586-39-0Relevant articles and documents
A General Concurrent Template Strategy for Ordered Mesoporous Intermetallic Nanoparticles with Controllable Catalytic Performance
Ariga, Katsuhiko,Liu, Ben,Lv, Hao,Qin, Huaiyu,Yamauchi, Yusuke
supporting information, (2022/03/08)
We report a general concurrent template strategy for precise synthesis of mesoporous Pt-/Pd-based intermetallic nanoparticles with desired morphology and ordered mesostructure. The concurrent template not only supplies a mesoporous metal seed for re-crystallization growth of atomically ordered intermetallic phases with unique atomic stoichiometry but also provides a nanoconfinement environment for nanocasting synthesis of mesoporous nanoparticles with ordered mesostructure and rhombic dodecahedral morphology under elevated temperature. Using the selective hydrogenation of 3-nitrophenylacetylene as a proof-of-concept catalytic reaction, mesoporous intermetallic PtSn nanoparticles exhibited remarkably controllable intermetallic phase-dependent catalytic selectivity and excellent catalytic stability. This work provides a very powerful strategy for precise preparation of ordered mesoporous intermetallic nanocrystals for application in selective catalysis and fuel cell electrocatalysis.
A Magnetically Separable Pd Single-Atom Catalyst for Efficient Selective Hydrogenation of Phenylacetylene
Zhao, Linmin,Qin, Xuetao,Zhang, Xirui,Cai, Xiangbin,Huang, Fei,Jia, Zhimin,Diao, Jiangyong,Xiao, Dequan,Jiang, Zheng,Lu, Ruifeng,Wang, Ning,Liu, Hongyang,Ma, Ding
, (2022/04/19)
Selective hydrogenation of alkynes to alkenes plays a crucial role in the synthesis of fine chemicals. However, how to achieve high selectivity and effective separation of the catalyst and substrate while obtaining high activity is the key for this reaction. In this work, a Pd single-atom catalyst is anchored to the shell of magnetic core–shell particles that consist of a Ni-nanoparticles core and a graphene sheets shell (Ni@G) for semi-hydrogenation of phenylacetylene, delivering 93% selectivity to styrene at full conversion with a robust turnover frequency of 7074 h?1 under mild reaction conditions (303 K, 2?bar H2). Moreover, the catalyst can be recovered promptly from the liquid phase due to its magnetic separability, which makes it present good stability for enduring five cycles. Experimental and theoretical investigations reveal that H2 and substrates are activated by atomically dispersed Pd atoms and Ni@G hybrid support, respectively. The hydrogenation reaction occurs on the surface of Ni@G via hydrogen spillover from the metal to the support. Such a strategy opens an avenue for designing highly active, selective, and magnetically recyclable catalysts for selective hydrogenation in liquid reaction systems.
Development of LM98, a Small-Molecule TEAD Inhibitor Derived from Flufenamic Acid
Mélin, Léa,Abdullayev, Shuay,Fnaiche, Ahmed,Vu, Victoria,González Suárez, Narjara,Zeng, Hong,Szewczyk, Magdalena M.,Li, Fengling,Senisterra, Guillermo,Allali-Hassani, Abdellah,Chau, Irene,Dong, Aiping,Woo, Simon,Annabi, Borhane,Halabelian, Levon,LaPlante, Steven R.,Vedadi, Masoud,Barsyte-Lovejoy, Dalia,Santhakumar, Vijayaratnam,Gagnon, Alexandre
, p. 2982 - 3002 (2021/08/03)
The YAP-TEAD transcriptional complex is responsible for the expression of genes that regulate cancer cell growth and proliferation. Dysregulation of the Hippo pathway due to overexpression of TEAD has been reported in a wide range of cancers. Inhibition of TEAD represses the expression of associated genes, demonstrating the value of this transcription factor for the development of novel anti-cancer therapies. We report herein the design, synthesis and biological evaluation of LM98, a flufenamic acid analogue. LM98 shows strong affinity to TEAD, inhibits its autopalmitoylation and reduces the YAP-TEAD transcriptional activity. Binding of LM98 to TEAD was supported by 19F-NMR studies while co-crystallization experiments confirmed that LM98 is anchored within the palmitic acid pocket of TEAD. LM98 reduces the expression of CTGF and Cyr61, inhibits MDA-MB-231 breast cancer cell migration and arrests cell cycling in the S phase during cell division.
Selective and Additive-Free Hydrogenation of Nitroarenes Mediated by a DMSO-Tagged Molecular Cobalt Corrole Catalyst
Sch?fberger, Wolfgang,Timelthaler, Daniel,Topf, Christoph
supporting information, p. 2114 - 2120 (2021/07/22)
We report on the first cobalt corrole that effectively mediates the homogeneous hydrogenation of structurally diverse nitroarenes to afford the corresponding amines. The given catalyst is easily assembled prior to use from 4-tert-butylbenzaldehyde and pyrrole followed by metalation of the resulting corrole macrocycle with cobalt(II) acetate. The thus-prepared complex is self-contained in that the hydrogenation protocol is free from the requirement for adding any auxiliary reagent to elicit the catalytic activity of the applied metal complex. Moreover, a containment system is not required for the assembly of the hydrogenation reaction set-up as both the autoclave and the reaction vessels are readily charged under a regular laboratory atmosphere.
Iron-Catalyzed Direct Julia-Type Olefination of Alcohols
Landge, Vinod G.,Babu, Reshma,Yadav, Vinita,Subaramanian, Murugan,Gupta, Virendrakumar,Balaraman, Ekambaram
, p. 9876 - 9886 (2020/09/03)
Herein, we report an iron-catalyzed, convenient, and expedient strategy for the synthesis of styrene and naphthalene derivatives with the liberation of dihydrogen. The use of a catalyst derived from an earth-abundant metal provides a sustainable strategy to olefins. This method exhibits wide substrate scope (primary and secondary alcohols) functional group tolerance (amino, nitro, halo, alkoxy, thiomethoxy, and S- A nd N-heterocyclic compounds) that can be scaled up. The unprecedented synthesis of 1-methyl naphthalenes proceeds via tandem methenylation/double dehydrogenation. Mechanistic study shows that the cleavage of the C-H bond of alcohol is the rate-determining step.
Exploring the nitro group reduction in low-solubility oligo-phenylenevinylene systems: Rapid synthesis of amino derivatives
Acelas, Mauricio,Sierra, Andrés Felipe,Sierra, César A.
supporting information, p. 1335 - 1352 (2020/03/04)
A small series of amino oligo-phenylenevinylenes (OPVs) were successfully synthesized from their nitro-analogs in a rapid, simple, and highly efficient fashion employing a sodium sulfide/pyridine system as a reducing agent. In this research, classic and sustainable reduction methodologies including NH4HCO2/Zn and a choline chloride/tin (II) chloride deep eutectic solvent (DES) were also evaluated, showing degradation products, incomplete reactivity, and product isolation difficulties in all cases. The straightforward Na2S/pyridine synthetic protocol proved to maintain the E-E stereochemistry of the OPV backbone that has been previously assembled by the Mizoroki–Heck cross-coupling reaction. Also, the optoelectronic properties were determined and discussed, considering the amino group insertion in these conjugated systems as a contribution for future construction of novel materials with applications in supramolecular electronics, light harvesting, and photocatalysis.
Tetrahydropyrrole compound, preparation method, pharmaceutical composition and application thereof
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Paragraph 0408-0413, (2019/07/16)
The invention discloses a tetrahydropyrrole compound and a preparation method, a pharmaceutical composition and application thereof. The tetrahydropyrrole compound of the invention is as shown in thegeneral formula (I). The tetrahydropyrrole compound of the invention has an excellent inhibitory effect on the positive symptom of schizophrenia, and has equivalent or stronger efficacy in comparisonwith the positive medicine olanzapine. In addition, the compound of the invention has a dual inhibitory effect on a D2 receptor and a DAT receptor, can effectively treat schizophrenia and improve negative symptoms and cognitive functions, and helps reduce side-effect of centrum and secretion of lactogen.
Hydroxyl Assisted Rhodium Catalyst Supported on Goethite Nanoflower for Chemoselective Catalytic Transfer Hydrogenation of Fully Converted Nitrostyrenes
Hu, Zenan,Ai, Yongjian,Liu, Lei,Zhou, Junjie,Zhang, Gang,Liu, Hongqi,Liu, Xiangyu,Liu, Zhibo,Hu, Jianshe,Sun, Hong-bin,Liang, Qionglin
supporting information, p. 3146 - 3154 (2019/05/10)
Control of chemoselectivity is a special challenge for the reduction of nitroarenes bearing one or more unsaturated groups. Here, we report a flower-like Rh/α-FeOOH catalyst for the chemoselective hydrogenation of nitrostyrene to vinylaniline over full conversion, which benefits the new functionalized aminostyrene because the multisubstituted aminostyrenes are usually commercially unavailable. This catalyst does not only show desirable selectivity for the vinylanilines, but also exhibits the inertness to various other reducible groups over wide reaction duration. The catalytic selectivity for the reduction of the nitro group towards vinyl group was investigated by the control experiments and FT-IR analysis. We have found that the abundant hydroxyl groups in the α-FeOOH may contribute to the improvement of catalytic activity and selectivity. Furthermore, the catalyst exhibits excellent stability and keeps its catalytic performance even after 6 cycles. (Figure presented.).
Copper-Catalyzed Oxidative Difunctionalization of Terminal Unactivated Alkenes
Hussain, Muhammad Ijaz,Feng, Yangyang,Hu, Liangzhen,Deng, Qingfu,Zhang, Xiaohui,Xiong, Yan
, p. 7852 - 7859 (2018/05/30)
The copper(II)-promoted free-radical oxidative difunctionalization of terminal alkenes to access ketoazides by utilizing molecular oxygen has been reported. A series of styrene derivatives have been evaluated and were found to be compatible to give the desired difunctionalized products in moderate to good yields. The role of molecular oxygen both as an oxidant and oxygen atom source in this catalytic transformation has been unquestionably demonstrated by 18O-labeling studies and a radical mechanistic pathway involving the oxidative formation of azidyl radicals is also designed. This environment-friendly catalytic oxidative protocol can transform aldehyde to nitrile.
Enantioselective, Catalytic Vicinal Difluorination of Alkenes
Scheidt, Felix,Sch?fer, Michael,Sarie, Jér?me C.,Daniliuc, Constantin G.,Molloy, John J.,Gilmour, Ryan
supporting information, p. 16431 - 16435 (2018/11/23)
The enantioselective, catalytic vicinal difluorination of alkenes is reported by II/IIII catalysis using a novel, C2-symmetric resorcinol derivative. Catalyst turnover via in situ generation of an ArIIIIF2 species is enabled by Selectfluor oxidation and addition of an inexpensive HF–amine complex. The HF:amine ratio employed in this process provides a handle for regioselective orthogonality as a function of Br?nsted acidity. Selectivity reversal from the 1,1-difluorination pathway (geminal) to the desired 1,2-difluorination (vicinal) is disclosed (>20:1 in both directions). Validation with electron deficient styrenes facilitates generation of chiral bioisosteres of the venerable CF3 unit that is pervasive in drug discovery (20 examples, up to 94:06 e.r.). An achiral variant of the reaction is also presented using p-TolI (up to >95 % yield).
