- Solvent-free condensations of ketones with malononitrile catalysed by methanesulfonic acid/morpholine system
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The preparation of ylidenemalononitriles via Knoevenagel condensations of ketones with malononitrile under solvent-free conditions is described. Good yields and short reaction time are the features observed with methanesulfonic acid (MSA)/morpholine used as the catalyst. The wide applicability of the protocol is shown by the fact that not only unconjugated, but also aryl-alkyl ketones gave satisfactory yields.
- Gora,Kozik,Jamrozy,Luczynski,Brzuzan,Wozny
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Read Online
- Enantioselective direct vinylogous Michael addition reaction catalyzed by organic molecules
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Chiral 2-azanorbornyl-3-methanol is used as an organocatalyst for the highly enantioselective direct vinylogous Michael addition reaction of vinyl malononitriles to α,β-unsaturated aldehydes. In many cases, the products can be obtained in almost optically
- Lu, Jun,Liu, Feng,Zhou, Wei-Juan,Loh, Teck-Peng
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Read Online
- Asymmetric organocatalytic vinylogous Michael addition triggered triple-cascade reactions of 2-hydroxycinnamaldehydes and vinylogous nucleophiles: construction of benzofused oxabicyclo[3.3.1]nonane scaffolds
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An organocatalytic vinylogous Michael addition triggered triple-cascade reaction has been developed. 2-Hydroxycinnamaldehydes worked under iminium activation with either acyclic or cyclic ketone-derived α,α-dicyanoalkenes, yielding the benzofused oxabicyclo[3.3.1]nonanes bearing one quaternary stereocenter with excellent stereoselectivities.
- Wu, Hui-Chun,Wang, Chen,Chen, Ying-Han,Liu, Yan-Kai
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supporting information
p. 1762 - 1765
(2021/02/27)
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- Synthesis method of methylene malononitrile compounds
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The invention discloses a synthesis method of methylene malononitrile compounds. According to the method, in the air atmosphere, a ketone compound and malononitrile are taken as raw materials, Ru/C istaken as a catalyst, the raw materials and the catalyst
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Paragraph 0068-0072; 0083-0089
(2020/04/02)
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- INHIBITORS OF THE PD-1/PD-L1 PROTEIN/PROTEIN INTERACTION
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The present invention provides novel compounds of formula (I) that are useful as inhibitors of the PD-1/PD-L1 protein/protein interaction.
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Page/Page column 36
(2017/08/01)
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- Synthesis of methyl 3-azidothieno[2,3-b]pyridine-2-carboxylates and application of the huisgen reaction
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The preparation of new substituted methyl 3-azidothieno[2,3-b]pyridine carboxylates by azotization of methyl 3-aminothieno[2,3-b]pyridine and subsequent treatment with sodium azide is described. Via Huisgen's 1,3-dipolar cycloaddition between substituted alkynes and the prepared azides, methyl 1,2,3-triazolo-thieno[2,3-b]pyridine carboxylates have been obtained.
- Chaouni, Wafaa,Aadil, Mina,Djellal, Ahmed,Kirsch, Gilbert
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p. 509 - 518
(2014/06/10)
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- Synthesis and bioactivity of novel amino-pyrazolopyridines
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Here we describe the synthesis and biological activity of novel amino-pyrazolopyridines with anti-NF-κB and pro-apoptotic potential. α-Methylene ketones were used as a starting point for synthesis of amino-pyrazolopyridine 3. The alkylidene malononitriles 1 were obtained by the Knoevenagel reaction of ketones with malononitriles. Vilsmeier-Haack reaction allowed direct access to 2-chloro-3-cyanopyridines 2. Those products, by refluxing with hydrazine hydrate, allowed cyclization to amino-pyrazolopyridines 3a-g, which were not previously described in the literature. Bioactivity results indicated that amino-pyrazolopyridines 3a, 3b and 3g induced apoptotic cell death in K562 cancer cells with an IC50 of 36.5 ± 3.9 μM, 27.6 ± 4.5 μM and 35.0 ± 2.3 μM, respectively, after 72 h. In addition, compounds 3a, 3b and 3g exerted NF-κB inhibition activity with an IC50 of 4.7 ± 1.6 μM, 6.9 ± 1.9 μM and 39.8 ± 3.9 μM, respectively, after 8 h in K562 cells activated with TNFα. Compounds 3b and 3g showed interesting differential toxicity as viability of peripheral blood mononuclear cells (PBMCs) from healthy donors remained largely unaffected by this treatment.
- Orlikova, Barbora,Chaouni, Wafaa,Schumacher, Marc,Aadil, Mina,Diederich, Marc,Kirsch, Gilbert
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p. 450 - 457
(2014/09/03)
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- Improved synthesis of mono- and disubstituted 2-halonicotinonitriles from alkylidene malononitriles
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Pyridines with 2,3,4 and/or 5 substitution remain challenging to prepare. Existing strategies to form multisubstituted 2-halonicotinonitriles via enamines suffer from dimerization of the starting alkylidene malononitriles resulting in low yields. Through alteration of reaction conditions, a new high yielding method into enamines was realized by condensing DMF-DMA and alkylidene malononitriles in the presence of substoichiometric acetic anhydride. Cyclization of the resulting enamines under Pinner conditions provided 2-halonicotinonitriles in high overall yields.
- Longstreet, Ashley R.,Campbell, Brian S.,Gupton, B. Frank,McQuade, D. Tyler
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supporting information
p. 5298 - 5301
(2013/11/06)
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- [5C + 1N] Annulation of 2,4-pentadienenitriles with hydroxylamine: A synthetic route to multi-substituted 2-aminopyridines
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A facile and efficient synthetic route to multi-substituted 2-aminopyridines has been developed via a formal [5C + 1N] annulation of readily available 2,4-pentadienenitriles with hydroxylamine (NH2OH) under very mild conditions, which involves
- Xin, Xiaoqing,Huang, Peng,Xiang, Dexuan,Zhang, Rui,Zhao, Fengyu,Zhang, Ning,Dong, Dewen
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p. 1001 - 1006
(2013/02/26)
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- Facile metal free regioselective transfer hydrogenation of polarized olefins with ammonia borane
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Transfer hydrogenation of polarized olefins bearing strongly electron-withdrawing groups on one side of the double bond was achieved with ammonia borane under mild conditions without using a catalyst. Mechanistic studies proved the character of the direct H transfers proceeding stepwise with a unique hydroboration intermediate and hydride before proton transfer.
- Yang, Xianghua,Fox, Thomas,Berke, Heinz
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supporting information; experimental part
p. 2053 - 2055
(2011/03/22)
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- Enantioselective Michael addition of dicyanoolefins to α,β- unsaturated aldehydes in aqueous medium
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A pool of water-compatible catalysts, namely dialkyl-(S)-prolinols, has been developed for the enantioselective direct vinylogous Michael addition reaction of vinylmalononitriles to α,β-unsaturated aldehydes in aqueous medium. In many cases, the products can be obtained in almost optically pure form (>96% ee) after a single recrystallization.
- Lu, Jun,Liu, Feng,Loh, Teck-Peng
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supporting information; experimental part
p. 1781 - 1784
(2009/07/10)
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- Transfer hydrogenation of activated C=C bonds catalyzed by ruthenium amido complexes: Reaction scope, limitation, and enantioselectivity
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(Chemical Equation Presented) It was found that the chemoselectivity could be completely switched from C=O to C=C bonds in the transfer hydrogenation of activated α,β-unsaturated ketones catalyzed by diamine-ruthenium complex. Moreover, this addition via metal hydride had been applied to the reduction of various activated olefins. The electron-withdrawing ability of functional groups substituted on C=C bonds at the α- or β-position had strong influence on the reactivity. In addition, a wide variety of chiral diamine-Ru(II)-(arene) systems was investigated to explore the asymmetric transfer hydrogenation of prochiral α,α-dicyanoolefins. Two parameters had been systematically studied, (i) the structure of the N-sulfonylated chiral diamine ligands, in which several chiral diamines substituted on the benzene ring of DPEN were first reported, and (ii) the structure of the metal precursors, and high enantioselectivitiy (up to 89% ee) at the β-carbon was obtained.
- Xue, Dong,Chen, Ying-Chun,Cui, Xin,Wang, Qi-Wei,Zhu, Jin,Deng, Jin-Gen
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p. 3584 - 3591
(2007/10/03)
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- Regiochemistry in alkylation, acylation and methoxycarbonylation of alkali salts from 2-substituted alkenylpropanedinitriles
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Alkali salts (4-) of several 2-substituted alkenylpropanedinitriles are prepared, isolated and characterised by 1H and 13C NMR spectroscopy. By treating the salt 4a- with 4a a dimer, 2-dicyanomethylene-6-methyl-4,6-diphenyl-1,2,5,6-tetrahydronicotinonitrile 6, is formed, for which a single-crystal X-ray structure is presented. Alkylation of the ambident salts 4- with MeX (X = I, Tf, or Br) leads to regioisomers, 1-and 3-alkylation, and comparison with O vs. C-alkylation of ketones is made. Double alkylation is also observed, 3-alkylation followed by 1-alkylation. Thus from 4a- a mixture of (E)-and (Z)-2-methyl-2-(1-phenylprop-1-enyl)propanedinitrile 9b is formed, and the X-ray structure of the former is presented. Acylation of 4a- with benzoyl chloride gives only the 3-regioisomer; using equimolar amounts of reactants gives a ring-closure product, 2-oxo-4,6-diphenyl-2H-pyran-3-carbonitrile 12, while excess of benzoyl chloride gives the double-acylation product, (Z)-4,4-dicyano-1,3-diphenylbuta-1,3-dienyl benzoate (Z)-13, for which the X-ray structure is presented. Acylation of 4a- with acetyl chloride gives both regioisomers; the 1-acylated product evaded isolation, and the 3-acylation product reacted further to give the (E)- and (Z)-form of 4,4-dicyano-1-methyl-3-phenylbuta-1,3-dienyl acetate 15. The X-ray structure of the latter isomer, (Z)-15, is presented. Methoxycarbonylation of salts 4- with methyl chloroformate gives both regioisomers, while use of methyl cyanoformate gives only the 3-regioisomer, in addition to a Michael adduct from reaction of the CN- group with protonated salt 4-.
- Karlsen, Hege,Songe, Pal H.,Sunsby, Lise Kristin,Hagen, Lise Cathrine,Kolsaker, Per,Romming, Christian
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p. 497 - 507
(2007/10/03)
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- SYNTHESE DE NOUVEAUX DERIVES 3-AMINO THIENO ET SELENOLOPYRIDINIQUES
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Cyclisation of alkylidenemalonitriles by the Vilsmeier-Haack reagent gives 2-chloro 3-cyano pyridines.These compounds are used as starting material for the synthesis of thieno and selenolopyridines.Key words: Alkylidenemalonitriles; Vilsmeier-Haack; 2-chloro 3-cyano pyridines; thienopyridines; selenolopyridines.
- Aadil, M.,Kirsch, G.
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- SYNTHESIS AND CHEMICAL REACTIVITY OF 4,4-DISUBSTITUTED PYRANAMINES
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The synthesis of a variety of 4,4-disubstituted 4H-pyranamines from alkylarylpropenenitriles and benzoylacetonitrile is reported.The reaction requirements demanded a different approach from the general synthesis of 2-amino-4H-pyrans.Electronic and steric
- Martin-Leon, Nazario,Segura, Jose L.,Seoane, Carlos,Soto, Jose L.
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p. 2434 - 2452
(2007/10/02)
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