- 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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-
- Photo-induced thiolate catalytic activation of inert Caryl-hetero bonds for radical borylation
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Substantial effort is currently being devoted to obtaining photoredox catalysts with high redox power. Yet, it remains challenging to apply the currently established methods to the activation of bonds with high bond dissociation energy and to substrates with high reduction potentials. Herein, we introduce a novel photocatalytic strategy for the activation of inert substituted arenes for aryl borylation by using thiolate as a catalyst. This catalytic system exhibits strong reducing ability and engages non-activated Caryl–F, Caryl–X, Caryl–O, Caryl–N, and Caryl–S bonds in productive radical borylation reactions, thus expanding the available aryl radical precursor scope. Despite its high reducing power, the method has a broad substrate scope and good functional-group tolerance. Spectroscopic investigations and control experiments suggest the formation of a charge-transfer complex as the key step to activate the substrates.
- K?nig, Burkhard,Wang, Hua,Wang, Shun
-
supporting information
p. 1653 - 1665
(2021/06/17)
-
- 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
-
supporting information
p. 15396 - 15405
(2021/10/12)
-
- SYNTHESIS OF 5-(3-PYRIDYL)-2,2'-BITHIOPHENE(SENSITIZER)
-
Disclosed herein is a novel simple, short process for synthesis of the photosensitizer, 5-(3-pyridyl)-2,2'-bithiophene.
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-
Page/Page column 11-12
(2021/02/05)
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- Enzyme-like Supramolecular Iridium Catalysis Enabling C?H Bond Borylation of Pyridines with meta-Selectivity
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The use of secondary interactions between substrates and catalysts is a promising strategy to discover selective transition metal catalysts for atom-economy C?H bond functionalization. The most powerful catalysts are found via trial-and-error screening due to the low association constants between the substrate and the catalyst in which small stereo-electronic modifications within them can lead to very different reactivities. To circumvent these limitations and to increase the level of reactivity prediction in these important reactions, we report herein a supramolecular catalyst harnessing Zn???N interactions that binds to pyridine-like substrates as tight as it can be found in some enzymes. The distance and spatial geometry between the active site and the substrate binding site is ideal to target unprecedented meta-selective iridium-catalyzed C?H bond borylations with enzymatic Michaelis–Menten kinetics, besides unique substrate selectivity and dormant reactivity patterns.
- Al-Shehimy, Shaymaa,Gramage-Doria, Rafael,Roisnel, Thierry,Trouvé, Jonathan,Zardi, Paolo
-
supporting information
p. 18006 - 18013
(2021/05/07)
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- Improvement in the Palladium-Catalyzed Miyaura Borylation Reaction by Optimization of the Base: Scope and Mechanistic Study
-
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.
-
supporting information
p. 103 - 109
(2020/12/22)
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- Compounds comprising benzophenone group, Organic electronic device comprising organic layers comprising the photo-cured of the monomer compounds
-
The compound represented by Formula I or II is provided as an organic material layer material of an organic electronic device. The benzophenone functional group-containing compound represented by the following Chemical I or Chemical Formula II: I (Chemical Formula Ar -) (R). 1 -R2 -Bpm In the formula, m is 1 and 10, and Ar is a substituted or unsubstituted m having a C-order linking group. 6 -C60 Substituted or unsubstituted m having aryl group, C nd-linking group3 -C60 Substituted or unsubstituted fused m with heteroaryl groups or C primary linking groups6 -C60 Aryl group, R1 And R2 Each independently represents a simple bond, O - a substituted or unsubstituted C. 6 -C30 Arylene group, substituted or unsubstituted C3 -C30 Heteroarylene group, substituted or unsubstituted C1 -C10 The alkylene group and Bp are 1 divalent linking groups derived from benzophenone functional groups. Chemical Formula II. In the formula, n is at least 1 and Ar ' is a substituted or unsubstituted m having a C-order linking group. 6 -C60 Aryl group Substituted or unsubstituted m having a C nd order linker3 -C60 Substituted or unsubstituted fused m with heteroaryl groups or C primary linking groups6 -C60 Aryl group, R3 And R4 Each independently represents a simple bond, O - a substituted or unsubstituted C. 6 -C30 Arylene group, substituted or unsubstituted C3 -C30 Heteroarylene group, substituted or unsubstituted C6 -C30 Fused arylene groups, substituted or unsubstituted C1 -C10 The alkylene group and Bp ' are 1 divalent linking groups derived from benzophenone functional groups.
- -
-
Paragraph 0293-0294; 0305-0306
(2021/03/09)
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- Remarkably Efficient Iridium Catalysts for Directed C(sp2)-H and C(sp3)-H Borylation of Diverse Classes of Substrates
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Here we describe the discovery of a new class of C-H borylation catalysts and their use for regioselective C-H borylation of aromatic, heteroaromatic, and aliphatic systems. The new catalysts have Ir-C(thienyl) or Ir-C(furyl) anionic ligands instead of the diamine-type neutral chelating ligands used in the standard C-H borylation conditions. It is reported that the employment of these newly discovered catalysts show excellent reactivity and ortho-selectivity for diverse classes of aromatic substrates with high isolated yields. Moreover, the catalysts proved to be efficient for a wide number of aliphatic substrates for selective C(sp3)-H bond borylations. Heterocyclic molecules are selectively borylated using the inherently elevated reactivity of the C-H bonds. A number of late-stage C-H functionalization have been described using the same catalysts. Furthermore, we show that one of the catalysts could be used even in open air for the C(sp2)-H and C(sp3)-H borylations enabling the method more general. Preliminary mechanistic studies suggest that the active catalytic intermediate is the Ir(bis)boryl complex, and the attached ligand acts as bidentate ligand. Collectively, this study underlines the discovery of new class of C-H borylation catalysts that should find wide application in the context of C-H functionalization chemistry.
- Chattopadhyay, Buddhadeb,Hassan, Mirja Md Mahamudul,Hoque, Md Emdadul
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supporting information
p. 5022 - 5037
(2021/05/04)
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- Discovery of S64315, a Potent and Selective Mcl-1 Inhibitor
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Myeloid cell leukemia 1 (Mcl-1) has emerged as an attractive target for cancer therapy. It is an antiapoptotic member of the Bcl-2 family of proteins, whose upregulation in human cancers is associated with high tumor grade, poor survival, and resistance to chemotherapy. Here we report the discovery of our clinical candidate S64315, a selective small molecule inhibitor of Mcl-1. Starting from a fragment derived lead compound, we have conducted structure guided optimization that has led to a significant (3 log) improvement of target affinity as well as cellular potency. The presence of hindered rotation along a biaryl axis has conferred high selectivity to the compounds against other members of the Bcl-2 family. During optimization, we have also established predictive PD markers of Mcl-1 inhibition and achieved both efficient in vitro cell killing and tumor regression in Mcl-1 dependent cancer models. The preclinical candidate has drug-like properties that have enabled its development and entry into clinical trials.
- Szlavik, Zoltan,Csekei, Marton,Paczal, Attila,Szabo, Zoltan B.,Sipos, Szabolcs,Radics, Gabor,Proszenyak, Agnes,Balint, Balazs,Murray, James,Davidson, James,Chen, Ijen,Dokurno, Pawel,Surgenor, Allan E,Daniels, Zoe Marie,Hubbard, Roderick E.,Le Toumelin-Braizat, Ga?tane,Claperon, Audrey,Lysiak-Auvity, Ga?lle,Girard, Anne-Marie,Bruno, Alain,Chanrion, Maia,Colland, Frédéric,Maragno, Ana-Leticia,Demarles, Didier,Geneste, Olivier,Kotschy, Andras
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p. 13762 - 13795
(2020/12/02)
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- Organic compound with high mobility, and application thereof
-
The invention relates to an organic compound with high mobility, and application thereof. The organic compound provided by the invention takes a benzene ring connected with a five-membered parallel ring structure as a core, and has good thermal stability, high glass transition temperature and appropriate HOMO energy level. A device adopting the organic compound provided by the invention can effectively improve the photoelectric property of an OLED device and prolong the service life of the OLED device through structural optimization.
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-
Paragraph 0063-0064; 0065; 0067
(2020/09/23)
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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.
-
supporting information
p. 18231 - 18242
(2020/11/02)
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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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- Synthesis and evaluation of 6-[18F]fluoro-3-(pyridin-3-yl)-1H-indole as potential PET tracer for targeting tryptophan 2, 3-dioxygenase (TDO)
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Introduction: The increase in expression of tryptophan 2, 3-dioxygenases (TDO) and indoleamine 2,3-dioxygenase (IDO) have been reported as potential tumor biomarkers. TDO and IDO are enzymes that catalyze the first and rate-limiting step of the kynurenine pathway. Positron emitting tomography (PET) tracers investigating the kynurenine pathway may allow for the detection of different disease pathologies in vivo including cancer. However, current PET tracers being developed for TDO and IDO have suffered from either multi-step low yielding syntheses or de-fluorination of the tracer in vivo. Results: TDO inhibitors based on 6-fluoroindole with C3 substituents are a class of small molecules that have been shown to bind to TDO effectively, restore tryptophan concentration and decrease the production of immunosuppressive metabolites. The compound 6-fluoro-3-(pyridine-3-yl)-1H-indole has been reported to have high in vitro affinity for TDO. Herein we report the fully automated radiosynthesis of 6-[18F]fluoro-3-(pyridine-3-yl)-1H-indole [18F]4 using a copper-mediated nucleophilic 18F-fluorination resulting in a non-corrected yield of 5 to 6% of the tracer with a radiochemical purity of >99% after 4 h. Small animal dynamic PET/CT imaging of [18F]4 intravenously injected into normal C57BL/6 mice revealed rapid accumulation in heart and brain, reaching maximum occupancy in heart (10.9% ID/g) and brain (8.1% ID/g) at 1.75 min and 2.25 min, respectively. Furthermore, these in vivo studies revealed no de-fluorination of the tracer, as evidence by the absence of [18F]fluoride accumulation in bone. Conclusion: In vitro studies demonstrate that 4 has good affinity for hTDO and the radiolabeled analogue [18F]4 can be synthesized with suitable radiochemical yields. [18F]4 demonstrates good uptake in the brain and the radiolabeled compound shows no de-fluorination in vivo in C57BL/6 mice.
- Bhalla, Rajiv,Mardon, Karine,Migotto, Mary-anne,Qiao, Zheng,Reutens, David C.,Stimson, Damion H. R.
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- Compounds comprising benzophenone group, Organic electronic device comprising organic layers comprising the photo-cured of the monomer compounds
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The present invention provides a compound containing a benzophenone functional group represented by chemical formula I: Ar-(R_1-R_2-Bp)_m or chemical formula II as a material for an organic material layer of an organic electronic device, wherein the compound is the compound containing the benzophenone functional group.COPYRIGHT KIPO 2020
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Paragraph 0298; 0310-0311
(2020/08/12)
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- Stoichiometric and Catalytic Aryl?Cl Activation and Borylation using NHC-stabilized Nickel(0) Complexes
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NHC-nickel (NHC=N-heterocyclic carbene) complexes are efficient catalysts for the C?Cl bond borylation of aryl chlorides using NaOAc as a base and B2pin2 (pin=pinacolato) as the boron source. The catalysts [Ni2(ICy)4(μ-(η2:η2)-COD)] (1, ICy=1,3-dicyclohexylimidazolin-2-ylidene; COD=1,5-cyclooctadiene), [Ni(ICy)2(η2-C2H4)] (2), and [Ni(ICy)2(η2-COE)] (3, COE=cyclooctene) compare well with other nickel catalysts reported previously for aryl-chloride borylation with the advantage that no further ligands had to be added to the reaction. Borylation also proceeded with B2neop2 (neop=neopentylglycolato) as the boron source. Stoichiometric oxidative addition of different aryl chlorides to complex 1 was highly selective affording trans-[Ni(ICy)2(Cl)(Ar)] (Ar=4-(F3C)C6H4, 11; 4-(MeO)C6H4, 12; C6H5, 13; 3,5-F2C6H3, 14).
- Kuehn, Laura,Jammal, Dominik G.,Lubitz, Katharina,Marder, Todd B.,Radius, Udo
-
supporting information
p. 9514 - 9521
(2019/04/26)
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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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- Anthracene organic luminescence compound, and preparation method and application thereof
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The invention relates to the technical field of organic optoelectronic materials and relates to an anthracene organic luminescence compound, a preparation method thereof and an organic electroluminescence device. The anthracene organic luminescence compound has a structure shown as a formula I: the formula 1 is shown in the description. Compared with other electron transfer layer materials or luminescent layer materials, the novel anthracene organic luminescence compound provided by the invention used as an electron transfer layer material or luminescent layer material of the organic electroluminescence device has the advantage that the luminous efficiency of the device prepared from the material is obviously promoted, and service life is obviously prolonged. The anthracene organic luminescence compound has the advantages of relatively short synthetic route, simple process, easily acquired raw materials, low cost and suitability for industrial production.
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Paragraph 0109-0117
(2019/07/01)
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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
-
supporting information
p. 7972 - 7979
(2019/05/22)
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- COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF
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The present invention is an organic compound for forming an organic thin film disposed between a first electrode and a second electrode of an organic electric element. The organic compound comprises at least two amine functional groups at the end of a core material containing at least one pyridine and/or at least two epoxy functional groups at the end of the core material containing at least one pyridine. According to an embodiment of the present invention, the solubility of a low molecular weight organic compound having low solubility can be improved.(AA) Before immersing a solvent(BB) After immersing a solventCOPYRIGHT KIPO 2019
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Paragraph 0074; 0077-0081; 0099; 0101-0105
(2019/12/25)
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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
-
supporting information
p. 3262 - 3266
(2019/02/13)
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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
-
supporting information
p. 9124 - 9128
(2019/06/17)
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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.
- -
-
Paragraph 0515
(2019/07/13)
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- Iron(II)-Based Metalloradical Activation: Switch from Traditional Click Chemistry to Denitrogenative Annulation
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A unique concept for the intermolecular denitrogenative annulation of 1,2,3,4-tetrazoles and alkynes was discovered by using a catalytic amount of Fe(TPP)Cl and Zn dust. The reaction precludes the traditional, more favored click reaction between an organic azide and alkynes, and instead proceeds by an unprecedented metalloradical activation. The method is anticipated to advance access to the construction of important basic nitrogen heterocycles, which will in turn enable discoveries of new drug candidates.
- Roy, Satyajit,Khatua, Hillol,Das, Sandip Kumar,Chattopadhyay, Buddhadeb
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supporting information
p. 11439 - 11443
(2019/07/17)
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- Room-temperature borylation and one-pot two-step borylation/Suzuki-Miyaura cross-coupling reaction of aryl chlorides
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A highly efficient room-temperature borylation strategy of aryl chlorides is described. Utilizing Buchwald's second-generation preformed catalyst, boronate esters were obtained for a wide range of substrates in high yield. The method was also applied to Suzuki-Miyaura cross-coupling reaction in a one-pot two-step sequential manner, providing a facile and convenient access to the direct synthesis of biaryl compounds from aryl chlorides.
- Ji, Hong,Wu, Li-Yang,Cai, Jiang-Hong,Li, Guo-Rong,Gan, Na-Na,Wang, Zhao-Hua
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p. 13643 - 13648
(2018/04/24)
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- Efficient Synthesis of Aryl Boronates via Cobalt-Catalyzed Borylation of Aryl Chlorides and Bromides
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An efficient catalytic system based on a Co(II)-NHC precursor has been developed for the cross coupling of bis(pinacolato)diboron with aryl halides including aryl chlorides, affording the aryl boronates in good to excellent yields. A wide range of functional groups are tolerated under mild reaction conditions. The reaction shows excellent chemoselectivity for bromide over chloride. Preliminary mechanistic investigations show that the catalytic cycle may rely on a cobalt(I)-(III) redox couple.
- Verma, Piyush Kumar,Mandal, Souvik,Geetharani
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p. 4049 - 4054
(2018/05/22)
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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 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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- Cobalt-Catalyzed C-F Bond Borylation of Aryl Fluorides
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A mild and practical cobalt-catalyzed defluoroborylation of fluoroarenes is presented for the first time. The method permits straightforward functionalization of fluoroarenes, with high selectivity for borylation of C-F over C-H bonds, and a tolerance for aerobic conditions. Furthermore, two-step 18F-fluorination was achieved for expanding the scope of 18F-positron emission tomography probes.
- Lim, Soobin,Song, Dalnim,Jeon, Seungwon,Kim, Youngsuk,Kim, Hyunseok,Lee, Sanghee,Cho, Hyungdo,Lee, Byung Chul,Kim, Sang Eun,Kim, Kimoon,Lee, Eunsung
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supporting information
p. 7249 - 7252
(2018/11/23)
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- COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT COMPRISING THE SAME, AND ELECTRONIC DEVICE THEREOF
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Disclosed are a compound represented by chemical formula 1, an organic electric device comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, and an electronic device including the same. By including the compound represented by the chemical formula 1 in the organic material layer, the driving voltage of the organic electric device can be lowered, and the luminous efficiency and lifespan can be improved.COPYRIGHT KIPO 2019
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Page/Page column 22; 23; 25; 26; 40
(2019/01/29)
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- COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT COMPRISING THE SAME, AND ELECTRONIC DEVICE THEREOF
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Disclosed are a compound represented by chemical formula 1, an organic electric device comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, and an electronic device including the same. By including the compound represented by the chemical formula 1 in the organic material layer, the driving voltage of the organic electric device can be lowered, and the luminous efficiency and lifespan can be improved.COPYRIGHT KIPO 2019
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Paragraph 0107; 0139-0142; 0153-0156
(2019/01/25)
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- Low-Temperature Cross-Linkable Small Molecules for Fully Solution-Processed OLEDs
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Cross-linkable hole-transporting, host, and electron-transporting materials with a new cross-linking group, uracil, are designed and synthesized. These compounds exhibited good solubility in common organic solvents and excellent solvent resistance after cross-linking at a low temperature of 120 °C. The OLED was fabricated by all-solution processing using cross-linkable synthetic compounds, except for the electrodes. This device exhibited a current efficiency of 39.2 cd A?1 and a power efficiency of 15.3 lm W?1.
- Lee, Sungkoo,Seo, Min Hye
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supporting information
p. 17419 - 17423
(2018/11/10)
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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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- 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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- Isonicotinate Ester Catalyzed Decarboxylative Borylation of (Hetero)Aryl and Alkenyl Carboxylic Acids through N-Hydroxyphthalimide Esters
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Decarboxylative borylation of aryl and alkenyl carboxylic acids with bis(pinacolato)diboron was achieved through N-hydroxyphthalimide esters using tert-butyl isonicotinate as a catalyst under base-free conditions. A variety of aryl carboxylic acids possessing different functional groups and electronic properties can be smoothly converted to aryl boronate esters, including those that are difficult to decarboxylate under transition-metal catalysis, offering a new method enabling use of carboxylic acid as building blocks in organic synthesis. Mechanistic analysis suggests the reaction proceeds through coupling of a transient aryl radical generated by radical decarboxylation with a pyridine-stabilized persistent boryl radical. Activation of redox active esters may proceed via an intramolecular single-electron-transfer (SET) process through a pyridine-diboron-phthalimide adduct and accounts for the base-free reaction conditions.
- Cheng, Wan-Min,Shang, Rui,Zhao, Bin,Xing, Wei-Long,Fu, Yao
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p. 4291 - 4294
(2017/08/23)
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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; 0078
(2017/07/12)
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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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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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- Organic compound taking triazine and benzimidazole as cores and application thereof to OLED (Organic Light Emitting Diode)
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The invention relates to an organic compound taking triazine and benzimidazole as cores and application thereof to an OLED (Organic Light Emitting Diode) device. The compound provided by the invention has relatively high glass transition temperature and molecule thermal stability; the compound has low absorption and high refractive index in the field of visible light; after the compound is applied to a CPL (Circular Polarizing Filter) layer of an OLED device, the light extraction efficiency of the OLED device can be effectively improved; the compound also has a deep HOMO energy level and high electron mobility and can be used as a hole-blocking/electron transferring layer material of the OLED device; and the compound can be used for effectively stopping a hole or energy from being transmitted to one side of an electron layer from a light emitting layer, so that the compounding efficiency of the hole and electrons on the light emitting layer is improved, and furthermore, the luminous efficiency of the OLED device is improved and the service life of the OLED device is prolonged.
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Paragraph 0055; 0056; 0057; 0058
(2017/08/31)
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- Direct Access to α,α-Difluoroacylated Arenes by Palladium-Catalyzed Carbonylation of (Hetero)Aryl Boronic Acid Derivatives
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A palladium-catalyzed carbonylative coupling of (hetero)aryl boronates or boronic acid salts with carbon monoxide and α-bromo-α,α-difluoroamides and bromo-α,α-difluoroesters is described herein. The method is useful for the synthesis of a diverse selection of (hetero)aryl α,α-difluoro-β-ketoamides and α,α-difluoro-β-ketoesters, which are useful building blocks for the generation of functionalized difluoroacylated and difluoroalkyl arenes. The method could be further extended to a one-pot protocol for the formation of difluoroacetophenones.
- Andersen, Thomas L.,Frederiksen, Mette W.,Domino, Katrine,Skrydstrup, Troels
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supporting information
p. 10396 - 10400
(2016/08/24)
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- Structural Diversity of Cadmium(II) Coordination Polymers Induced by Tuning the Coordination Sites of Isomeric Ligands
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When the coordination sites of ligands were shifted, the solvothermal reactions of four positional isomeric asymmetrical pyridyldicarboxylatic acids with Cd(NO3)2 generated four new coordination polymers, [Cd(L1)(DMF)3]·DMF·H2O (1), [H2N(CH3)2]2[Cd(L2)2]·3DMF·H2O (2), [Cd(L3)(H2O)2] (3), and [Cd(L4)]·1.5DMF (4), where DMF = N,N-dimethylformamide, H2L1 = 2-(3′-carboxylphenyl)isonicotinic acid, H2L2 = 2-(4′-carboxylphenyl)isonicotinic acid, H2L3 = 5-(3′-carboxylphenyl)nicotic acid, and H2L4 = 2-(3′-pyridyl)terephthalic acid. 1 shows a rare 2D fabric structure. 2 discloses a grid-layer structure with heterochiral helical chains and in which three sets of layers stack in different directions, affording an unprecedented 2D + 2D + 2D → 3D polycatenating framework with 3D intersecting porous systems. 3 also displays a 2D layer possessing strong intralayer π···π interactions and interlayer hydrogen bonds. 4 contains a rare Cd2(COO)4 paddle-wheel unit and forms a 3D framework with 1D open channels. The carboxyl and pyridyl groups of the positional isomeric H2L1-H2L4 ligands show distinct bridging fashions, which leads to the production of versatile architectures of 1-4, and their effects on the crystal structures are discussed. 1-4 reveal solid-state photoluminescence stemming from intraligand charge transfer. 2 and 4 show high selectivity for CO2 over CH4 but with different CO2 adsorption enthalpies. Grand canonical Monte Carlo simulations identified the multiple adsorption sites in 2 for CO2.
- Liu, Bo,Zhou, Hui-Fang,Hou, Lei,Wang, Jian-Ping,Wang, Yao-Yu,Zhu, Zhonghua
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supporting information
p. 8871 - 8880
(2016/10/26)
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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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- Efficient phosphine ligands for the one-pot palladium-catalyzed borylation/Suzuki-Miyaura cross-coupling reaction
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We report the synthesis of 2-(anthracen-9-yl)-1H-inden-3-yl dicyclohexylphosphine and its use in palladium-catalyzed borylation/Suzuki-Miyaura cross-coupling reaction to prepare a variety of symmetrical and unsymmetrical biaryl compounds in excellent yield. This journal is
- Chen, You,Peng, Hui,Pi, Yun-Xiao,Meng, Tong,Lian, Ze-Yu,Yan, Meng-Qi,Liu, Yan,Liu, Sheng-Hua,Yu, Guang-Ao
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supporting information
p. 3236 - 3242
(2015/03/18)
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- Boryl substitution of functionalized aryl-, heteroaryl- and alkenyl halides with silylborane and an alkoxy base: expanded scope and mechanistic studies
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A transition-metal-free method has been developed for the boryl substitution of functionalized aryl-, heteroaryl- and alkenyl halides with a silylborane in the presence of an alkali-metal alkoxide. The base-mediated boryl substitution of organohalides with a silylborane was recently reported to provide the corresponding borylated products in good to high yields, and exhibit good functional group compatibility and high tolerance to steric hindrance. In this study, the scope of this transformation has been extended significantly to include a wide variety of functionalized aryl-, heteroaryl- and alkenyl halides. In particular, the boryl substitution of (E)- and (Z)-alkenyl halides proceeded smoothly to afford the corresponding alkenyl boronates in good to high yields with retention of the configuration using modified reaction conditions. The results of the mechanistic studies suggest that this boryl substitution proceeds via a carbanion-mediated mechanism.
- Yamamoto, Eiji,Ukigai, Satoshi,Ito, Hajime
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p. 2943 - 2951
(2015/06/17)
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- Mitigation of Acetylcholine Esterase Activity in the 1,7-Diazacarbazole Series of Inhibitors of Checkpoint Kinase 1
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Checkpoint kinase 1 (ChK1) plays a key role in the DNA damage response, facilitating cell-cycle arrest to provide sufficient time for lesion repair. This leads to the hypothesis that inhibition of ChK1 might enhance the effectiveness of DNA-damaging therapies in the treatment of cancer. Lead compound 1 (GNE-783), the prototype of the 1,7-diazacarbazole class of ChK1 inhibitors, was found to be a highly potent inhibitor of acetylcholine esterase (AChE) and unsuitable for development. A campaign of analogue synthesis established SAR delineating ChK1 and AChE activities and allowing identification of new leads with improved profiles. In silico docking using a model of AChE permitted rationalization of the observed SAR. Compounds 19 (GNE-900) and 30 (GNE-145) were identified as selective, orally bioavailable ChK1 inhibitors offering excellent in vitro potency with significantly reduced AChE activity. In combination with gemcitabine, these compounds demonstrate an in vivo pharmacodynamic effect and are efficacious in a mouse p53 mutant xenograft model.
- Gazzard, Lewis,Williams, Karen,Chen, Huifen,Axford, Lorraine,Blackwood, Elizabeth,Burton, Brenda,Chapman, Kerry,Crackett, Peter,Drobnick, Joy,Ellwood, Charles,Epler, Jennifer,Flagella, Michael,Gancia, Emanuela,Gill, Matthew,Goodacre, Simon,Halladay, Jason,Hewitt, Joanne,Hunt, Hazel,Kintz, Samuel,Lyssikatos, Joseph,Macleod, Calum,Major, Sarah,Médard, Guillaume,Narukulla, Raman,Ramiscal, Judi,Schmidt, Stephen,Seward, Eileen,Wiesmann, Christian,Wu, Ping,Yee, Sharon,Yen, Ivana,Malek, Shiva
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p. 5053 - 5074
(2015/07/02)
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- SiliaCat diphenylphosphine palladium(II) catalyzed borylation of aryl halides
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We investigate the heterogeneously catalyzed direct synthesis of boronic acid pinacol esters using a wide range of aryl chlorides, bromides, and iodides, and bis(pinacolato)diboron as the borylating agent over the sol-gel entrapped SiliaCat diphenylphosphine palladium(II) catalyst. Optimization of the reaction conditions, scale-up of the optimized process, and analysis of palladium leaching enabled us to establish a new selective route for direct access to a diverse set of boronic acid pinacol esters. Clean borylation for scale-up: With the easy access and broad availability of diverse borylated species, the Suzuki-Miyaura reaction has become routine in industry and in research labs. We report a new selective route for direct access to a diverse set of boronic acid pinacol esters over the sol-gel entrapped SiliaCat diphenylphosphine palladium(II) catalyst that can be easily scaled-up.
- Pandarus, Valerica,Marion, Olivier,Gingras, Genevieve,Beland, Francois,Ciriminna, Rosaria,Pagliaro, Mario
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p. 1340 - 1348
(2014/05/20)
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- Silica-supported tripod triarylphosphines: Application to palladium-catalyzed borylation of chloroarenes
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Silica-supported tripod triarylphosphines that have a Ph3Ptype core tripodally immobilized on a silica surface enabled the Pd-catalyzed borylation of chloroarenes with bis(pinacolato)diboron under mild conditions. The immobilization in tripod was crucial for the excellent performance of the Ph3P-based ligands.
- Iwai, Tomohiro,Harada, Tomoya,Tanaka, Ryotaro,Sawamura, Masaya
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supporting information
p. 584 - 586
(2014/05/20)
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- Iridium-catalyzed C-H borylation of heteroarenes: Scope, regioselectivity, application to late-stage functionalization, and mechanism
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A study on the iridium-catalyzed C-H borylation of heteroarenes is reported. Several heteroarenes containing multiple heteroatoms were found to be amenable to C-H borylation catalyzed by the combination of an iridium(I) precursor and tetramethylphenanthroline. The investigations of the scope of the reaction led to the development of powerful rules for predicting the regioselectivity of borylation, foremost of which is that borylation occurs distal to nitrogen atoms. One-pot functionalizations are reported of the heteroaryl boronate esters formed in situ, demonstrating the usefulness of the reported methodology for the synthesis of complex heteroaryl structures. Application of this methodology to the synthesis and late-stage functionalization of biologically active compounds is also demonstrated. Mechanistic studies show that basic heteroarenes can bind to the catalyst and alter the resting state from the olefin-bound complex observed during arene borylation to a species containing a bound heteroarene, leading to catalyst deactivation. Studies on the origins of the observed regioselectivity show that borylation occurs distal to N-H bonds due to rapid N-H borylation, creating an unfavorable steric environment for borylation adjacent to these bonds. Computational studies and mechanistic studies show that the lack of observable borylation of C-H bonds adjacent to basic nitrogen is not the result of coordination to a bulky Lewis acid prior to C-H activation, but the combination of a higher-energy pathway for the borylation of these bonds relative to other C-H bonds and the instability of the products formed from borylation adjacent to basic nitrogen.
- Larsen, Matthew A.,Hartwig, John F.
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supporting information
p. 4287 - 4299
(2014/04/03)
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- Clean and fast cross-coupling of aryl halides in one-pot
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Unsymmetrically coupled biaryls are synthesized in high yield starting from different aryl bromides and bis(pinacolato)diboron by carrying out the Miyaura borylation reaction followed by the Suzuki-Miyaura reaction in the same reaction pot over 1-2 mol % SiliaCat DPP-Pd. The SiliaCat DPP-Pd catalyst is air-stable and the method does not require the use of inert conditions. The use of non-toxic isopropanol or 2-butanol as reaction solvent further adds to the environmental benefits of this new green synthetic methodology.
- Pandarus, Valerica,Gingras, Genevieve,Beland, Francois,Ciriminna, Rosaria,Pagliaro, Mario
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p. 897 - 901
(2014/05/20)
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- Synthesis of pinacol arylboronates from aromatic amines: A metal-free transformation
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A metal-free borylation process based on Sandmeyer-type transformation using arylamines derivatives as the substrates has been developed. Through optimization of the reaction conditions, this novel conversion can be successfully applied to a wide range of aromatic amines, affording borylation products in moderate to good yields. Various functionalized arylboronates, which are difficult to access by other methods, can be easily obtained with this metal-free transformation. Moreover, this transformation can be followed by Suzuki-Miyaura cross-coupling without purification of the borylation products, which enhances the practical usefulness of this method. A possible reaction mechanism involving radical species has been proposed.
- Qiu, Di,Jin, Liang,Zheng, Zhitong,Meng, He,Mo, Fanyang,Wang, Xi,Zhang, Yan,Wang, Jianbo
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p. 1923 - 1933
(2013/03/29)
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