- Palladium nanoparticles on graphite oxide and its functionalized graphene derivatives as highly active catalysts for the Suzuki-Miyaura coupling reaction
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Pd2+-exchanged graphite oxide and chemically derived graphenes therefrom were employed as supports for Pd nanoparticles. The influence of catalyst preparation, carbon functionalization, and catalyst morphology on the catalytic activity in the Suzuki-Miyaura coupling reactions was investigated. The catalysts were characterized by means of spectroscopy (FT-IR, solid-state 13C NMR, AAS, XPS), X-ray scattering (WAXS), surface area analysis (BET, methylene blue adsorption), and electron microscopy (TEM, ESEM). In contrast to the conventional Pd/C catalyst, graphite oxide and graphene-based catalysts gave much higher activities with turnover frequencies exceeding 39 000 h-1, accompanied by very low palladium leaching (1 ppm).
- Scheuermann, Gil M.,Steurer, Peter,Muelhaupt, Rolf,Rumi, Luigi,Bannwarth, Willi
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- Palladium-catalyzed coupling of functionalized bromoarenes to a polystyrene-bound aryl tributylstannane
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The Stille reaction with a polystyrene-bound stannyl component, catalyzed by a palladacycle complex, provides a convenient and clean method for the synthesis of substituted biaryls on the resin. Several functional groups useful for the construction of supported polydentate amino alcohols were successfully introduced.
- Brody, Marcus S.,Finn
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- Palladium-loaded renewable polymer as a green heterogeneous catalyst for cross-coupling reactions under microwave irradiation
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A new palladium catalyst was prepared by immobilising ligand 2, 2'-dipyridylamine on the backbone of an acidic rosin polymer from gum rosin, on to which palladium(II) was bound via coordination. The catalyst at a low loading of 0.2 mol% was found to be highly effective for Suzuki-Miyaura coupling reactions of aryl halides and arylboronic acids under microwave irradiation in the presence of 1 equiv. of Na2CO3, affording excellent yields of the corresponding biaryls. Moreover, the catalyst exhibited very good recyclability over three cycles.
- Pan, Dan,Wu, Aiqun,Li, Pengfei,Xu, Haitang,Lei, Fuhou,Shen, Liqun
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- Suzuki coupling catalyzed by ligand-free palladium(II) species at room temperature and by exposure to air
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Ligand-free palladium acetate and palladium chloride have been evaluated as catalysts in the Suzuki cross-coupling of aryl boronic acid with aryl and vinyl bromide in ethanol at room temperature and with exposure to air. The substrates with a wide variety of functional groups, including base-sensitive ones are tolerated.
- Deng, Yijian,Gong, Liuzhu,Mi, Aiqiao,Liu, Hui,Jiang, Yaozhong
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- Rapid Fluorous Stille Coupling Reactions Conducted under Microwave Irradiation
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Palladium-catalyzed fluorous Stille cross-coupling reactions with organic halides or triflates require only 90-120 s for completion when conducted under microwave irradiation. Comparable thermal reactions require about 1 day. Fourteen different coupling products were synthesized and isolated in good yields after three-phase extraction (FC-84, dichloromethane, water) and chromatography. The examples extend the scope of the fluorous Stille coupling with respect to both the tin and halide/triflate components. Applications in parallel synthesis are suggested.
- Larhed, Mats,Hoshino, Masahide,Hadida, Sabine,Curran, Dennis P.,Hallberg, Anders
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- An efficient microwave-assisted suzuki reaction using a new pyridine-pyrazole/Pd(II) species as catalyst in aqueous media
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A new pyridine-pyrazole N-N ligand has been conveniently synthesized and characterized by 1H-, 13C-NMR, IR spectroscopies, HRMS and X-ray single-crystal crystallography analyses. The ligand adds to palladium(II) under basic conditions to give high yields of an air-stable and water-soluble complex that was fully characterized by NMR and HRMS. The complex was investigated as a catalyst for the Suzuki reaction in aqueous media under microwave irradiation. The compound proved to be an effective catalyst.
- Shen, Liqun,Huang, Suyu,Nie, Yuanmei,Lei, Fuhou
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- Design, synthesis, and biological evaluation of novel dual FFA1 and PPARδ agonists possessing phenoxyacetic acid scaffold
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The free fatty acid receptor 1 (FFA1/GPR40) and peroxisome proliferator-activated receptor δ (PPARδ) have been widely considered as promising targets for type 2 diabetes mellitus (T2DM) due to their respective roles in promoting insulin secretion and impr
- Zhou, Zongtao,Cai, Zongyu,Zhang, Congzi,Yang, Benhui,Chen, Lianru,He, Yepu,Zhang, Luyong,Li, Zheng
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- Palladium-Catalyzed Reductive Carbonylation of (Hetero) Aryl Halides and Triflates Using Cobalt Carbonyl as CO Source
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An efficient protocol for the reductive carbonylation of (hetero) aryl halides and triflates under CO gas-free conditions using Pd/Co2(CO)8 and triethylsilane has been developed. The mild reaction conditions, enhanced chemoselectivity and, easy access to heterocyclic and vinyl carboxaldehydes highlights its importance in organic synthesis.
- Dogga, Bhushanarao,Joseph, Jayan T.,Kumar, C. S. Ananda
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supporting information
p. 309 - 313
(2020/12/23)
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- Cost-effective bio-derived mesoporous carbon nanoparticles-supported palladium catalyst for nitroarene reduction and Suzuki–Miyaura coupling by microwave approach
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A new heterogeneous catalyst was synthesized by immobilizing Pd on areca nut kernel-derived carbon nanospheres (CNSs). The CNSs, without any further activation processes, accommodated 3% of Pd on their surface. The new Pd/CNS material was used for the reduction of nitroarenes and Suzuki–Miyaura coupling of bromoarenes with aryl boronic acids. The reactions were conducted under microwave irradiation at 160 °C using 12 mol% of Pd/CNS (0.36% actual Pd content). The reduction of nitroarenes into their respective amino compounds was achieved in 10–20 min (conversion up to 100%); by contrast, the Suzuki–Miyaura reactions yielded up to 98% at 150 °C with 10 mol% of Pd/CNS catalyst. The products were identified using gas chromatography and nuclear magnetic resonance spectroscopy. The catalyst was isolated from reaction mixture and reused without any significant loss in the activity. Thus, the present work introduces one-pot-derived porous CNSs as efficient catalytic support to Pd, establishing an alternative to existing Pd/C in terms of cost and efficiency.
- Supriya,Ananthnag, Guddekoppa S.,Shetti, Vijayendra S.,Nagaraja,Hegde, Gurumurthy
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- Sustainable Ligand-Free, Palladium-Catalyzed Suzuki–Miyaura Reactions in Water: Insights into the Role of Base
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A simple and efficient system was developed for the ligand-free Pd-catalyzed Suzuki–Miyaura reaction in water under mild conditions. Quaternary ammonium hydroxides with long chains were found to be very suitable bases. This ligand-free Pd-catalyzed Suzuki–Miyaura reaction showed improved durability in water with Pd loadings decreased to ppm level. Bases were shown to stabilize active palladium species in addition to acting as a base during the catalytic process. In the catalytic system with a strong base, the soluble active PdII ion exhibited anti-reduction properties, which prevented aggregation and deactivation of Pd species. The entire catalytic system could be recycled after separating the product by simple filtration. The water-compatible and air-stable effective catalytic protocol described herein represents an attractive and green synthetic advance in Suzuki–Miyaura couplings.
- Wang, Yanyan,Liu, Yuanyuan,Zhang, Wei-qiang,Sun, Huaming,Zhang, Kan,Jian, Yajun,Gu, Quan,Zhang, Guofang,Li, Jiyang,Gao, Ziwei
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p. 5265 - 5273
(2019/11/29)
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- Base-Free Suzuki–Miyaura Coupling Reaction Using Palladium(II) Supported Catalyst in Water
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Abstract: The carbon–carbon bond formation via Suzuki–Miyaura reaction was performed in water as green solvent. Pd(OAc)2(PPh3)2 supported on magnesium hydroxide and cerium carbonate hydroxide composite was prepared and characterized by various techniques. The cross-coupling reaction of aryl halides carried out in water using mild conditions. The effects of temperature, solvents, the amount of catalyst and leaving groups were studied to find the optimization conditions for cross-coupling reaction. Various aryl halides were smoothly transformed into the biaryls in good yields. In addition, the catalyst also exhibited stability and catalytic performance in the cross-coupling of aryl halides. Graphical Abstract: [Figure not available: see fulltext.] A new approach is developed for carbon–carbon bond formation via Suzuki–Miyaura reaction.2 Pd(OAc)2(PPh3)2?supported on mixed magnesium hydroxide and cerium carbonate hydroxide were prepared and characterized by XRD, XPS, SEM–EDX techniques. The cross-coupling reaction of aryl halides can be carried out in water and under mild conditions (80 °C).
- Tomar, Ravi,Singh, Nidhi,Kumar, Neeraj,Tomar, Vartika,Chandra, Ramesh
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- One-Pot Tandem Photoredox and Cross-Coupling Catalysis with a Single Palladium Carbodicarbene Complex
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The combination of conventional transition-metal-catalyzed coupling (2 e? process) and photoredox catalysis (1 e? process) has emerged as a powerful approach to catalyze difficult cross-coupling reactions under mild reaction conditions. Reported is a palladium carbodicarbene (CDC) complex that mediates both a Suzuki–Miyaura coupling and photoredox catalysis for C?N bond formation upon visible-light irradiation. These two catalytic pathways can be combined to promote both conventional transition-metal-catalyzed coupling and photoredox catalysis to mediate C?H arylation under ambient conditions with a single catalyst in an efficient one-pot process.
- Hsu, Yu-Cheng,Wang, Vincent C.-C.,Au-Yeung, Ka-Chun,Tsai, Chung-Yu,Chang, Chun-Chi,Lin, Bo-Chao,Chan, Yi-Tsu,Hsu, Chao-Ping,Yap, Glenn P. A.,Jurca, Titel,Ong, Tiow-Gan
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supporting information
p. 4622 - 4626
(2018/03/21)
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- 4-Aryliden-2-methyloxazol-5(4H)-one as a new scaffold for selective reversible MAGL inhibitors
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This study reports on a preliminary structure-activity relationship exploration of 4-aryliden-2-methyloxazol-5(4H)-one-based compounds as MAGL/FAAH inhibitors. Our results highlight that this scaffold may serve for the development of selective MAGL inhibi
- Granchi, Carlotta,Rizzolio, Flavio,Bordoni, Vittorio,Caligiuri, Isabella,Manera, Clementina,Macchia, Marco,Minutolo, Filippo,Martinelli, Adriano,Giordano, Antonio,Tuccinardi, Tiziano
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p. 137 - 146
(2016/01/12)
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- Acyclic aminocarbene-like palladium complex-catalyzed Suzuki-Miyaura reaction at low catalyst loadings
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A series of air-stable aminocarbene-like palladium(II) complexes were easily prepared by the reaction of bis-aromaticisocyanide-dichloropalladium(II) with N-arylbenzamidines. 0.1 mol % of the optimal palladium complex 3a showed excellent catalytic activity for Suzuki-Miyaura cross-coupling reaction at room temperature and the desired products were isolated in up to 98% yields. Moreover, a large-scale reaction showed that 0.01 mol % 3a was enough to catalyze the coupling reaction efficiently at room temperature to give the desired product in 93% yield.
- Fang, Yi,Wang, Shun-Yi,Ji, Shun-Jun
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p. 9679 - 9683
(2015/12/04)
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- Efficient one-pot cross-coupling of two aryl halides by stannylation/stille reaction in water under microwave irradiation
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A simple and highly efficient one-pot approach has been developed for the Pd(PPh3)4-catalyzed cross-coupling of two different aryl or heteroaryl bromides/iodides. This method involves the combined use of microwave irradiation and water as a single solvent to achieve sequential stannylation and Stille cross-coupling reactions, which allows rapid access to a wide variety of biaryls in good to high yields. Furthermore, utilizing this step-economical protocol, 2,5-dibromopyridine was iteratively diarylated and the Boscalid intermediate was also synthesized in a one-pot manner. Copyright
- Tan, Xin,Zhou, Zi Jie,Zhang, Jia Xin,Duan, Xin Hong
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supporting information
p. 5153 - 5157
(2014/09/29)
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- Transforming Suzuki-Miyaura cross-couplings of MIDA boronates into a green technology: No organic solvents
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New technology has been developed that enables Suzuki-Miyaura couplings involving widely utilized MIDA boronates to be run in water as the only medium, mainly at room temperature. The protocol is such that no organic solvent is involved at any stage; from the reaction through to product isolation. Hence, using the E factor scale as a measure of greenness, the values for these cross-couplings approach zero.
- Isley, Nicholas A.,Gallou, Fabrice,Lipshutz, Bruce H.
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supporting information
p. 17707 - 17710
(2014/01/06)
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- Dissection of complex molecular recognition interfaces
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The synthesis of a family of zinc porphyrins and pyridine ligands equipped with peripheral H-bonding functionality has provided access to a wide range of closely related supramolecular complexes featuring between zero and four intramolecular H-bonds. An automated UV/vis titration system was used to characterize 120 different complexes, and these data were used to construct a large of number of different chemical double mutant cycles to quantify the intramolecular H-bonding interactions. The results probe the quantitative structure-activity relationship that governs cooperativity in the assembly of complex molecular recognition interfaces. Specifically, variations in the chemical structures of the complexes have allowed us to change the supramolecular architecture, conformational flexibility, geometric complementarity, the number and nature of the H-bond interactions, and the overall stability of the complex. The free energy contributions from individual H-bonds are additive, and there is remarkably little variation with architecture in the effective molarity for the formation of intramolecular interactions. Intramolecular H-bonds are not observed in complexes where they are geometrically impossible, but there are no cases where excellent geometric complementarity leads to very high affinities. Similarly, changes in conformational flexibility seem to have limited impact on the values of effective molarity (EM). The major variation that was found for all of the 48 intramolecular interactions that were examined using double mutant cycles is that the values of EM for intramolecular carboxylate ester-phenol H-bonds (200 mM) are an order of magnitude larger than those found for phosphonate diester-phenol H-bonds (30 mM). The corresponding intermolecular phosphonate diester-phenol H-bonds are 2 orders of magnitude more stable than carboxylate ester-phenol H-bonds, and the large differences in EM may be due to some kind of compensation effect, where the stronger H-bond is harder to make, because it imposes tighter constraints on the geometry of the complex.
- Hunter, Christopher A.,Misuraca, Maria Cristina,Turega, Simon M.
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supporting information; experimental part
p. 582 - 594
(2011/04/16)
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- [Pd(Cl)2(P(NC5H10)(C6H 11)2)2] - A highly effective and extremely versatile palladium-based negishi catalyst that efficiently and reliably operates at low catalyst loadings
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[Pd(Cl)2(P(NC5H10)-(C6H 11)2]2] (1) has been prepared in quantitative yield by reacting commercially available [Pd(cod)(Cl)2] (cod = cyclooctadiene) with readily prepared 1-(dicyclohexylphosphanyl)piperidine in toluene under N2 within a few minutes at room temperature. Complex 1 has proved to be an excellent Negishi catalyst, capable of quantitatively coupling a wide variety of electronically activated, non-activated, deactivated, sterically hindered, heterocyclic, and functionalized aryl bromides with various (also heterocyclic) arylzinc reagents, typically within a few minutes at 100°C in the presence of just 0.01 mol% of catalyst. Aryl bromides containing nitro, nitrile, ether, ester, hydroxy, carbonyl, and carboxyl groups, as well as acetais, lactones, amides, anilines, alkenes, carboxylic acids, acetic acids, and pyridines and pyrimidines, have been successfully used as coupling partners. Furthermore, electronic and steric variations are tolerated in both reaction partners. Experimental observations strongly indicate that a molecular mechanism is operative.
- Bolliger, Jeanne L.,Frech, Christian M.
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experimental part
p. 11072 - 11081
(2010/11/16)
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- Abnormal N-heterocyclic carbene promoted Suzuki-Miyaura coupling reaction: A comparative study
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A C2-protected imidazolium salt that generates an abnormal N-heterocyclic carbene (NHC) was applied for the palladium-catalyzed Suzuki-Miyaura coupling reactions. The abnormal NHC precursor promoted the reactions while suppressing homocoupling of aryl boronic acid, which was observed with the corresponding normal NHC precursor. The related well-defined abnormal NHC-based palladium complexes also showed better activity than the normal NHC-based analogues, exhibiting faster reaction rates especially at the initial stage of the reaction.
- Xu, Xiangya,Xu, Baochang,Li, Yongxin,Hong, Soon Hyeok
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scheme or table
p. 6343 - 6349
(2011/02/17)
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- An oxidative rearrangement of 6-phenylbicyclo[3.2.0]heptan-6-ol to 1,1′-biphenyl-carbaldehydes: A mechanistic study
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Acid-catalyzed rearrangement of 6-phenylbicyclo[3.2.0]heptan-6-ol gave 1,1′-biphenyl and 1,1′-biphenyl-carbaldehydes in small amounts as well as the expected rearrangement products. A detailed study of the reaction mechanism revealed that the conversion occurs via an oxidative process through the consecutive formation of cycloheptadienes, cycloheptatrienes, and 1,1′-biphenyls. The acid-catalyzed rearrangement of 6-phenylbicyclo[3.2.0] hept-2-en-6-ols gave 1- and 2-phenylcycloheptatrienes directly, from which 1,1′-biphenyl and 1,1′-biphenyl-carbaldehydes were obtained by oxidation.
- Ceylan, Mustafa,Findik, Esra,Secen, Hasan
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experimental part
p. 559 - 568
(2009/02/07)
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- Non-thiol farnesyltransferase inhibitors: Utilization of the far aryl binding site by arylthienylacryloyl-aminobenzophenones
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We recently described two novel aryl binding sites of farnesyltransferase. The 4- and 5-arylsubstituted thienylacryloyl moieties turned out as appropriate substituents for our benzophenone-based AAX-peptidomimetic capable for occupying the far aryl binding site.
- Mitsch, Andreas,Altenkaemper, Mirko,Sattler, Isabel,Schlitzer, Martin
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- Structure-activity relationships of novel anti-malarial agents part 8. Effect of different central aryls in biarylacryloylaminobenzophenones on antimalarial activity
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Replacement of the 2,5-disubstituted furyl residue present in the known antimalarial agents 8 by other aryl residues resulted in a more or less reduced antimalarial activity in most cases. The only exemption was the 2,4-thienylene compound 11a displaying activity with an IC50 value of 120 nM. In conclusion, the 2,5-furylene compound 8e remains to represent the most active antimalarial agent in this series of farnesyltransferase inhibitors.
- Wiesner,Mitsch,Altenkaemper,Ortmann,Jomaa,Schlitzer, Martin
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p. 854 - 856
(2007/10/03)
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- Activation of Reducing Agents. Sodium Hydride Containing Complex Reducing Agents. 32. NiCRAL's as Very Efficient Agents in Promoting Cross-Coupling of Aryl Halides
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Nickel-containing complex reducing agents NiCRA-bpy are shown to be the first nickel reagents able to efficiently perform cross-coupling of aryl halides.The presence of KI in the reaction medium generally improves the procedure.The mechanism and influence of the structures of the substrates are discused.
- Lourak, Mouhsine,Vanderesse, Regis,Fort, Yves,Caubere, Paul
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p. 4844 - 4848
(2007/10/02)
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