgSAs were the true catalytic centers for the 1e?-reduction of the C-I moieties. The oxidation state of AgSAs kept 0 in both the resting and the working states. A “work-in-tandem” mechanism involving AgSAs as the catalytic centers and AgNPs as the light absorber to achieve the borylation of aryl iodides under visible light irradiation is proposed. The current approach not only provides an alternative system for borylation and sulfenylation of aryl iodides, but also reveals a new activity of silver(I) salts involving AgSAs under visible light irradiation.
- Cui, Enxin,Guo, Lirong,Li, Haibin,Qiao, Dan,Tung, Chen-Ho,Wang, Yifeng
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p. 255 - 263
(2021/09/06)
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- Preparation method of aryl borate catalyzed by cesium neovalerate
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The preparation method comprises the following steps: dissolving a compound of formula (I) and a diboron compound in an organic solvent, then adding an organic solvent dissolved with cesium neovalerate, palladium acetate and triphenylphosphine, and carrying out reaction to obtain aryl boronic acid ester. In the formula (I) R1. R2, R3, R4 and R5 are each independently selected from H, C. 1 - C10 Alkyl group, C2 - C10 Alkenyl, C2 - C10 Alkynyl group, C1 - C10 Alkoxy, hydroxy, hydroxy-substituted C1 - C10 Alkyl, phenyl, C1 - C10 Alkylamino. X Is selected from F, Cl, Br, i. The preparation method has the advantages of low production cost, high product yield, high purity, simple operation and suitability for industrial mass production.
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Paragraph 0038-0041
(2021/09/22)
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- Design, Synthesis and Biological Evaluation of Boron-Containing Macrocyclic Polyamine Dimers and Their Zinc(II) Complexes for Boron Neutron Capture Therapy
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Boron neutron capture therapy (BNCT) is considered to have potential for cancer therapy based on the nuclear reaction between boron (10B) atoms and thermal neutrons, yielding 4He2+ (α) and 7Li3+ ions.
- Aoki, Shin,Sakurai, Yoshinori,Suzuki, Minoru,Tanaka, Tomohiro,Ueda, Hiroki
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- Cross-Coupling through Ag(I)/Ag(III) Redox Manifold
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In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e? redox steps. Definite proof is herein provided for the required elementary steps to accomplish the oxidative trifluoromethylation of arenes through AgI/AgIII redox catalysis (i. e. CEL coupling), namely: i) easy AgI/AgIII 2e? oxidation mediated by air; ii) bpy/phen ligation to AgIII; iii) boron-to-AgIII aryl transfer; and iv) ulterior reductive elimination of benzotrifluorides from an [aryl-AgIII-CF3] fragment. More precisely, an ultimate entry and full characterization of organosilver(III) compounds [K]+[AgIII(CF3)4]? (K-1), [(bpy)AgIII(CF3)3] (2) and [(phen)AgIII(CF3)3] (3), is described. The utility of 3 in cross-coupling has been showcased unambiguously, and a large variety of arylboron compounds was trifluoromethylated via [AgIII(aryl)(CF3)3]? intermediates. This work breaks with old stereotypes and misconceptions regarding the inability of Ag to undergo cross-coupling by itself.
- Demonti, Luca,Mézailles, Nicolas,Nebra, Noel,Saffon-Merceron, Nathalie
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supporting information
p. 15396 - 15405
(2021/10/12)
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- Sequential Ir/Cu-Mediated Method for the Meta-Selective C-H Radiofluorination of (Hetero)Arenes
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This article describes a sequential Ir/Cu-mediated process for the meta-selective C-H radiofluorination of (hetero)arene substrates. In the first step, Ir-catalyzed C(sp2)-H borylation affords (hetero)aryl pinacolboronate (BPin) esters. The intermediate organoboronates are then directly subjected to copper-mediated radiofluorination with [18F]tetrabutylammonium fluoride to afford fluorine-18 labeled (hetero)arenes in high radiochemical yield and radiochemical purity. This entire process is performed on a benchtop without Schlenk or glovebox techniques and circumvents the need to isolate (hetero)aryl boronate esters. The reaction was automated on a TracerLab FXFN module with 1,3-dimethoxybenzene and a meta-tyrosine derivative. The products, [18F]1-fluoro-3,5-dimethoxybenzene and an 18F-labeled meta-tyrosine derivative, were obtained in 37 ± 5% isolated radiochemical yield and >99% radiochemical purity and 25% isolated radiochemical yield and 99% radiochemical purity, and 0.52 Ci/μmol (19.24 GBq/μmol) molar activity (Am), respectively.
- Wright, Jay S.,Sharninghausen, Liam S.,Preshlock, Sean,Brooks, Allen F.,Sanford, Melanie S.,Scott, Peter J. H.
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supporting information
p. 6915 - 6921
(2021/05/29)
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- Visible-Light-Induced Ni-Catalyzed Radical Borylation of Chloroarenes
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A highly selective and general photoinduced C-Cl borylation protocol that employs [Ni(IMes)2] (IMes = 1,3-dimesitylimidazoline-2-ylidene) for the radical borylation of chloroarenes is reported. This photoinduced system operates with visible light (400 nm) and achieves borylation of a wide range of chloroarenes with B2pin2 at room temperature in excellent yields and with high selectivity, thereby demonstrating its broad utility and functional group tolerance. Mechanistic investigations suggest that the borylation reactions proceed via a radical process. EPR studies demonstrate that [Ni(IMes)2] undergoes very fast chlorine atom abstraction from aryl chlorides to give [NiI(IMes)2Cl] and aryl radicals. Control experiments indicate that light promotes the reaction of [NiI(IMes)2Cl] with aryl chlorides generating additional aryl radicals and [NiII(IMes)2Cl2]. The aryl radicals react with an anionic sp2-sp3 diborane [B2pin2(OMe)]- formed from B2pin2 and KOMe to yield the corresponding borylation product and the [Bpin(OMe)]?- radical anion, which reduces [NiII(IMes)2Cl2] under irradiation to regenerate [NiI(IMes)2Cl] and [Ni(IMes)2] for the next catalytic cycle.
- Tian, Ya-Ming,Guo, Xiao-Ning,Krummenacher, Ivo,Wu, Zhu,Nitsch, J?rn,Braunschweig, Holger,Radius, Udo,Marder, Todd B.
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supporting information
p. 18231 - 18242
(2020/11/02)
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- Visible Light-Induced Borylation of C-O, C-N, and C-X Bonds
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Boronic acids are centrally important functional motifs and synthetic precursors. Visible light-induced borylation may provide access to structurally diverse boronates, but a broadly efficient photocatalytic borylation method that can effect borylation of a wide range of substrates, including strong C-O bonds, remains elusive. Herein, we report a general, metal-free visible light-induced photocatalytic borylation platform that enables borylation of electron-rich derivatives of phenols and anilines, chloroarenes, as well as other haloarenes. The reaction exhibits excellent functional group tolerance, as demonstrated by the borylation of a range of structurally complex substrates. Remarkably, the reaction is catalyzed by phenothiazine, a simple organic photocatalyst with MW 200 that mediates the previously unachievable visible light-induced single electron reduction of phenol derivatives with reduction potentials as negative as approximately - 3 V versus SCE by a proton-coupled electron transfer mechanism. Mechanistic studies point to the crucial role of the photocatalyst-base interaction.
- Arman, Hadi D.,Dang, Hang. T.,Haug, Graham C.,He, Ru,Jin, Shengfei,Larionov, Oleg V.,Nguyen, Viet D.,Nguyen, Vu T.,Schanze, Kirk S.
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supporting information
(2020/02/04)
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- Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations
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Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.
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Page/Page column 29-33; 51-53; 86-88; 99-101
(2020/06/03)
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- Single-Site Cobalt-Catalyst Ligated with Pyridylimine-Functionalized Metal-Organic Frameworks for Arene and Benzylic Borylation
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We report a highly active single-site heterogeneous cobalt-catalyst based on a porous and robust pyridylimine-functionalized metal-organic frameworks (pyrim-MOF) for chemoselective borylation of arene and benzylic C-H bonds. The pyrim-MOF having UiO-68 topology, constructed from zirconium-cluster secondary building units and pyridylimine-functionalized dicarboxylate bridging linkers, was metalated with CoCl2 followed by treatment of NaEt3BH to give the cobalt-functionalized MOF-catalyst (pyrim-MOF-Co). Pyrim-MOF-Co has a broad substrate scope, allowing the C-H borylation of halogen-, alkoxy-, alkyl-substituted arenes as well as heterocyclic ring systems using B2pin2 or HBpin (pin = pinacolate) as the borylating agent to afford the corresponding arene- or alkyl-boronate esters in good yields. Pyrim-MOF-Co gave a turnover number (TON) of up to 2500 and could be recycled and reused at least 9 times. Pyrim-MOF-Co was also significantly more robust and active than its homogeneous control, highlighting the beneficial effect of active-site isolation within the MOF framework that prevents intermolecular decomposition. The experimental and computational studies suggested (pyrim?-)CoI(THF) as the active catalytic species within the MOF, which undergoes a mechanistic pathway of oxidative addition, turnover limiting σ-bond metathesis, followed by reductive elimination to afford the boronate ester.
- Akhtar, Naved,Antil, Neha,Balendra,Begum, Wahida,Kumar, Ajay,Manna, Kuntal,Newar, Rajashree,Shukla, Sakshi
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supporting information
p. 10473 - 10481
(2020/08/05)
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- Highly Selective and Divergent Acyl and Aryl Cross-Couplings of Amides via Ir-Catalyzed C-H Borylation/N-C(O) Activation
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Herein, we demonstrate that amides can be readily coupled with nonactivated arenes via sequential Ir-catalyzed C-H borylation/N-C(O) activation. This methodology provides facile access to biaryl ketones and biaryls by the sterically controlled Ir-catalyzed C-H borylation and divergent acyl and decarbonylative amide N-C(O) and C-C activation. The methodology diverts the traditional acylation and arylation regioselectivity, allowing us to directly utilize readily available arenes and amides to produce valuable ketone and biaryl motifs.
- Gao, Pengcheng,Szostak, Michal
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supporting information
p. 6010 - 6015
(2020/07/30)
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- Visible- And UV-Light-Induced Decarboxylative Radical Reactions of Benzoic Acids Using Organic Photoredox Catalysts
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Photoinduced decarboxylative radical reactions of benzoic acids with electron-deficient alkenes, diborane, and acetonitrile under organic photoredox catalysis conditions and mild heating afforded adducts, arylboronate esters, and the reduction product, respectively. The reaction is thought to involve single-electron transfer promoted the generation of aryl radicals via decarboxylation. A diverse range of benzoic acids were found to be suitable substrates for this photoreaction. Only our two-molecule organic photoredox system can work well for the direct photoinduced decarboxylation of benzoic acids.
- Kubosaki, Suzuka,Takeuchi, Haruka,Iwata, Yutaka,Tanaka, Yosuke,Osaka, Kazuyuki,Yamawaki, Mugen,Morita, Toshio,Yoshimi, Yasuharu
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p. 5362 - 5369
(2020/05/19)
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- Luminescent tungsten(vi) complexes as photocatalysts for light-driven C-C and C-B bond formation reactions
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The realization of photocatalysis for practical synthetic application hinges on the development of inexpensive photocatalysts which can be prepared on a large scale. Herein an air-stable, visible-light-absorbing photoluminescent tungsten(vi) complex which can be conveniently prepared at the gram-scale is described. This complex could catalyse photochemical organic transformation reactions including borylation of aryl halides, such as aryl chloride, reductive coupling of benzyl bromides for C-C bond formation, reductive coupling of phenacyl bromides, and decarboxylative coupling of redox-active esters of alkyl carboxylic acid with high product yields and broad functional group tolerance.
- Chan, Kaai-Tung,Che, Chi-Ming,Du, Lili,Liu, Yungen,Phillips, David Lee,To, Wai-Pong,Tong, Glenna So Ming,Wu, Liang-Liang,Yu, Daohong
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p. 6370 - 6382
(2020/07/15)
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- Facile and economical Miyaura borylation and one-pot Suzuki–Miyaura cross-coupling reaction
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Facile and economical method for Miyaura borylation reaction between B2pin2 and aryl bromides is reported. The catalytic system containing 2 mol% PdCl2(PPh3)2 and KOAc serves to enable borylations to occur under solvent-free and atmospheric conditions. The developed protocol can be applied to synthesize symmetrical and unsymmetrical biaryls via one-pot two-step Suzuki–Miyaura cross-coupling reaction and also offers the up-scalability.
- Boontiem, Phongsakorn,Kiatisevi, Supavadee
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- Direct C?H Borylation of Arenes Catalyzed by Saturated Hydride-Boryl-Iridium-POP Complexes: Kinetic Analysis of the Elemental Steps
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The saturated trihydride IrH3{κ3-P,O,P-[xant(PiPr2)2]} (1; xant(PiPr2)2=9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) activates the B?H bond of two molecules of pinacolborane (HBpin) to give H2, the hydride-boryl derivatives IrH2(Bpin){κ3-P,O,P-[xant(PiPr2)2]} (2) and IrH(Bpin)2{κ3-P,O,P-[xant(PiPr2)2]} (3) in a sequential manner. Complex 3 activates a C?H bond of two molecules of benzene to form PhBpin and regenerates 2 and 1, also in a sequential manner. Thus, complexes 1, 2, and 3 define two cycles for the catalytic direct C?H borylation of arenes with HBpin, which have dihydride 2 as a common intermediate. C?H bond activation of the arenes is the rate-determining step of both cycles, as the C?H oxidative addition to 3 is faster than to 2. The results from a kinetic study of the reactions of 1 and 2 with HBpin support a cooperative function of the hydride ligands in the B?H bond activation. The addition of the boron atom of the borane to a hydride facilitates the coordination of the B?H bond through the formation of κ1- and κ2-dihydrideborate intermediates.
- Esteruelas, Miguel A.,Martínez, Antonio,Oliván, Montserrat,O?ate, Enrique
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supporting information
p. 12632 - 12644
(2020/09/09)
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- Catalytic C?H Borylation Using Iron Complexes Bearing 4,5,6,7-Tetrahydroisoindol-2-ide-Based PNP-Type Pincer Ligand
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Catalytic C?H borylation has been reported using newly designed iron complexes bearing a 4,5,6,7-tetrahydroisoindol-2-ide-based PNP pincer ligand. The reaction tolerated various five-membered heteroarenes, such as pyrrole derivatives, as well as six-membered aromatic compounds, such as toluene. Successful examples of the iron-catalyzed sp3 C?H borylation of anisole derivatives were also presented.
- Kato, Takeru,Kuriyama, Shogo,Nakajima, Kazunari,Nishibayashi, Yoshiaki
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supporting information
p. 2097 - 2101
(2019/05/28)
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- A mesoporous NNN-pincer-based metal-organic framework scaffold for the preparation of noble-metal-free catalysts
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Through topology-guided synthesis, a Zr-based mesoporous MOF was successfully constructed, adopting a β-cristobalite-type structure. The MOF is embedded with well-arranged terpyridine coordination sites for facile post-synthetic metalation, and can be effectively used as a general scaffold for the preparation of noble-metal-free catalysts. For instance, the scaffolded metal@MOF material exhibits highly efficient catalytic activity for alkene epoxidation and arene borylation.
- Zhang, Yingmu,Li, Jialuo,Yang, Xinyu,Zhang, Peng,Pang, Jiandong,Li, Bao,Zhou, Hong-Cai
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p. 2023 - 2026
(2019/02/19)
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- Expanding the Variety of Zirconium-based Inorganic Building Units for Metal–Organic Frameworks
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Two new zirconium-based metal–organic frameworks with the composition [Zr6O4(OH)4(OAc)6(BDC)3] (CAU-26) and [Zr5O4(OH)4(OAc)4(BDC)2] (CAU-27) are
- Leubner, Sebastian,Zhao, Haishuang,Van Velthoven, Niels,Henrion, Micka?l,Reinsch, Helge,De Vos, Dirk E.,Kolb, Ute,Stock, Norbert
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supporting information
p. 10995 - 11000
(2019/07/12)
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- Visible-Light-Induced Organocatalytic Borylation of Aryl Chlorides
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The preparation of arylboronates from unactivated aryl chlorides in a transition-metal-free manner is rather challenging. There are only few examples to achieve this goal by using ultraviolet irradiation. Based on the mechanistic understanding of the diboron/methoxide/pyridine reaction system, we achieved photoactivation of the in situ generated super electron donor and developed a visible-light-induced organocatalytic method for efficient borylation of unactivated aryl chlorides.
- Zhang, Li,Jiao, Lei
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supporting information
p. 9124 - 9128
(2019/06/17)
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- Copper-catalysed borylation of aryl chlorides
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We report herein the first Cu-catalysed borylation of a wide range of aryl chlorides with different electronic and steric properties using a readily prepared NHC-stabilised Cu catalyst and KOtBu as the base with B2pin2 (pin = pinacolato) as the boron reagent. The aryl chlorides are converted into their corresponding arylboronic esters in good yields. The new procedure shows broad functional group tolerance, and B2neop2 (neop = neopentyl glycolato) can also be applied as the boron reagent.
- Kuehn, Laura,Huang, Mingming,Radius, Udo,Marder, Todd B.
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supporting information
p. 6601 - 6606
(2019/07/16)
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- Hydrogenation of (Hetero)aryl Boronate Esters with a Cyclic (Alkyl)(amino)carbene–Rhodium Complex: Direct Access to cis-Substituted Borylated Cycloalkanes and Saturated Heterocycles
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We herein report the hydrogenation of substituted aryl- and heteroaryl boronate esters for the selective synthesis of cis-substituted borylated cycloalkanes and saturated heterocycles. A cyclic (alkyl)(amino)carbene-ligated rhodium complex with two dimethyl groups at the ortho-alkyl scaffold of the carbene showed high reactivity in promoting the hydrogenation, thereby enabling the hydrogenation of (hetero)arenes with retention of the synthetically valuable boronate group. This process constitutes a clean, atom-economic, as well as chemo- and stereoselective route for the generation of cis-configured, diversely substituted borylated cycloalkanes and saturated heterocycles that are usually elusive and difficult to prepare.
- Ling, Liang,He, Yuan,Zhang, Xue,Luo, Meiming,Zeng, Xiaoming
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supporting information
p. 6554 - 6558
(2019/04/17)
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- Nickel-Catalyzed C(sp2)-H Borylation of Arenes
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In this study, C(sp2)-H borylation of arenes was accomplished by a nickel catalyst, resulting in good yield. Alkyl and alkoxy arenes were successfully functionalized, affording C(sp2)-H borylated compounds. It was unraveled that the well-defined abnormal N-heterocyclic carbene based Ni(II) complex breaks into Ni nanoparticles (Ni-NPs), which act as catalytically active species. A series of controlled reactions under stoichiometric conditions along with spectroscopic studies and single-crystal X-ray crystallographic study helped us to understand the formation of Ni-NPs along with formation of a boron(III) compound during this reaction.
- Das, Arpan,Hota, Pradip Kumar,Mandal, Swadhin K.
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- METHODS OF MANUFACTURING OF BORON COMPOUND WITHOUT TRANSITION METALS
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The present invention refers to aryl boron compound number bath method relates to search, more particularly transition metal catalyst to a tank without the use of boron compounds number is given to the aryl organic halo [ceyn [ceyn] freight method are disclosed to boron. (by machine translation)
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Paragraph 0065; 0066; 0071; 0072; 0076
(2018/05/03)
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- COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND A ELECTRONIC DEVICE THEREOF
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The present invention relates to a compound for an organic electronic element including a benzo fluorine compound and a derivative thereof, an organic electronic element utilizing the same, and an electronic device thereof. According to the present invention, the light emitting efficiency, the color purity, and the lifetime of the organic electronic element can be improved. [Reference numerals] (401) Substrate;(402) Anode;(404) Hole transport layer;(405) Light emitting layer;(406) Electron transport layer;(408) Cathode
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Paragraph 0084; 0087; 0127-0129
(2018/10/24)
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- Palladium-Catalyzed Synthesis of 2,3-Diaryl- N-methylindoles from ortho-Alkynylanilines and Aryl Pinacol Boronic Esters
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A palladium-catalyzed synthesis of 2,3-diaryl-N-methylindoles from o-alkynylanilines and aryl pinacol boronic esters was developed. The system possesses high functional group tolerance and a broad substrate scope with a variety of aryl pinacol boronic est
- Luo, Yue-Gui,Basha, R. Sidick,Reddy, Daggula Mallikarjuna,Xue, Yong-Jing,Chen, Te-Hsuan,Lee, Chin-Fa
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supporting information
p. 6872 - 6876
(2018/11/21)
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- LiHMDS-Promoted Palladium or Iron-Catalyzed ipso-Defluoroborylation of Aryl Fluorides
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A novel and efficient method for the synthesis of arylboronic acid pinacol esters via a palladium- or iron-catalyzed cross-coupling reaction of aryl fluorides with bis(pinacolato)diboron (B2pin2) in the presence of LiHMDS was developed. The Pd-catalyzed defluoroborylation of fluoroarenes is compatible with a variety of functional groups such as primary and secondary amine, ketone, trifluoromethyl, alkoxy, and boryl. Remarkably, no external ligand is required for enhanced conversion efficiency.
- Zhao, Xianghu,Wu, Mingsheng,Liu, Yisen,Cao, Song
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supporting information
p. 5564 - 5568
(2018/09/12)
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- Pd II -Porphyrin Complexes - The First Use as Safer and Efficient Catalysts for Miyaura Borylation
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We have developed a simple and convenient procedure for the preparation of pinacol arylboronates from aryl/heteroaryl bromides and bis(pinacolato)diborane using a Pd II -porphyrin complex as a catalyst. Seven different Pd II -porphyrin complexes (Pd II -T m HPP, Pd II -T m CPP, Pd II -TPP, Pd II -TST p SPP, Pd II -T p CPP, Pd II -T p TP, and Pd II -T p AP) have been synthesized and investigated for their catalytic influence in the Miyaura borylation.
- Rao, Kanusu Umamaheswara,Venkateswarlu, Katta
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supporting information
p. 1055 - 1060
(2018/03/23)
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- Ir-Catalyzed Intramolecular Transannulation/C(sp2)-H Amination of 1,2,3,4-Tetrazoles by Electrocyclization
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An efficient strategy for the intramolecular denitrogenative transannulation/C(sp2)-H amination of 1,2,3,4-tetrazoles bearing C8-substituted arenes, heteroarenes, and alkenes is described. The process involves the generation of the metal-nitrene intermediate from tetrazole by the combination of [CpIrCl2]2 and AgSbF6. It has been shown that the reaction proceeds via an unprecedented electrocyclization process. The method has been successfully applied for the synthesis of a diverse array of α-carbolines and 7-azaindoles.
- Das, Sandip Kumar,Roy, Satyajit,Khatua, Hillol,Chattopadhyay, Buddhadeb
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supporting information
p. 8429 - 8433
(2018/07/09)
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- Metal-organic layers stabilize earth-abundant metal-terpyridine diradical complexes for catalytic C-H activation
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We report the synthesis of a terpyridine-based metal-organic layer (TPY-MOL) and its metalation with CoCl2 and FeBr2 to afford CoCl2·TPY-MOL and FeBr2·TPY-MOL, respectively. Upon activation with NaEt3
- Lin, Zekai,Thacker, Nathan C.,Sawano, Takahiro,Drake, Tasha,Ji, Pengfei,Lan, Guangxu,Cao, Lingyun,Liu, Shubin,Wang, Cheng,Lin, Wenbin
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p. 143 - 151
(2018/01/02)
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- C-H borylation by platinum catalysis
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Herein, we describe the platinum-catalyzed borylation of aromatic C-H bonds. N-Heterocyclic carbene-ligated platinum catalysts are found to be efficient catalysts for the borylation of aromatic C(sp2)-H bonds when bis(pinacolato)diboron is used as the boron source. The most remarkable feature of these Pt catalysts is their lack of sensitivity towards the degree of steric hindrance around the C-H bonds undergoing the borylation reaction. These Pt catalysts allow for the synthesis of sterically congested 2,6-disubstituted phenylboronic esters, which are otherwise difficult to synthesize using existing C-H borylation methods. Furthermore, platinum catalysis allows for the site-selective borylation of the C-H bonds ortho to fluorine substituents in fluoroarene systems. Preliminary mechanistic studies and work towards the synthetic application of this platinum catalyzed C-H borylation process are described.
- Furukawa, Takayuki,Tobisu, Mamoru,Chatani, Naoto
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p. 332 - 342
(2017/05/09)
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- Preparation method of aryl borate ester and allyl borate ester
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The invention discloses a preparation method of aryl borate ester and allyl borate ester. The method comprises the following step: under the catalytic action of pyridine or a derivative thereof, carrying out 1) or 2) to obtain substituted boric acid ester shown as a formula I-1 or a formula I-2: 1) a reaction of a halide, bi-boric acid ester and alkoxide; 2) a reaction of a halide and a bi-boric acid ester-alkoxide complex. The method is an efficient preparation method of the aryl borate ester and the allyl borate ester. In the preparation method provided by the invention, the inexpensive pyridine or the derivative thereof is taken as a catalyst instead of a transition metal catalyst, the reaction conditions are mild, the reaction yield is high, residues of trace transition metal in a boronation product are avoided, and the cost of an aryl and allyl borate ester synthesis reaction is lowered.
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Paragraph 0073-0074; 0076
(2017/07/12)
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- Room Temperature Ni0/PCy3-Catalyzed Coupling Reactions of Aryl Arenesulfonates with Bis(pinacolato)diboron
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Room temperature Ni0/PCy3-catalyzed cross-coupling reactions of aryl arenesulfonates with bis(pinacolato)diboron are described. The Ni0/PCy3 catalysts, generated from Ni(COD)2 and PCy3, or air-stable 4-MeOC6H4NiII(PCy3)2OTs, were efficient catalyst systems for the Miyaura borylation reactions of a variety of aryl arenesulfonates with bis(pinacolato)diboron. The mild reaction condition, the easy availability of the catalysts and good yields make these reactions potentially useful in organic synthesis (Cy = cyclohexyl, COD = cyclooctadiene, OTs = tosyl).
- Dong, Jie,Guo, Hui,Hu, Qiao-Sheng
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supporting information
p. 7087 - 7090
(2017/12/28)
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- Transition-Metal-Free, Visible-Light-Enabled Decarboxylative Borylation of Aryl N-Hydroxyphthalimide Esters
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Herein, we report a conceptually novel borylation reaction proceeding via a mild photoinduced decarboxylation of redox-activated aromatic carboxylic acids. This work constitutes the first application of cheap and easily prepared N-hydroxyphthalimide esters as aryl radical precursors and does not require the use of expensive transition metals or ligands. The reaction is operationally simple, scalable, and displays broad scope and functional group tolerance.
- Candish, Lisa,Teders, Michael,Glorius, Frank
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p. 7440 - 7443
(2017/06/13)
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- Chemoselective coupling of 1,1-bis[(pinacolato)boryl]alkanes for the transition-metal-frec borylation of aryl and vinyl halides: A combined experimental and theoretical investigation
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A new transition-metal-frec borylation of aryl and vinyl halides using l,l-bis[(pinacolato)boryl]alkanes as boron sources is described. In this transformation one of the boron groups from 1,1-bis[(pinacolato)boryl]alkanes is selectively transferred to aryl and vinyl halides in the presence of sodium tert-butoxide as the only activator to form organoboronate esters. Under the developed borylation conditions, a broad range of organohalides are borylated with excellent chemo-selectivity and functional group compatibility, thus offering a rare example of a transition-metal-frec borylation protocol. Experimental and theoretical studies have becn performed to elucidate the reaction mechanism, revealing the unusual formation of Lewis acid/base adduct betwecn organohalides and α-borylcarbanion, generated in situ from the reaction of l,l-bis[(pinacolato)boryl]alkanes with an alkoxide base, to facilitate the borylation reactions.
- Lee, Yeosan,Baek, Seung-Yeol,Park, Jinyoung,Kim, Seoung-Tae,Tussupbayev, Samat,Kim, Jeongho,Baik, Mu-Hyun,Cho, Seung Hwan
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supporting information
p. 975 - 984
(2017/05/16)
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- Pyridine-catalyzed radical borylation of aryl halides
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A pyridine-catalyzed transition-metal-free borylation reaction of haloarenes has been developed based on the selective cross-coupling of an aryl radical and a pyridine-stabilized boryl radical. Arylboronates were produced from haloarenes under mild conditions. This borylation reaction features a broad substrate scope, operational simplicity, and gram-scale synthetic ability.
- Zhang, Li,Jiao, Lei
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supporting information
p. 607 - 610
(2017/05/15)
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- Radical Metal-Free Borylation of Aryl Iodides
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A simple metal-free borylation of aryl iodides mediated by a fluoride sp 2 -sp 3 diboron adduct is described. The reaction conditions are compatible with various functional groups. Electronic effects of substituents do not affect the borylation while steric hindrance does. The reaction proceeds via a radical mechanism in which pyridine serves to stabilize the boryl radicals, generated in situ.
- Pinet, Sandra,Liautard, Virginie,Debiais, Mégane,Pucheault, Mathieu
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p. 4759 - 4768
(2017/10/03)
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- Metal-Organic Frameworks Stabilize Solution-Inaccessible Cobalt Catalysts for Highly Efficient Broad-Scope Organic Transformations
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New and active earth-abundant metal catalysts are critically needed to replace precious metal-based catalysts for sustainable production of commodity and fine chemicals. We report here the design of highly robust, active, and reusable cobalt-bipyridine- and cobalt-phenanthroline-based metal-organic framework (MOF) catalysts for alkene hydrogenation and hydroboration, aldehyde/ketone hydroboration, and arene C-H borylation. In alkene hydrogenation, the MOF catalysts tolerated a variety of functional groups and displayed unprecedentedly high turnover numbers of ~2.5 × 106 and turnover frequencies of ~1.1 × 105 h-1. Structural, computational, and spectroscopic studies show that site isolation of the highly reactive (bpy)Co(THF)2 species in the MOFs prevents intermolecular deactivation and stabilizes solution-inaccessible catalysts for broad-scope organic transformations. Computational, spectroscopic, and kinetic evidence further support a hitherto unknown (bpy?-)CoI(THF)2 ground state that coordinates to alkene and dihydrogen and then undergoing σ-complex-assisted metathesis to form (bpy)Co(alkyl)(H). Reductive elimination of alkane followed by alkene binding completes the catalytic cycle. MOFs thus provide a novel platform for discovering new base-metal molecular catalysts and exhibit enormous potential in sustainable chemical catalysis.
- Zhang, Teng,Manna, Kuntal,Lin, Wenbin
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supporting information
p. 3241 - 3249
(2016/03/19)
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- Cobalt-Catalyzed C(sp2)-H Borylation: Mechanistic Insights Inspire Catalyst Design
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A comprehensive study into the mechanism of bis(phosphino)pyridine (PNP) cobalt-catalyzed C-H borylation of 2,6-lutidine using B2Pin2 (Pin = pinacolate) has been conducted. The experimentally observed rate law, deuterium kinetic isotope effects, and identification of the catalyst resting state support turnover limiting C-H activation from a fully characterized cobalt(I) boryl intermediate. Monitoring the catalytic reaction as a function of time revealed that borylation of the 4-position of the pincer in the cobalt catalyst was faster than arene borylation. Cyclic voltammetry established the electron withdrawing influence of 4-BPin, which slows the rate of C-H oxidative addition and hence overall catalytic turnover. This mechanistic insight inspired the next generation of 4-substituted PNP cobalt catalysts with electron donating and sterically blocking methyl and pyrrolidinyl substituents that exhibited increased activity for the C-H borylation of unactivated arenes. The rationally designed catalysts promote effective turnover with stoichiometric quantities of arene substrate and B2Pin2. Kinetic studies on the improved catalyst, 4-(H)2BPin, established a change in turnover limiting step from C-H oxidative addition to C-B reductive elimination. The iridium congener of the optimized cobalt catalyst, 6-(H)2BPin, was prepared and crystallographically characterized and proved inactive for C-H borylation, a result of the high kinetic barrier for reductive elimination from octahedral Ir(III) complexes.
- Obligacion, Jennifer V.,Semproni, Scott P.,Pappas, Iraklis,Chirik, Paul J.
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supporting information
p. 10645 - 10653
(2016/09/04)
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- Benzocarbazoles dioxane derivatives, its preparation process and its use in medicine
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The invention relates to a benzodioxane derivative, a preparation method thereof and application of the derivative in medicines. Specifically, the invention relates to a novel benzodioxane derivative shown as a formula (I), medial salt thereof or a medicine composition containing the derivative, and a preparation method of the derivative. The invention further relates to a use of the benzodioxane derivative and the medial salt thereof or the medicine composition containing the derivative in preparing therapeutic agent, especially GPR 40 agonist, and a drug for treating the diseases such as diabetes, metabolic disorders and the like, wherein each substituent group in the formula (I) is as defined in the description.
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Paragraph 0406; 0408-0411
(2016/10/10)
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- 2-Aryl-indenylphosphine ligands: Design, synthesis and application in Pd-catalyzed Suzuki-Miyaura coupling reactions
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A focused library of phosphine ligands was constructed for structural optimization. The catalyst can be used to perform the Suzuki-Miyaura cross-coupling reaction of aryl and heteroaryl chlorides.
- Lian, Ze-Yu,Yuan, Jia,Yan, Meng-Qi,Liu, Yan,Luo, Xue,Wu, Qing-Guo,Liu, Sheng-Hua,Chen, Jian,Zhu, Xiao-Lei,Yu, Guang-Ao
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supporting information
p. 10090 - 10094
(2016/11/06)
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- High-Turnover Aromatic C-H Borylation Catalyzed by POCOP-Type Pincer Complexes of Iridium
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The catalytic C-H borylation of arenes with HBpin (pin = pinacolate) using POCOP-type pincer complexes of Ir has been demonstrated, with turnover numbers exceeding 10 000 in some cases. The selectivity of C-H activation was based on steric preferences and largely mirrored that found in other Ir borylation catalysts. Catalysis in the (POCOP)Ir system depends on the presence of stoichiometric quantities of sacrificial olefin, which is hydrogenated to consume the H2 equivalents generated in the borylation of C-H bonds with HBpin. Smaller olefins such as ethylene or 1-hexene were more advantageous to catalysis than sterically encumbered tert-butylethylene (TBE). Olefin hydroboration is a competing side reaction. The synthesis and isolation of multiple complexes potentially relevant to catalysis permitted examination of several key elementary reactions. These experiments indicate that the C-H activation step in catalysis ostensibly involves oxidative addition of an aromatic C-H bond to the three-coordinate (POCOP)Ir species. The olefin is mechanistically critical to gain access to this 14-electron, monovalent Ir intermediate. C-H activation at Ir(I) here is in contrast to the olefin-free catalysis with state-of-the-art Ir complexes supported by neutral bidentate ligands, where the C-H activating step is understood to involve trivalent Ir-boryl intermediates.
- Press, Loren P.,Kosanovich, Alex J.,McCulloch, Billy J.,Ozerov, Oleg V.
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supporting information
p. 9487 - 9497
(2016/08/12)
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- METHODS FOR PRODUCING BORYLATED ARENES
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Methods for the borylation of aromatic compounds using cobalt catalysts are provided.
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Paragraph 0317-0318
(2015/12/30)
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- Zinc-Catalyzed Dual C-X and C-H Borylation of Aryl Halides
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A zinc-catalyzed combined C-X and C-H borylation of aryl halides using B2pin2 (pin=OCMe2CMe2O) to produce the corresponding 1,2-diborylarenes under mild conditions was developed. Catalytic C-H bond activation occurs ortho to the halide groups if such a site is available or meta to the halide if the ortho position is already substituted. This method thus represents a novel use of a groupXII catalyst for C-H borylation. This transformation does not proceed via a free aryne intermediate, but a radical process seems to be involved. Two B or not two B: A novel catalytic system based on a ZnII-dtbpy precursor was developed for the preparation of 1,2-diborylarenes. This method represents a new type of catalytic process for diborylation of aryl halides via both C-X and C-H activation.
- Bose, Shubhankar Kumar,Deissenberger, Andrea,Eichhorn, Antonius,Steel, Patrick G.,Lin, Zhenyang,Marder, Todd B.
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supporting information
p. 11843 - 11847
(2015/10/05)
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- C-H Functionalization at Sterically Congested Positions by the Platinum-Catalyzed Borylation of Arenes
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Despite significant progress in the area of C-H bond functionalization of arenes, no general method has been reported for the functionalization of C-H bonds at the sterically encumbered positions of simple arenes, such as mesitylene. Herein, we report the development of the first platinum-based catalyst for C-H borylation of arenes and heteroarenes. Notably, this method exhibited high tolerance toward steric hindrance and provided rapid access to a series of 2,6-disubstituted phenylboronic esters, valuable building blocks for further elaborations.
- Furukawa, Takayuki,Tobisu, Mamoru,Chatani, Naoto
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supporting information
p. 12211 - 12214
(2015/10/12)
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