- Streamlined Routes to Phenacyl Azides and 2,5-Diarylpyrazines Enabled by Deep Eutectic Solvents
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A Deep Eutectic Solvent like choline chloride/glycerol (1:2 mol mol–1) proved to be an effective, sustainable reaction medium to easily synthesize both phenacyl azides and symmetrical 2,5-diarylpyrazines of interest in pharmacology and in coordination chemistry. Notable features of our report include: (i) nucleophilic substitution reactions of α-halo carbonyl compounds to the corresponding phenacyl azides compatible with the eutectic mixture, (ii) the reduction of phenacyl azides to α-amino carbonyl compounds, which undergo spontaneous dimerisation/cyclisation/aromatisation in the same eutectic mixture to provide valuable pyrazines. Telescoped, one-pot, two-steps stoichiometric/catalytic processes have also been successfully developed to furnish 2,5-diarylpyrazines in up to 95 % yield.
- Vitale, Paola,Cicco, Luciana,Messa, Francesco,Perna, Filippo Maria,Salomone, Antonio,Capriati, Vito
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p. 5557 - 5562
(2019/08/21)
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- A facile transformation of alkynes into α-amino ketones by an N-bromosuccinimide-mediated one-pot strategy
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A facile transformation of alkynes into α-amino ketones by an N-bromosuccinimide-mediated one-pot cascade strategy is described. A variety of α-amino ketones are obtained in moderate to good yields under mild conditions. To overcome the multi-step synthesis, N-bromosuccinimide is involved in multiple tasks, playing a key role in the reaction course.
- Wei, Ting,Zeng, Yongming,He, Wei,Geng, Lili,Hong, Liang
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supporting information
p. 383 - 385
(2018/04/11)
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- Remote C(sp3)-H Oxygenation of Protonated Aliphatic Amines with Potassium Persulfate
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This letter describes the development of a method for selective remote C(sp3)-H oxygenation of protonated aliphatic amines using aqueous potassium persulfate. Protonation serves to deactivate the proximal C(sp3)-H bonds of the amine substrates and also renders the amines soluble in the aqueous medium. These reactions proceed under relatively mild conditions (within 2 h at 80 °C with amine as limiting reagent) and do not require a transition metal catalyst. This method is applicable to a variety of types of C(sp3)-H bonds, including 3°, 2°, and benzylic C-H sites in primary, secondary, and tertiary amine substrates.
- Lee, Melissa,Sanford, Melanie S.
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supporting information
p. 572 - 575
(2017/02/10)
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- NOVEL COMPOUND, AGENT AND NK3 RECEPTOR ANTAGONIST
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PROBLEM TO BE SOLVED: To provide a NK3 receptor antagonist that inhibits the propagation of animals without adverse effect on an ecological system. SOLUTION: The present invention provides a compound represented by formula (I') (R1 is H, a hydroxy group or the like; R2 is a hydroxy group, a mercapto group or the like; R3 is a phenyl group or naphthyl group). SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0072; 0073
(2017/08/02)
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- Copper(II) and cobalt(II) tetrazole-saccharinate complexes as effective catalysts for oxidation of secondary alcohols
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Mononuclear Cu(II) and Co(II) complexes comprising 2-methyltetrazole-saccharinate bidentate N,N-chelating ligand have been synthesized for the first time and tested as homogeneous catalysts for oxidation of secondary alcohols in a solvent-free and microwave assisted protocol using aqueous tert-butyl hydroperoxide (TBHP) as oxidant. The developed catalytic system exhibits broad functional group compatibility, allowing efficient and selective conversion of a variety of secondary alcohols, including allylic ones, into the corresponding ketones. With typical 0.2 mol% content of the catalyst and under 20–50 W microwave irradiation, most reactions are complete within 10 min, presenting TONs up to 5.5 × 102 and TOFs up to 1.1 × 104 h?1. No additives and co-oxidants have been used, while TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxyl) acts as inhibitor in most cases. A plausible reaction mechanism involving the new catalytic systems is outlined.
- Frija, Luís M.T.,Alegria, Elisabete C.B.A.,Sutradhar, Manas,Cristiano, M. Lurdes S.,Ismael, Amin,Kopylovich, Maximilian N.,Pombeiro, Armando J.L.
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p. 283 - 290
(2016/11/04)
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- Hit-to-lead evaluation of a novel class of sphingosine 1-phosphate lyase inhibitors
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Inhibition of sphingosine-1-phosphate lyase has recently been proposed as a potential treatment option for inflammatory disorders such as multiple sclerosis, rheumatoid arthritis, and inflammatory bowel disease. In this report we describe our hit-to-lead evaluation of the isoxazolecarboxamide 6, a high-throughput screening hit (in vitro IC50 = 1.0 μM, cell IC50 = 1.8 μM), as a novel S1P lyase inhibitor. We were able to establish basic structure-activity relationships around 6 and succeeded in obtaining X-ray structural information which enabled structure-based design. With the discovery of 28, enzyme activity was quickly improved to IC50 = 120 nM and cell potency to IC50 = 230 nM. The main liability in the established isoxazolecarboxamide hit series was determined to be metabolic stability. In particular we identified that future lead-optimization efforts to overcome this problem should focus on blocking the N-dealkylation on the secondary amine.
- Dinges, Jurgen,Harris, Christopher M.,Wallace, Grier A.,Argiriadi, Maria A.,Queeney, Kara L.,Perron, Denise C.,Dominguez, Eric,Kebede, Tegest,Desino, Kelly E.,Patel, Hetal,Vasudevan, Anil
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p. 2297 - 2302
(2016/04/20)
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- Efficient palladium and ruthenium nanocatalysts stabilized by phosphine functionalized ionic liquid for selective hydrogenation
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Pd and Ru nanoparticles were synthesized in ionic liquid by using tri(m-sulfonyl)triphenyl phosphine 1-butyl-2,3-dimethyl-imidazolium salt ([BMMIM]3[tppt]) as a stabilizing agent. The well-dispersed Pd and Ru NPs with mean diameters of 2.4 nm and 1.7 nm were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). It was demonstrated that [BMMIM]3[tppt] stabilized Pd and Ru NPs displayed high activity and excellent selectivity in the hydrogenation of functionalized olefins, aromatic nitro compounds and aromatic aldehydes. The Pd and Ru NPs showed better catalytic performance than corresponding commercially available Pd/C and Ru/C catalysts. The present catalytic system could be easily reused at least six times without significant decrease in activity and selectivity.
- Wu, Zhifeng,Jiang, Heyan
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p. 34622 - 34629
(2015/05/04)
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- Probing the 'bipolar' nature of the carbonic anhydrase active site: Aromatic sulfonamides containing 1,3-oxazol-5-yl moiety as picomolar inhibitors of cytosolic CA I and CA II isoforms
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Abstract A series of potent inhibitors of human carbonic anhydrase (CA) isoforms I and II has been prepared via a direct, chemoselective sulfochlorination of a range of 1,3-oxazolyl benzenes and thiophenes, followed by primary sulfonamide synthesis. The latter functionality is a known zinc-binding group (ZBG) responsible for anchoring the inhibitors to the CA's zinc metal ion. The compound's periphery as well as the overall scaffold geometry was designed to enable optimal interactions with the two distinct sides of the enzyme's active site, one of which is lined with hydrophobic residues and while the other is predominantly hydrophilic. As a result, several compounds inhibiting the therapeutically important cytosolic CA I and CA II in picomolar range have been identified. These compounds are one of the most potent CA inhibitors identified to-date. Not only the remarkable (>10 000-fold), cytosolic CA I and CA II selectivity vs. the membrane-bound CA IX and CA XII isoforms, but also the pronounced CA II/I selectivity observed in some cases, allow considering this series as a set of isoform-selective chemical biology tools and promising starting points for drug candidate development.
- Krasavin, Mikhail,Korsakov, Mikhail,Dorogov, Mikhail,Tuccinardi, Tiziano,Dedeoglu, Nurcan,Supuran, Claudiu T.
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p. 334 - 347
(2015/07/28)
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- Flexible stereoselective functionalizations of ketones through umpolung with hypervalent iodine reagents
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The functionalization of carbonyl compounds in the α-position has gathered much attention as a synthetic route because of the wide biological importance of such products. Through polarity reversal, or "umpolung", we show here that typical nucleophiles, such as oxygen, nitrogen, and even carbon nucleophiles, can be used for addition reactions after tethering them to enol ethers. Our findings allow novel retrosynthetic planning and rapid assembly of structures previously accessible only by multistep sequences. A Nu approach: An efficient α-functionalization of ketones with a range of simple and useful nucleophiles is possible by using hypervalent iodine reagents (see scheme; Nu′ can be the Nu itself or a protected form of this nucleophile group).
- Mizar, Pushpak,Wirth, Thomas
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supporting information
p. 5993 - 5997
(2014/06/10)
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- 7-alkyl- and 7-cycloalkyl-5-aryl-pyrrolo[2,3-d]pyrimidines - Potent inhibitors of the tyrosine kinase c-Src
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7-Substituted-5-aryl-pyrrolo[2,3-d]pyrimidines have been prepared starting from α-bromoacetophenones. These compounds represent a novel class of potent inhibitors of the tyrosine kinase pp60c-Src with good specificity towards other tyrosine kinases (EGF-R, v-Abl).
- Widler, Leo,Green, Jonathan,Missbach, Martin,Susa, Mira,Altmann, Eva
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p. 849 - 852
(2007/10/03)
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- ARYLSULFONYLIMIDAZOLONE DERIVATIVES AS AN ANTITUMOR AGENT
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The present invention relates to a novel arylsulfonylimidazolone derivative represented by the following formula (I) which shows a superior antineoplastic activity in contrast to the known sulfonylurea antitumor agents as well as little side effect: and its pharmaceutically acceptable salt and stereoisomer, in which +E,uns - -+EE , R1, and R2 are as defined in the specification.
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- A facile procedure for reduction of azides to amines with aluminium triiodide
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It has been demonstrated that a wide variety of aromatic and aliphatic azides can be efficiently reduced to the corresponding amines in good yields with freshly prepared aluminium triiodide. Other functional groups such as ether, ester, nitro and halides remain uneffected.
- Barua, Apurba,Bez, Ghanashyam,Barua, Nabin C.
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p. 128 - 129
(2007/10/03)
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- Occurrence of an Inducible DADP+-Dependent D-Phenylserine Dehydrogenase in Pseudomonas syringae NK-15 Isolated from Soil
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We found an inducible NADP+-dependent D-phenylserine dehydrogenase in a soil bacterium identified as Pseudomonas syringae NK-15.The enzyme catalyzed the oxidation of the 3-hydroxyl group of D-threo-3-phenylserine to yield D-2-amino-3-keto-3-phenylpropionate, which was spontaneously decarboxylated into 2-aminoacetophenone.The enzyme had an optimum reactivity at about pH 10.4.The Km for D-threo-3-phenylserine and NADP+ were 0.44 mM and 29 μM, respectively.
- Packdibamrung, Kanoktip,Misono, Haruo,Nagata, Shinji,Nagasaki, Susumu
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p. 1969 - 1970
(2007/10/02)
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- Antibacterial water-soluble cutting fluids resistant to yeast-like fungi
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A bactericide is added to conventional water-soluble cutting fluids to suppress deterioration by micro-organisms. Such fluids are however accompanied by the drawbacks that the bactericide has a narrow antibacterial spectrum and moreover its effects last a short time. It is the object of the present invention to offers water--soluble cutting fluids which remain resistant to a wide variety of microorganisms for a long time. The present invention therefore offers water-soluble cutting fluids to which has been added a specific amine selected from amines known to date.
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- Preparation of esters of phosphorus acids
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Esters of phosphorus acids are prepared by an improved process whereby aromatic alcohols and phosphorus halides are reacted at specified temperatures in the presence of amine catalysts thereby providing high yields of substantially pure esters and allowing preparation of selected halogen-containing mono- and di-esters of phosphorus acids wherein halogen is directly bonded to phosphorus having substantially no side reactant contamination. The phosphorus esters are useful as intermediates in the preparation of plasticizers, oil additives and functional fluids.
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