- Access to Hydroxy-Functionalized Polypropylene through Coordination Polymerization
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Preparation of polyethylenes containing hydroxy groups has been already industrialized through radical copolymerization under harsh conditions followed by alcoholysis. By contrast, hydroxy-functionalized polypropylene has proven a rather challenging goal
- Cui, Dongmei,Douair, Iskander,Maron, Laurent,Wang, Tiantian,Wu, Chunji,Zhong, Yuanhao
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supporting information
p. 4947 - 4952
(2020/02/13)
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- Pyrazolopyrimidine [3,4-d] compound as well as preparation method and application thereof
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The invention relates to a compound which is a Bruton tyrosine kinase inhibitor. In addition, the invention discloses a pharmaceutical ingredient and a preparation that comprise the compound, and an application of the kinase inhibitor. The compound can be used independently or combined with other compounds for treating kinase mediated or kinase-dependent symptoms.
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Paragraph 0297; 0299; 0300; 0301
(2019/06/10)
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- Regioselective Arene and Heteroarene Functionalization: N-Alkenoxypyridinium Salts as Electrophilic Alkylating Agents for the Synthesis of α-Aryl/α-Heteroaryl Ketones
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A direct regioselective functionalization of arenes and heteroarenes using N-alkenoxypyridinium salts as electrophilic alkylating agents for the synthesis of α-aryl/heteroaryl ketones has been developed. The method generates alkylating agents from alkynes and N-pyridine oxide followed by site-selective electrophilic substitution with a broad range of arenes and heteroarenes including benzene derivates, phenols, ethers, indoles, pyrroles, furans, and thiophenes in one pot. Kinetic isotope effect measurements and DFT studies reveal that this reaction likely proceeds through a carbon-cation intermediate.
- Zhai, Rong L.,Xue, Yun S.,Liang, Ting,Mi, Jia J.,Xu, Zhou
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supporting information
p. 10051 - 10059
(2018/07/30)
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- Efficient One-Pot Multifunctionalization of Alkynes en Route to α-Alkoxyketones, α-Thioketones, and α-Thio Thioketals by using an Umpolung Strategy
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The use of polarized synthons is a highly desirable strategy, as it generally enables unprecedented retrosynthetic disconnections for the synthesis of unique substances. Herein, a new approach for α-oxygenated ketones, α-thioketones and α-thio thioketals via an intermolecular umpolung reaction between nucleophiles (alcohols/thioalcohols) and N-alkenoxypyridinium salts, which were generated from the corresponding alkynes, has been developed for the first time. The reactions proceed with good substrate scope and excellent functional group tolerance in one-pot manner. Applications of the products, α-oxygenated ketones, to the synthesis of other valuable synthetic moieties has also been successfully achieved.
- Xu, Zhou,Zhai, Rongliang,Liang, Ting,Zhang, Liming
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supporting information
p. 14133 - 14137
(2017/10/16)
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- Improved Synthesis of C2 and C6 Monoderivatives of α- And β-Cyclodextrin via the Click Chemistry Approach
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An efficient multigram-scale azide-alkyne coupling of cyclodextrin derivatives mono-6-azido-6-deoxy-β-cyclodextrin, mono-2-O-propargyl-β-cyclodextrin, and mono-2-O-propargyl-α-cyclodextrin with terminal alkynyl aryl ethers or azides, mediated by copper(I) is reported. This process uses a stoichiometric ratio of substrates and 5 mol% of the copper catalyst to give the products with full conversion; thus, no chromatographic purification is necessary. The yields of both α- and β-cyclodextrin derivatives are in the range of 80 to 99%.
- Chmurski, Kazimierz,Stepniak, Pawel,Jurczak, Janusz
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supporting information
p. 1838 - 1843
(2015/06/30)
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- Rhodium-catalyzed intramolecular hydroarylation of 1-halo-1-alkynes: Regioselective synthesis of semihydrogenated aromatic heterocycles
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The regioselective intramolecular hydroarylation of (3-halo-2-propynyl) anilines, (3-halo-2-propynyl) aryl ethers, or (4-halo-3-butynyl) aryl ethers was efficiently catalyzed by Rh2(OCOCF3)4 to give semihydrogenated aromatic heterocycles, such as 4-halo-1,2-dihydroquinolines, 4-halo-3-chromenes, or 4-(halomethylene)chromans, in good to excellent yields. Some synthetic applications taking advantage of the halo-substituents of the products are also illustrated. Ring a rhodium! Regioselective intramolecular hydroarylation of haloacetylenes efficiently catalyzed by [Rh 2(tfa)4] (see scheme; tfa=OCOCF3) gave semihydrogenated aromatic heterocycles in good to excellent yields. Copyright
- Murase, Hirohiko,Senda, Kousuke,Senoo, Masato,Hata, Takeshi,Urabe, Hirokazu
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supporting information
p. 317 - 322
(2014/01/17)
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- 1,4-Dihydroindeno[1,2-c]pyrazoles with acetylenic side chains as novel and potent multitargeted receptor tyrosine kinase inhibitors with low affinity for the hERG ion channel
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The synthesis of a novel series of 1,4-dihydroindeno[1,2-c]pyrazoles with acetylene-type side chains is described. Optimization of those compounds as KDR kinase inhibitors identified 8, which displayed an oral activity in an estradiol-induced murine uterine edema model (ED50 = 3 mg/kg) superior to Sutent (ED50 = 9 mg/kg) and showed potent antitumor efficacy in an MX-1 human breast carcinoma xenograft tumor growth model (tumor growth inhibition = 90% at 25 mg/kg·day po). The compound was docked into a homology model of the homo-tetrameric pore domain of the hERG potassium channel to identify strategies to improve its cardiac safety profile. Systematic interruption of key binding interactions between 8 and Phe656, Tyr652, and Ser624 yielded 90, which only showed an IC50 of 11.6 μM in the hERG patch clamp assay. The selectivity profile for 8 and 90 revealed that both compounds are multitargeted receptor tyrosine kinase inhibitors with low nanomolar potencies against the members of the VEGFR and PDGFR kinase subfamilies.
- Dinges, Jürgen,Albert, Daniel H.,Arnold, Lee D.,Ashworth, Kimba L.,Akritopoulou-Zanze, Irini,Bousquet, Peter F.,Bouska, Jennifer J.,Cunha, George A.,Davidsen, Steven K.,Diaz, Gilbert J.,Djuric, Stevan W.,Gasiecki, Alan F.,Gintant, Gary A.,Gracias, Vijaya J.,Harris, Christopher M.,Houseman, Kathryn A.,Hutchins, Charles W.,Johnson, Eric F.,Li, Hu,Marcotte, Patrick A.,Martin, Ruth L.,Michaelides, Michael R.,Nyein, Michelle,Sowin, Thomas J.,Su, Zhi,Tapang, Paul H.,Xia, Zhiren,Zhang, Henry Q.
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p. 2011 - 2029
(2008/02/04)
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- AMINO ALCOHOL DERIVATIVE OR PHOSPHONIC ACID DERIVATIVE AND MEDICINAL COMPOSITION CONTAINING THESE
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The present invention relates to amino alcohol derivatives or phosphonic acid derivatives having excellent immunosuppressive activity, pharmacologically acceptable salts thereof or pharmacologically acceptable esters thereof, and to pharmaceutical compositions comprising said compounds as an active ingredient: [wherein, ???R1 and R2 each represent a hydrogen atom, or a protecting group of the amino group; ???R3 represents a hydrogen atom, or a protecting group of the hydroxyl group; ???R4 represents a lower alkyl group; ???n represents an integer of from 1 to 6; ???X represents an oxygen atom or a nitrogen atom unsubstituted or substituted with a lower alkyl group or the like; ???Y represents an ethylene group; ???Z represents a C1-C10 alkylene group; ???R5 represents an aryl group, or an aryl group substituted with substituents; ???R6 and R7 each represents a hydrogen atom; provided that when R5 represents a hydrogen atom, then Z represents a group other than a single bond or a straight chain C1-C10 alkylene group] .
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- Diastereoselective intramolecular SmI2-H2O-amine mediated couplings
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The effectiveness of SmI2-H2O-amine mixture for intramolecular couplings was discussed. Diastereoselectivities in the coupling of O-cyclohexanyliodophenol derivatives were provided into heterocycles. The amount of coupled product improved significantly as SmI2, the substrate and amine were premixed followed by a gradual addition of water.
- Dahlen, Anders,Petersson, Annika,Hilmersson, Goeran
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p. 2423 - 2426
(2007/10/03)
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- Tin Radical Addition to Alkynyl Sulfides: Reactivity of the Intermediate Thioalkyl-Substituted β-(Tributylstannyl)vinyl Radicals
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Phenyl and benzyl alkynyl sulfides 1a-g and 3a, phenylalkynylamines 19a,b, ethers 22a,b, and selenide 31 reacted with tributyltin radicals to give intermediate β-stannylvinyl radicals, whose fate depended on the nature of the side chain. 4-Phenylthio-substituted but-1-en-2-yl radicals underwent stereospecific 5-exo cyclization on the adjacent phenyl ring.The resulting spirocyclohexadienyl radicals gave thiophenes and thiopyrans by carbon-sulfur bond scission or ring expansion on the exocyclic double bond, respectively.Similar behavior was exhibited by the corresponding selenium-containing radical, which afforded a selenophene almost exclusively. (Benzylthio)alkyl-substituted radicals gave products deriving from intramolecular SH2 substitution at the sulfur atom, whereas propargyl sulfides yielded a stannylallene via a β-scission reaction.No 6(or more)-membered ring closure was observed with pentynyl and hexynyl phenyl sulfides 1b,c, which gave only the (E)-addition products of tin hydride; oxygen- and nitrogen-containing vinyl radicals also gave the (E)-adducts exclusively.An interaction between the unpaired electron orbital and the empty low-energy orbitals of the heteroatom might explain why sulfur and selenium can undergo 5-exo cyclization.
- Capella, Laura,Montevecchi, Pier Carlo,Nanni, Daniele
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p. 3368 - 3374
(2007/10/02)
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