- Functionalized heterocycle-appended porphyrins: Catalysis matters
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The scope and limitations of the condensation of labile 2,3-diaminoporphyrin derivatives with aromatic aldehydes to provide functionalized imidazole- and pyrazine-appended porphyrins were investigated in detail. The presence of an acidic catalyst in the reaction was found to be a tool that allows the reaction path to be switched. The influence of the electronic origin of the substituents in the carbonyl components of the condensation on the yields and selectivity of the reaction was revealed. Metal-promoted cross-coupling transformations were found to be convenient for the further targeted construction of functional derivatives based on the prepared bromo-substituted pyrazinoporphyrins. Overall, these strategies provide a versatile technique for the elaboration of a variety of functionalized heterocycle-appended porphyrins for further application in the development of hybrid materials. This journal is
- Abdulaeva, Inna A.,Birin, Kirill P.,Gorbunova, Yulia G.,Polivanovskaia, Daria A.,Tsivadze, Aslan Yu
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- Sandmeyer-type reaction to pinacol arylboronates in water phase: A green borylation process
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Copper(I)-catalyzed cross-coupling reactions of aryl diazonium salts with bis(pinacolato)diboron can proceed smoothly in the water phase at room temperature to give the corresponding arylboronate esters in good to high yields. The Sandmeyer-type borylation not only provides direct access to arylboronates bearing halo and acidic substituents, but also achieves a green borylation process. Georg Thieme Verlag Stuttgart · New York.
- Zhang, Jie,Wang, Xiaolong,Yu, Haitao,Ye, Jiahai
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- Highly Stable Zr(IV)-Based Metal-Organic Frameworks for the Detection and Removal of Antibiotics and Organic Explosives in Water
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Antibiotics and organic explosives are among the main organic pollutants in wastewater; their detection and removal are quite important but challenging. As a new class of porous materials, metal-organic frameworks (MOFs) are considered as a promising platform for the sensing and adsorption applications. In this work, guided by a topological design approach, two stable isostructural Zr(IV)-based MOFs, Zr6O4(OH)8(H2O)4(CTTA)8/3 (BUT-12, H3CTTA = 5′-(4-carboxyphenyl)-2′,4′,6′-trimethyl-[1,1′:3′,1″-terphenyl]-4,4″-dicarboxylic acid) and Zr6O4(OH)8(H2O)4(TTNA)8/3 (BUT-13, H3TTNA = 6,6′,6″-(2,4,6-trimethylbenzene-1,3,5-triyl)tris(2-naphthoic acid)) with the the-a topological structure constructed by D4h 8-connected Zr6 clusters and D3h 3-connected linkers were designed and synthesized. The two MOFs are highly porous with the Brunauer-Emmett-Teller surface area of 3387 and 3948 m2 g-1, respectively. Particularly, BUT-13 features one of the most porous water-stable MOFs reported so far. Interestingly, these MOFs represent excellent fluorescent properties, which can be efficiently quenched by trace amounts of nitrofurazone (NZF) and nitrofurantoin (NFT) antibiotics as well as 2,4,6-trinitrophenol (TNP) and 4-nitrophenol (4-NP) organic explosives in water solution. They are responsive to NZF and TNP at parts per billion (ppb) levels, which are among the best performing luminescent MOF-based sensing materials. Simultaneously, both MOFs also display high adsorption abilities toward these organic molecules. It was demonstrated that the adsorption plays an important role in the preconcentration of analytes, which can further increase the fluorescent quenching efficiency. These results indicate that BUT-12 and -13 are favorable materials for the simultaneous selective detection and removal of specific antibiotics and organic explosives from water, being potentially useful in monitoring water quality and treating wastewater.
- Wang, Bin,Lv, Xiu-Liang,Feng, Dawei,Xie, Lin-Hua,Zhang, Jian,Li, Ming,Xie, Yabo,Li, Jian-Rong,Zhou, Hong-Cai
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- Effects of main chain and acceptor content on phase behaviors of hydrogen-bonded main-chain/side-chain combined liquid crystalline polymers
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Main-chain/side-chain combined liquid crystalline polymers (MCSCLCPs) are usually difficult to synthesize and their degrees of polymerization are relatively low, which bring difficulties in studying their structure-property relationships. In order to solve this problem, we prepared a new series of MCSCLCPs containing mesogen-jacketed liquid crystalline polymer (MJLCP) main chains via hydrogen-bonding (H-B). A pyridine derivative with a triphenylene (Tp) unit is the H-B acceptor. In addition to the temperature dependence, the phase behavior of the resulting complex is strongly influenced by the content of the H-B acceptor and the rigidity of the side-chain core of the MJLCP. The resulting complexes exhibit different phase structures: (1) a columnar nematic phase or a smectic A (SmA) phase formed by the supramolecular MJLCP chain as a whole; (2) hierarchical nanostructures including a hexagonal columnar phase or a SmA phase of the whole polymer chain plus a discotic nematic phase associated with the Tp moieties.
- Yang, Shuai-Qi,Qu, Wei,Pan, Hong-Bing,Zhang, Yu-Dong,Zheng, Shi-Jun,Fan, Xing-He,Shen, Zhihao
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- Synthesis, structures and luminescent properties of two coordination polymers based on 5-(4-carboxyphenyl)-2, 6-pyridinedicarboxylic acid
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Two coordination polymers, Zn7O(cpda)3(OH) 3 (1) and [Tb(H2cpda)(Hcpda)(H2O)] ·(H2O) (2) (H3cpda = 5-(4-carboxyphenyl)-2, 6-pyridinedicarboxylic acid), were synthesized and chara
- Zhang, Wenqian,Yu, Jiancan,Cui, Yuanjing,Rao, Xingtang,Yang, Yu,Qian, Guodong
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- Palladium-catalyzed borylation of aryl bromides and chlorides using phosphatrioxa-adamantane ligands
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Catalysts based on the combination of Pd(OAc)2 and the electron-deficient phosphatrioxa-adamantane ligands are described for borylation of aryl bromides and chlorides. Catalytic evaluation of a small library of phosphatrioxa-adamantane ligands provided some insights on the preferred ligand steric profile for borylation reactions. The corresponding aryl boronate esters were accessed under mild conditions (25–70 °C) and isolated in high yields (up to 96%).
- Lamola, Jairus L.,Moshapo, Paseka T.,Holzapfel, Cedric W.,Christopher Maumela, Munaka
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supporting information
(2021/12/13)
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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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- Polysulfide Anions as Visible Light Photoredox Catalysts for Aryl Cross-Couplings
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Polysulfide anions are endowed with unique redox properties, attracting considerable attentions for their applications in alkali metals-sulfur batteries. However, the employment of these anionic species in redox catalysis for small molecule synthesis remains underdeveloped due to their moderate-poor electrochemical potential in the ground state, whereas some of them are characterized by photoabsorptions in visible spectral regions. Herein, we disclose the use of polysulfide anions as visible light photoredox catalysts for aryl cross-coupling reactions. The reaction design enables single-electron reduction of aryl halides upon the photoexcitation of tetrasulfide dianions (S42-). The resulting aryl radicals are engaged in (hetero)biaryl cross-coupling, borylation, and hydrogenation in a redox catalytic regime involving S4?-/S42- and S3?-/S32- redox couples.
- Li, Haoyu,Tang, Xinxin,Pang, Jia Hao,Wu, Xiangyang,Yeow, Edwin K. L.,Wu, Jie,Chiba, Shunsuke
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supporting information
p. 481 - 487
(2021/01/13)
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- N-(1H-IMIDAZOL-2-YL)BENZAMIDE COMPOUND AND PHARMACEUTICAL COMPOSITION COMPRISING THE SAME AS ACTIVE INGREDIENT
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N-(1H-imidazol-2-yl)benzamide compound of formula (I), or a pharmaceutically acceptable salt, a prodrug, a solvate, or a stereoisomer thereof which is a novel compound exhibiting excellent inhibitory activity against IRAK-4, can be used without side effects for efficient prevention and treatment of diseases mediated by IRAK-4 receptors, particularly autoimmune diseases or lymphomas.
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Page/Page column 31
(2021/04/10)
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- Potential Foldamers Based on an ortho-Terphenyl Amino Acid
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We describe the synthesis and characterization of a new class of oligomers built from a terphenyl-based amino acid. These oligomeric amides are of interest because the adoption of specific conformations could potentially be driven by the coordinated formation of inter-residue hydrogen bonds and aromatic interactions. Although high-resolution structural data have proven inaccessible, circular dichroism and nuclear magnetic resonance studies suggest that the new oligomers fold concomitantly with discrete self-association in chloroform.
- Kleman, Adam F.,Dufek, Deseree L.,Fobe, Theodore L.,McCaslin, Darrell R.,Cary, Brian P.,Shirts, Michael R.,Gellman, Samuel H.
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supporting information
p. 4855 - 4859
(2021/06/28)
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- Recyclable Pd2dba3/XPhos/PEG-2000 System for Efficient Borylation of Aryl Chlorides: Practical Access to Aryl Boronates
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Pd2dba3/XPhos in poly(ethylene glycol) (PEG-2000) is shown to be a highly stable and efficient catalyst for the borylation of aryl chlorides with bis(pinacolato)diboron. The borylation reaction proceeds smoothly at 110 °C, delivering a wide variety of aryl boronates in good to excellent yields with high functional group tolerance. The crude products were easily isolated via simple extraction of the reaction mixture with cyclohexane. Moreover, both expensive Pd2dba3 and XPhos in PEG-2000 system could be readily recycled and reused more than six times without loss of catalytic efficiency.
- Cai, Mingzhong,Huang, Bin,Luo, Chengkai,Xu, Caifeng
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- Unveiling Extreme Photoreduction Potentials of Donor-Acceptor Cyanoarenes to Access Aryl Radicals from Aryl Chlorides
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Since the seminal work of Zhang in 2016, donor-acceptor cyanoarene-based fluorophores, such as 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), have been widely applied in photoredox catalysis and used as excellent metal-free alternatives to noble metal Ir- and Ru-based photocatalysts. However, all the reported photoredox reactions involving this chromophore family are based on harnessing the energy from a single visible light photon, with a limited range of redox potentials from -1.92 to +1.79 V vs SCE. Here, we document the unprecedented discovery that this family of fluorophores can undergo consecutive photoinduced electron transfer (ConPET) to achieve very high reduction potentials. One of the newly synthesized catalysts, 2,4,5-tri(9H-carbazol-9-yl)-6-(ethyl(phenyl)amino)isophthalonitrile (3CzEPAIPN), possesses a long-lived (12.95 ns) excited radical anion form, 3CzEPAIPN?-*, which can be used to activate reductively recalcitrant aryl chlorides (Ered ≈ -1.9 to -2.9 V vs SCE) under mild conditions. The resultant aryl radicals can be engaged in synthetically valuable aromatic C-B, C-P, and C-C bond formation to furnish arylboronates, arylphosphonium salts, arylphosphonates, and spirocyclic cyclohexadienes.
- Cao, Jilei,Tang, Xinxin,Toh, Ren Wei,Wang, Han,Wu, Jie,Wu, Xiangyang,Xu, Jinhui,Yang, Xiaona,Yeow, Edwin K. L.,Zhou, Rong
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supporting information
p. 13266 - 13273
(2021/09/07)
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- Improvement in the Palladium-Catalyzed Miyaura Borylation Reaction by Optimization of the Base: Scope and Mechanistic Study
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Aryl boronic acids and esters are important building blocks in API synthesis. The palladium-catalyzed Suzuki-Miyaura borylation is the most common method for their preparation. This paper describes an improvement of the current reaction conditions. By using lipophilic bases such as potassium 2-ethyl hexanoate, the borylation reaction could be achieved at 35 °C in less than 2 h with very low palladium loading (0.5 mol %). A preliminary mechanistic study shows a hitherto unrecognized inhibitory effect by the carboxylate anion on the catalytic cycle, whereas 2-ethyl hexanoate minimizes this inhibitory effect. This improved methodology enables borylation of a wide range of substrates under mild conditions.
- Barroso, Santiago,Joksch, Markus,Puylaert, Pim,Tin, Sergey,Bell, Stephen J.,Donnellan, Luke,Duguid, Stewart,Muir, Colin,Zhao, Peichao,Farina, Vittorio,Tran, Duc N.,De Vries, Johannes G.
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supporting information
p. 103 - 109
(2020/12/22)
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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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- Synthesis and evaluation of tiaprofenic acid-derived UCHL5 deubiquitinase inhibitors
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The ubiquitin–proteasome system (UPS) plays an important role in maintaining protein homeostasis by degrading intracellular proteins. In the proteasome, poly-ubiquitinated proteins are deubiquitinated by three deubiquitinases (DUBs) associated with 19S re
- Gurusingha Arachchige, Harshani S.,Herath Mudiyanselage, Poornima D.H.,VanHecke, Garrett C.,Patel, Kush,Cheaito, Hassan A.,Dou, Q. Ping,Ahn, Young-Hoon
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supporting information
(2020/12/25)
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- Evaluation of the role of graphene-based Cu(i) catalysts in borylation reactions
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Carbon-supported catalysts have been considered as macromolecular ligands which modulate the activity of the metallic catalytic center. Understanding the properties and the factors that control the interactions between the metal and support allows a fine tuning of the catalyzed processes. Although huge effort has been devoted to comprehending binding energies and charge transfer for single atom noble metals, the interaction of graphenic surfaces with cheap and versatile Cu(i) salts has been scarcely studied. A methodical experimental and theoretical analysis of different carbon-based Cu(i) materials in the context of the development of an efficient, general, scalable, and sustainable borylation reaction of aliphatic and aromatic halides has been performed. We have also examined the effect of microwave (MW) radiation in the preparation of these type of materials using sustainable graphite nanoplatelets (GNP) as a support. A detailed analysis of all the possible species in solution revealed that the catalysis is mainly due to an interesting synergetic Cu2O/graphene performance, which has been corroborated by an extensive theoretical study. We demonstrated through DFT calculations at a high level of theory that graphene enhances the reactivity of the metal in Cu2O against the halide derivative favoring a radical departure from the halogen. Moreover, this material is able to stabilize radical intermediates providing unexpected pathways not observed using homogeneous Cu(i) catalysed reactions. Finally, we proved that other common carbon-based supports like carbon black, graphene oxide and reduced graphene oxide provided poorer results in the borylation process.
- Cid, M. B.,Díaz, Cristina,Franco, Mario,Lamsabhi, Al Mokhtar,Sainz, Raquel,Tortosa, Mariola
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p. 3501 - 3513
(2021/06/06)
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- Borylation of Diazonium Salts by Highly Emissive and Crystalline Carbon Dots in Water
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Efficient borylation reaction of diazonium salts in water is realized for the first time by using easily prepared, highly emissive and crystalline carbon dots. Electron-donating and electron-withdrawing groups on diazonium salts were well tolerated with moderate to good conversion efficiency. Compared with widely used metal complexes, organic dyes and quantum dots, the approach presented herein uses carbon dots, which are nontoxic and possess good biological and medicinal compatibility and high reactivity. Therefore, this approach presents a new prospective use for carbon dots in green chemistry.
- Lei, Tao,Wei, Si-Meng,Feng, Ke,Chen, Bin,Tung, Chen-Ho,Wu, Li-Zhu
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p. 1715 - 1719
(2020/03/23)
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- Photocatalytic C–X borylation of aryl halides by hierarchical SiC nanowire-supported Pd nanoparticles
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Hierarchical SiC nanowire-supported Pd nanoparticles showed high photocatalytic activity for the C-X (X = Br, I) borylation of aryl halides at 30 °C. The SiC/Pd Mott-Schottky contact enhances the rapid transfer of the photogenerated electrons from SiC to the Pd nanoparticles. As a result, the concentrated energetic electrons in the Pd nanoparticles can facilitate the cleavage of C-I or C-Br bonds, which normally requires high-temperature thermal processes. We show that the present Pd/SiC photocatalyst is capable of catalyzing the transformation of a large variety of aryl halides to their corresponding boronate esters under visible light irradiation, with excellent yields.
- Jiao, Zhi-Feng,Zhao, Ji-Xiao,Guo, Xiao-Ning,Guo, Xiang-Yun
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p. 357 - 363
(2019/12/28)
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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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- SUBSTITUTED IMIDAZOLES FOR THE INHIBITION OF TGF-BETA AND METHODS OF TREATMENT
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This disclosure relates to low molecular weight substituted imidazoles that inhibit the TGF-b signaling pathway. More specifically, this disclosure relates to methods of using said imidazoles for the treatment of diseases related to the TGF-b signaling pathways including, but not limited to, atherosclerosis, Marfan syndrome, Loeys-Dietz syndrome, obesity, diabetes, multiple sclerosis, keratoconus, idiopathic pulmonary fibrosis, Alzheimer's Disease, chronic kidney disease, and scleroderma.
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Paragraph 00103
(2020/03/15)
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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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- Visible-light-mediated borylation of aryl and alkyl halides with a palladium complex
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Palladium catalyzed visible-light-mediated borylation of inactivated aryl and alkyl halides is reported; the method provided high yields and excellent functional group compatibility. Furthermore, arylsilicates were synthesized selectively using dimethylphenylsilyl boronic ester via changing the reaction conditions. Finally, the possible reaction mechanism is determined through fluorescence quenching and turn on/off experiments.
- Zhao, Jia-Hui,Zhou, Zhao-Zhao,Zhang, Yue,Su, Xuan,Chen, Xi-Meng,Liang, Yong-Min
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supporting information
p. 4390 - 4394
(2020/10/20)
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- Transformations of Aryl Ketones via Ligand-Promoted C?C Bond Activation
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The coupling of aromatic electrophiles (aryl halides, aryl ethers, aryl acids, aryl nitriles etc.) with nucleophiles is a core methodology for the synthesis of aryl compounds. Transformations of aryl ketones in an analogous manner via carbon–carbon bond activation could greatly expand the toolbox for the synthesis of aryl compounds due to the abundance of aryl ketones. An exploratory study of this approach is typically based on carbon–carbon cleavage triggered by ring-strain release and chelation assistance, and the products are also limited to a specific structural motif. Here we report a ligand-promoted β-carbon elimination strategy to activate the carbon–carbon bonds, which results in a range of transformations of aryl ketones, leading to useful aryl borates, and also to biaryls, aryl nitriles, and aryl alkenes. The use of a pyridine-oxazoline ligand is crucial for this catalytic transformation. A gram-scale borylation reaction of an aryl ketone via a simple one-pot operation is reported. The potential utility of this strategy is also demonstrated by the late-stage diversification of drug molecules probenecid, adapalene, and desoxyestrone, the fragrance tonalid as well as the natural product apocynin.
- Dai, Hui-Xiong,Li, Hanyuan,Li, Ling-Jun,Liu, Qi-Sheng,Ma, Biao,Wang, Mei-Ling,Wang, Xing,Wang, Zhen-Yu,Xu, Hui
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p. 14388 - 14393
(2020/07/06)
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- Hydride Transfer Enables the Nickel-Catalyzed ipso-Borylation and Silylation of Aldehydes
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Nickel-catalyzed ipso-borylations and silylations of aldehydes are described for the first time. The new functional-group interconversion protocol is characterized by its scalability, functional-group tolerance and wide substrate scope, including examples of late-stage functionalization of complex molecules. The key for the successful reaction outcome is the use of a ketone as a hydride acceptor that intercepts the nickel hydride to undergo a reductive pathway, thus allowing formation of the desired C?B and C?Si bonds.
- Srimontree, Watchara,Guo, Lin,Rueping, Magnus
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supporting information
p. 423 - 427
(2019/12/27)
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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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- Rh-Catalyzed Base-Free Decarbonylative Borylation of Twisted Amides
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We report the rhodium-catalyzed base-free decarbonylative borylation of twisted amides. The synthesis of versatile arylboronate esters from aryl twisted amides is achieved via decarbonylative rhodium(I) catalysis and highly selective N-C(O) insertion. The method is notable for a very practical, additive-free Rh(I) catalyst system. The method shows broad functional group tolerance and excellent substrate scope, including site-selective decarbonylative borylation/Heck cross-coupling via divergent N-C/C-Br cleavage and late-stage pharmaceutical borylation.
- Bie, Fusheng,Liu, Xuejing,Shi, Yijun,Cao, Han,Han, Ying,Szostak, Michal,Liu, Chengwei,Liu, Xuejing,Szostak, Michal,Liu, Chengwei
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p. 15676 - 15685
(2020/11/13)
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- Chemoselective Rhodium-Catalyzed Borylation of Bromoiodoarenes under Mild Conditions
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A chemoselective rhodium-catalyzed borylation has been developed for the preparation of aryl boronate esters. The reaction proceeds under mild conditions with excellent selectivity for C-I bonds in bromoiodoarenes and exhibits broad functional group tolerance. This procedure can act as a complementary approach toward bifunctional arenes along with other metal-catalyzed borylations. Additionally, the reaction's utility in the preparation of monomers for metal-catalyzed cross-coupling polymerization is demonstrated.
- Varni, Anthony J.,Bautista, Michael V.,Noonan, Kevin J.T.
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p. 6770 - 6777
(2020/07/21)
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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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- Controllable factors of supported IR complex catalysis for aromatic C?H borylation
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We have developed a catalyst in which an Ir complex and organic functionalities are coimmobilized on the silica surface. The catalytic activity for aromatic C?H borylation was significantly affected by (i) the linker length of the Ir?bipyridine complex, (ii) the coimmobilized organic functionality, and (iii) the substituents on the aromatic substrate compounds. The fine-tuned supported catalyst showed higher activity than the homogeneous Ir?bipyridine complex when using a specific substrate such as benzonitrile. We elucidated this property by conducting solid-state NMR, FT-IR, XAFS, and in situ FT-IR analysis.
- Chun, Wang-Jae,Maeda, Kyogo,Manaka, Yuichi,Motokura, Ken,Nakajima, Kiyotaka,Satter, Shazia Sharmin,Uemura, Yohei
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p. 14552 - 14559
(2020/12/21)
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- Photocatalyzed borylation using water-soluble quantum dots
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The synthesis of arylboronates by Sandmeyer-type reactions in the presence of water still remains a significant challenge. Herein, we report the use of water-soluble MPA-capped quantum dot (QD) photocatalysts for the borylation of diazonium salts in the presence of water. A biphasic system under mild acidic conditions remains critical to prevent decomposition and competitive disulphide bond formation. The present protocol offers a broader scope of substrates and borylating agents. Additionally, this catalytic system offers a significantly high turnover number (TON). The present methodology can effectively distinguish subtle reactivity differences between boronic acids and boronates. Mechanistic investigation suggests an excited-state electron transfer pathway.
- Chandrashekar, Hediyala B.,Maji, Arun,Halder, Ganga,Banerjee, Sucheta,Bhattacharyya, Sayan,Maiti, Debabrata
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supporting information
p. 6201 - 6204
(2019/06/07)
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- Copper-Photocatalyzed Borylation of Organic Halides under Batch and Continuous-Flow Conditions
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The copper-photocatalyzed borylation of aryl, heteroaryl, vinyl and alkyl halides (I and Br) was reported. The reaction proceeded using a new heteroleptic Cu complex under irradiation with blue LEDs, giving the corresponding boronic-acid esters in good to excellent yields. The reaction was extended to continuous-flow conditions to allow an easy scale-up. The mechanism of the reaction was studied and a mechanism based on a reductive quenching (CuI/CuI*/Cu0) was suggested.
- Nitelet, Antoine,Thevenet, Damien,Schiavi, Bruno,Hardouin, Christophe,Fournier, Jean,Tamion, Rodolphe,Pannecoucke, Xavier,Jubault, Philippe,Poisson, Thomas
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supporting information
p. 3262 - 3266
(2019/02/13)
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- Diverse Multi-Functionalized Oligoarenes and Heteroarenes for Porous Crystalline Materials
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A modular synthesis of multi-functionalized biphenyl, terphenyl and higher linear oligophenylene dicarboxylic acids and pyridine-terminated oligoarenes by stepwise palladium–catalyzed borylation/Suzuki–Miyaura cross-coupling reactions is described. The presence of several distinct functional groups such as azide, hydroxy, and alkyne, as well as coordinative functional end groups (carboxylic acid or pyridine) combined in a single oligoarene molecular unit at strategic positions offer an advantageous dual-utility. First, these compounds can serve as useful molecular bricks (ditopic organic linkers) in the construction of complex porous crystalline materials. Second, after the assembly into the crystalline coordination networks, orthogonal functional sites within the linker-backbone offer tremendous potential from application perspectives as they can be modified by a wide range of post-synthetic modifications including azide–alkyne click chemistry. This allows further tailoring of the supramolecular assemblies to yield novel multifunctional materials.
- Grosjean, Sylvain,Hassan, Zahid,W?ll, Christof,Br?se, Stefan
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p. 1446 - 1460
(2018/10/24)
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- Dual-Functionalized Mixed Keggin- and Lindqvist-Type Cu24-Based POM@MOF for Visible-Light-Driven H2 and O2 Evolution
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The development of logical visible-light-driven heterogeneous photosystems for water splitting is a subject of new research. As the first example of a noble-metal-free photocatalyst for both H2 and O2 production, a high-nuclear {Cus
- Shi, Dongying,Zheng, Rui,Liu, Chun-Sen,Chen, Di-Ming,Zhao, Junwei,Du, Miao
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supporting information
p. 7229 - 7235
(2019/05/07)
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- ARYL-BIPYRIDINE AMINE DERIVATIVES AS PHOSPHATIDYLINOSITOL PHOSPHATE KINASE INHIBITORS
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The invention relates to inhibitors of PI5P4K inhibitors useful in the treatment of cancers, neurodegenerative diseases, inflammatory disorders, and metabolic diseases, having the Formula (I): wherein A, X, Y, Z, Q, R1, R2, R3, R4, R5, and n are described herein.
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Paragraph 0760
(2019/07/13)
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- Method for preparing aryl boronate at room temperature
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The invention discloses a method for preparing aryl boronate represented by a formula I at a room temperature. The method comprises: carrying out a reaction on a diboron compound represented by a formula II and an aryl halide in an organic solvent for 0.5-8 h at a room temperature under the actions of an alkali, a chloro(2-dicyclohexylphosphino-2',4',6'-tri-isopropyl-1,1'-biphenyl)(2'-amino-1,1'-biphenyl-2-yl)palladium (II) catalyst and a 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl ligand, and carrying out post-treatment to obtain the corresponding aryl boronate. According to the present invention, the method has characteristics of mild reaction conditions, simple operation, wide application range, good compatibility with various functional groups on aryl, high efficiency and economy, can achieve high yield of aryl borate under normal pressure and normal pressure conditions, and is suitable for large-scale preparation of aryl borate. The formulas I and II are defined in the specification, wherein R' represents any one selected from phenyl with substituent, pyridyl, thienyl, indyl, pyrazolyl and naphthyl.
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Paragraph 0020-0022; 0040-0042
(2019/05/11)
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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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- Organophotocatalytic Arene Functionalization: C-C and C-B Bond Formation
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Organophotocatalytic C-C and C-B bond formation reactions of aryl halides have been developed in the presence of an organophotosensitizer, 3,7-di([1,1′-biphenyl]-4-yl)-10-(4-(trifluoromethyl)phenyl)-10H-phenoxazine that has highly negative reduction potential at its photoexcited state. The developed reaction conditions are mild and allow the intermolecular C-C bond formation of the generated aryl radical with electron-rich (hetero)arenes and C-B bond formation with bis(pinacolato)diboron.
- Lee, Da Seul,Kim, Chung Soo,Iqbal, Naila,Park, Gyeong Su,Son, Kyung-Sun,Cho, Eun Jin
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supporting information
p. 9950 - 9953
(2019/12/24)
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- Cleavage of C(aryl)?CH3 Bonds in the Absence of Directing Groups under Transition Metal Free Conditions
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Organic chemists now can construct carbon–carbon σ-bonds selectively and sequentially, whereas methods for the selective cleavage of carbon–carbon σ-bonds, especially for unreactive hydrocarbons, remain limited. Activation by ring strain, directing groups, or in the presence of a carbonyl or a cyano group is usually required. In this work, by using a sequential strategy site-selective cleavage and borylation of C(aryl)?CH3 bonds has been developed under directing group free and transition metal free conditions. Methyl groups of various arenes are selectively cleaved and replaced by boryl groups. Mechanistic analysis suggests that it proceeds by a sequential intermolecular oxidation and coupling of a transient aryl radical, generated by radical decarboxylation, involving a pyridine-stabilized persistent boryl radical.
- Dai, Peng-Fei,Ning, Xiao-Shan,Wang, Hua,Cui, Xian-Chao,Liu, Jie,Qu, Jian-Ping,Kang, Yan-Biao
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supporting information
p. 5392 - 5395
(2019/03/29)
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- Visible light-promoted formation of C-B and C-S bonds under metal- A nd photocatalyst-free conditions
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A green, efficient, photoinduced synthesis of arylboronic esters and aryl sulfides has been developed. Bench stable arylazo sulfones were used as radical precursors for a photocatalyst- A nd additive-free carbon-heteroatom bond formation under visible light. The protocols are applicable to a wide range of substrates, providing products in good yields.
- Blank, Lena,Fagnoni, Maurizio,Protti, Stefano,Rueping, Magnus
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p. 1243 - 1252
(2019/02/26)
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- Mechanism and Scope of Nickel-Catalyzed Decarbonylative Borylation of Carboxylic Acid Fluorides
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This Article describes the development of a base-free, nickel-catalyzed decarbonylative coupling of carboxylic acid fluorides with diboron reagents to selectively afford aryl boronate ester products. Detailed studies were conducted to assess the relative rates of direct transmetalation between aryl boronate esters and diboron reagents and a bisphosphine nickel(aryl)(fluoride) intermediate. These investigations revealed that diboron reagents undergo transmetalation with this Ni(aryl)(fluoride) intermediate at rates significantly faster than their aryl boronate ester congeners. Furthermore, the reactivity of both boron reagents toward transmetalation is enhanced with increasing electrophilicity of the boron center. These mechanistic insights were leveraged to develop a catalytic decarbonylative borylation of acid fluorides that proved applicable to a variety of (hetero)aryl carboxylic acid fluorides as well as diverse diboron reagents. The acid fluorides can be generated in situ directly from carboxylic acids. Furthermore, the mechanistic studies directed the identification of various air-stable Ni pre-catalysts for this transformation.
- Malapit, Christian A.,Bour, James R.,Laursen, Simon R.,Sanford, Melanie S.
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supporting information
p. 17322 - 17330
(2019/11/03)
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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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- Hydrogen Bond Directed ortho-Selective C?H Borylation of Secondary Aromatic Amides
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Reported is an iridium catalyst for ortho-selective C?H borylation of challenging secondary aromatic amide substrates, and the regioselectivity is controlled by hydrogen-bond interactions. The BAIPy-Ir catalyst forms three hydrogen bonds with the substrate during the crucial activation step, and allows ortho-C?H borylation with high selectivity. The catalyst displays unprecedented ortho selectivities for a wide variety of substrates that differ in electronic and steric properties, and the catalyst tolerates various functional groups. The regioselective C?H borylation catalyst is readily accessible and converts substrates on gram scale with high selectivity and conversion.
- Bai, Shao-Tao,Bheeter, Charles B.,Reek, Joost N. H.
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supporting information
p. 13039 - 13043
(2019/07/31)
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- Meta-Selective C-H Borylation of Benzamides and Pyridines by an Iridium-Lewis Acid Bifunctional Catalyst
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We report herein the iridium-catalyzed meta-selective C-H borylation of benzamides by using a newly designed 2,2′-bipyridine (bpy) ligand bearing an alkylaluminum biphenoxide moiety. We also demonstrate the iridium-catalyzed C3-selective C-H borylation of pyridine with a 1,10-phenanthroline (Phen) ligand bearing an alkylborane moiety. It is proposed that the Lewis acid-base interaction between the Lewis acid moiety and the aminocarbonyl group or the sp2-hybridized nitrogen atom accelerates the reaction and controls the site-selectivity.
- Yang, Lichen,Uemura, Nao,Nakao, Yoshiaki
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supporting information
p. 7972 - 7979
(2019/05/22)
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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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- Photoinduced Miyaura Borylation by a Rare-Earth-Metal Photoreductant: The Hexachlorocerate(III) Anion
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The first photoinduced carbon(sp2)–heteroatom bond forming reaction by a rare-earth-metal photoreductant, a Miyaura borylation, has been achieved. This simple, scalable, and novel borylation method that makes use of the hexachlorocerate(III) anion ([CeIIICl6]3?, derived from CeCl3) has a broad substrate scope and functional-group tolerance and can be conducted at room temperature. Combined with Suzuki–Miyaura cross-coupling, the method is applicable to the synthesis of various biaryl products, including through the use of aryl chloride substrates.
- Qiao, Yusen,Yang, Qiaomu,Schelter, Eric J.
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supporting information
p. 10999 - 11003
(2018/07/31)
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- INHIBITORS OF LOW MOLECULAR WEIGHT PROTEIN TYROSINE PHOSPHATASE (LMPTP) AND USES THEREOF
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Protein tyrosine phosphatases (PTPs) are key regulators of metabolism and insulin signaling. As a negative regulator of insulin signaling, the low molecular weight protein tyrosine phosphatase (LMPTP) is a target for insulin resistance and related conditions. Described herein are compounds capable of modulating the level of activity of low molecular weight protein tyrosine phosphatase (LMPTP) and compositions, and methods of using these compounds and compositions.
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Paragraph 00198
(2018/11/26)
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- Bedford-type palladacycle-catalyzed miyaura borylation of aryl halides with tetrahydroxydiboron in water
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A mild aqueous protocol for palladium catalyzed Miyaura borylation of aryl iodides, aryl bromides and aryl chlorides with tetrahydroxydiboron (BBA) as a borylating agent is developed. The developed methodology requires low catalyst loading of Bedford-type palladacycle catalyst (0.05 mol %) and works best under mild reaction conditions at 40 °C in short time of 6 h in water. In addition, our studies show that for Miyaura borylation using BBA in aqueous condition, maintaining a neutral reaction pH is very important for reproducibility and higher yields of corresponding borylated products. Moreover, our protocol is applicable for a broad range of aryl halides, corresponding borylated products are obtained in excellent yields up to 93% with 29 examples demonstrating its broad utility and functional group tolerance.
- Zernickel, Anna,Du, Weiyuan,Ghorpade, Seema A.,Sawant, Dinesh N.,Makki, Arwa A.,Sekar, Nagaiyan,Eppinger, J?rg
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p. 1842 - 1851
(2018/02/23)
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- Nickel-catalysed decarbonylative borylation of aroyl fluorides
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The first Ni(cod)2/PPh3 catalyst system has been established for decarbonylative borylation of aroyl fluorides with bis(pinacolato)diboron. A wide range of functional groups in the substrates were well tolerated. The ease of access of the starting aroyl fluorides indicates that these results might become an alternative to the existing decarbonylation events.
- Wang, Zhenhua,Wang, Xiu,Nishihara, Yasushi
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supporting information
p. 13969 - 13972
(2019/01/03)
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- Palladium-Catalyzed Decarbonylative Borylation of Carboxylic Acids: Tuning Reaction Selectivity by Computation
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Decarbonylative borylation of carboxylic acids is reported. Carbon electrophiles are generated directly after reagent-enabled decarbonylation of the in situ accessible sterically-hindered acyl derivative of a carboxylic acid under catalyst controlled conditions. The scope and the potential impact of this method are demonstrated in the selective borylation of a variety of aromatics (>50 examples). This strategy was used in the late-stage derivatization of pharmaceuticals and natural products. Computations reveal the mechanistic details of the unprecedented C?O bond activation of carboxylic acids. By circumventing the challenging decarboxylation, this strategy provides a general synthetic platform to access arylpalladium species for a wide array of bond formations from abundant carboxylic acids. The study shows a powerful combination of experiment and computation to predict decarbonylation selectivity.
- Liu, Chengwei,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
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supporting information
p. 16721 - 16726
(2018/11/30)
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- Copper-Catalyzed Monoorganylation of Trialkyl Borates with Functionalized Organozinc Pivalates
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Organozinc pivalates, a recently developed air- and moisture-stable organozinc species, were found for the first time as excellent organometallic species in the monoorganylation of trialkyl borates whereby boronic acids were prepared in high yields. The significant advantage of organozinc pivalates over another previously employed organometallic reagents, e. g., organolithium reagents, Grignard reagents and organozinc halides, is that the generation of multiorganylation byproducts such as borinic acids and trialkylboranes were completely suppressed. Additionally, the in situ generated boronates could be directly arranged into Suzuki-Miyaura type cross-coupling reactions to produce biaryls in high yields.
- Fu, Ying,Gou, Bei-Lei,Shi, Chun-Zhao,Du, Zhengyin,Shen, Tong
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p. 4253 - 4257
(2018/09/18)
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- Modulator-Controlled Synthesis of Microporous STA-26, an Interpenetrated 8,3-Connected Zirconium MOF with the the-i Topology, and its Reversible Lattice Shift
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A fully interpenetrated 8,3-connected zirconium MOF with the the-i topology type, STA-26 (St Andrews porous material-26), has been prepared using the 4,4′,4“-(2,4,6-trimethylbenzene-1,3,5-triyl)tribenzoate (TMTB) tritopic linker with formic acid as a modulating agent. In the as-prepared form STA-26 possesses Im (Formula presented.) m symmetry compared with the Pm (Formula presented.) m symmetry of the non-interpenetrated analogue, NU-1200, prepared using benzoic acid as a modulator. Upon removal of residual solvent there is a shift between the interpenetrating lattices and a resultant symmetry change to Cmcm which is fully reversible. This is observed by X-ray diffraction and 13C MAS NMR is also found to be remarkably sensitive to the structural transition. Furthermore, heating STA-26(Zr) in vacuum dehydroxylates the Zr6 nodes leaving coordinatively unsaturated Zr4+ sites, as shown by IR spectroscopy using CO and CD3CN as probe molecules. Nitrogen adsorption at 77 K together with grand canonical Monte Carlo simulations confirms a microporous, fully interpenetrated, structure with pore volume 0.53 cm3 g?1 while CO2 adsorption at 196 K reaches 300 cm3 STP g?1 at 1 bar. While the pore volume is smaller than that of its non-interpenetrated mesoporous analogue, interpenetration makes the structure more stable to moisture adsorption and introduces shape selectivity in adsorption.
- Bumstead, Alice M.,Cordes, David B.,Dawson, Daniel M.,Chakarova, Kristina K.,Mihaylov, Mihail Y.,Hobday, Claire L.,Düren, Tina,Hadjiivanov, Konstantin I.,Slawin, Alexandra M. Z.,Ashbrook, Sharon E.,Prasad, Ram R. R.,Wright, Paul A.
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supporting information
p. 6115 - 6126
(2018/03/27)
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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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- 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 0072-0075; 0077
(2017/07/12)
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