- Cyclobutadiene cobalt complexes as catalysts for insertion of diazo compounds into X–H bonds
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Novel cyclobutadiene cobalt complex with labile naphthalene ligand [(C4Et4)Co(C10H8)]PF6 catalyzes the insertion of ethyl diazoacetate into X–H bonds giving the corresponding products in 15–75% yields
- Perekalin, Dmitry S.,Shvydkiy, Nikita V.
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p. 350 - 351
(2021/06/07)
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- HALOALLYLAMINE COMPOUNDS AND APPLICATION THEREOF
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The present invention relates to the technical field of pharmaceuticals. Specifically, the present invention relates to a halo-allylamine compound, or a pharmaceutically acceptable salt, an ester, a stereoisomer or a tautomer thereof, and a pharmaceutical formulation and a pharmaceutical composition comprising the compounds, and use in preventing and/or treating a disease related to or mediated by the SSAO/VAP-1 protein,wherein R1, R2, R3, R4, R5, R6, L1 and Cy1 are defined in the specification.
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Paragraph 0259-0261
(2021/10/15)
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- Solution-Phase Synthesis of Backbone-Constrained Cationic Peptoid Hexamers with Antibacterial and Anti-Biofilm Activities
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Abstract: Submonomer synthesis in solution and block-coupling protocols were combined to prepare amphiphilic peptoid hexamers. The amphipathic character arises from the use of hydrophobic aliphatic tert-butyl side-chains imposing the cis-amide backbone co
- Charbonnel, Nicolas,Faure, Sophie,Forestier, Christiane,Roy, Olivier,Shyam, Radhe,Taillefumier, Claude
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p. 5813 - 5822
(2021/11/17)
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- Insertion of carbenoids into X-H bonds catalyzed by the cyclobutadiene rhodium complexes
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The cyclobutadiene rhodium complex [(C4Et4)RhCl]2 (generated from [(C4Et4)Rh(p-xylene)]PF6 and BnNEt3Cl) catalyzes the reaction of methyl α-diazophenylacetate with RnX
- Loskutova, Natalia L.,Shvydkiy, Nikita V.,Nelyubina, Yulia V.,Perekalin, Dmitry S.
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- Exploring the Conformation of Mixed Cis- Trans α,β-Oligopeptoids: A Joint Experimental and Computational Study
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The synthesis and conformational preferences of a set of new synthetic foldamers that combine both the α,β-peptoid backbone and side chains that alternately promote cis- and trans-amide bond geometries have been achieved and addressed jointly by experiment and molecular modeling. Four sequence patterns were thus designed and referred to as cis-β-trans-α, cis-α-trans-β, trans-β-cis-α, and trans-α-cis-β. α- and βNtBu monomers were used to enforce cis-amide bond geometries and α- and βNPh monomers to promote trans-amides. NOESY and molecular modeling reveal that the trans-α-cis-β and cis-β-trans-α tetramers show a similar pattern of intramolecular weak interactions. The same holds for the cis-α-trans-β and trans-β-cis-α tetramers, but the interactions are different in nature than those identified in the trans-α-cis-β-based oligomers. Interestingly, the trans-α-cis-β peptoid architecture allows establishment of a larger amount of structure-stabilizing intramolecular interactions.
- Dumonteil, Geoffrey,Bhattacharjee, Nicholus,Angelici, Gaetano,Roy, Olivier,Faure, Sophie,Jouffret, Laurent,Jolibois, Franck,Perrin, Lionel,Taillefumier, Claude
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p. 6382 - 6396
(2018/06/26)
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- NOVEL HETEROARYL AND HETEROCYCLE COMPOUNDS, COMPOSITIONS AND METHODS
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The invention relates to novel heteroaryl and heterocycle compounds of formula I and pharmaceutical compositions comprising them, uses and methods thereof for inhibiting the activity of PI3K and for treating inflammatory and autoimmune diseases and cancer.
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Paragraph `158
(2016/08/23)
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- Synthesis of Benzo[a]carbazoles and an Indolo[2,3-a]carbazole from 3-Aryltetramic Acids
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A simple and flexible approach to 3-pyrrolin-2-one fused carbazoles is disclosed. The key step involves the BF3-mediated electrophilic substitution of indoles with N-alkyl-substituted 3-aryltetramic acids, which provides access to indole-substituted 3-pyrrolin-2-ones. Scholl-type oxidative cyclizations of these materials led to the formation of the corresponding 3-pyrrolin-2-one-fused benzo[a]carbazoles and indolo[2,3-a]carbazoles. This work represents the first synthesis of the benzo[a]pyrrolo[3,4-c]carbazol-3(8H)-one ring system, while the indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-one ring system is found in a number of biologically active compounds including the protein kinase C (PKC) inhibitor, staurosporine.
- Truax, Nathanyal J.,Banales Mejia, Fernando,Kwansare, Deborah O.,Lafferty, Megan M.,Kean, Maeve H.,Pelkey, Erin T.
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p. 6808 - 6815
(2016/08/16)
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- Iridium porphyrin catalyzed N-H insertion reactions: Scope and mechanism
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Ir(TTP)CH3 catalyzed N-H insertion reactions between ethyl diazoacetate (EDA) or methyl phenyldiazoacetate (MPDA) and a variety of aryl, aliphatic, primary, and secondary amines to generate substituted glycine esters with modest to high yields. Aniline substrates generally gave yields above 80%, with up to 105 catalyst turnovers, and without slow addition of the diazo reagent. Good yields were also achieved with aliphatic amines, though higher catalyst loadings and slow addition of the amine were necessary in some cases. Primary amines reacted with EDA to generate both single- and double-insertion products, either of which could be produced selectively in high yield with the proper choice of stoichiometric ratios and reaction temperature. Notably, mixed trisubstituted amines, RN(CH2CO2Et) (CHPhCO2Me), were generated from the insertion of 1 equiv of EDA and 1 equiv of MPDA into primary amines. The N-H insertion mechanism was examined using substrate competition studies, trapping experiments, and multiple spectroscopic techniques. Substrate competition studies using pairs of amines with EDA or MPDA revealed Hammett correlations with respective slopes of ρ = 0.15 and ρ+ = -0.56 as well as kinetic isotope ratios of k H/kD = 1.0 ± 0.2 and 2.7 ± 0.2. Competitive amine binding to the iridium center was demonstrated by kinetics and equilibrium binding studies. Equilibrium binding constants ranged from 102 to 105. Monitoring the reaction by absorption spectroscopy revealed a transient metalloporphyrin complex. The lifetime of this species was dependent on the nature of the amine substrate, which suggests that the catalytic cycle proceeds through a metal-ylide intermediate.
- Anding, Bernie J.,Woo, L. Keith
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p. 2599 - 2607
(2013/06/26)
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- Equimolar CO2 capture by N-substituted amino acid salts and subsequent conversion
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Steric bulk controls CO2 absorption: N-substituted amino acid salts in poly(ethylene glycol) reversibly absorb CO2 in nearly 1:1 stoichiometry. Carbamic acid is thought to be the absorbed form of CO 2; this was supported by NMR and in situ IR spectroscopy, and DFT calculations. The captured CO2 could be converted directly into oxazolidinones and thus CO2 desorption could be sidestepped. Copyright
- Liu, An-Hua,Ma, Ran,Song, Chan,Yang, Zhen-Zhen,Yu, Ao,Cai, Yu,He, Liang-Nian,Zhao, Ya-Nan,Yu, Bing,Song, Qing-Wen
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supporting information
p. 11306 - 11310
(2013/01/15)
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- Synthesis, characterization and biological activities of novel (E)-3-(1-(alkyloxyamino)ethylidene)-1-alkylpyrrolidine-2,4-dione derivatives
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Twenty novel tetramic acid derivatives (E)-3-(1-(alkyloxyamino)ethylidene)- 1-alkylpyrrolidine-2,4-diones were synthesized by the reaction of 3-(1-hydroxyethylidene)pyrrolidine-2,4-diones with O-alkyl hydroxylamines. The title compounds were confirmed by
- Zhu, Zhao-Yong,Shi, Qing-Ming,Han, Bao-Feng,Wang, Xian-Feng,Qiang, Sheng,Yang, Chun-Long
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experimental part
p. 2467 - 2472
(2010/12/18)
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- Microwave-assisted solvent-free intramolecular 1,3-dipolar cycloaddition reactions leading to hexahydrochromeno[4,3-b]pyrroles: scope and limitations
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We report the microwave-assisted solvent-free synthesis of hexahydrochromeno[4,3-b]pyrroles. Intramolecular 1,3-dipolar cycloadditions proceed under these conditions within 15-40 min in 16-84% yields. An influence of the microwave irradiation upon various [3+2] cycloaddition reaction intermediates was studied. Additionally, a scope and limitations of these reactions including an influence of the dipolarophile geometry upon the cycloaddition selectivity and steric demands of the dipole upon its reactivity were also disclosed. These observations led us to postulate a preferable transition state of the reaction. Finally, an influence of the microwave irradiation to the isomerization of activated olefins was also described.
- Pospí?il, Ji?í,Potá?ek, Milan
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p. 337 - 346
(2007/10/03)
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- Synthesis, isolation and characterization of cationic gold(I) N-heterocyclic carbene (NHC) complexes
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A number of cationic gold(I) complexes have been synthesized and found to be stabilized by the use of N-heterocyclic carbene ligands. These species are often employed as in situ-generated reactive intermediates in gold catalyzed organic transformations. An isolated, well-defined species was tested in gold-mediated carbene transfer reactions from ethyl diazoacetate. The Royal Society of Chemistry 2006.
- De Fremont, Pierre,Stevens, Edwin D.,Fructos, Manuel R.,Mar Diaz-Requejo,Perez, Pedro J.,Nolan, Steven P.
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p. 2045 - 2047
(2008/09/18)
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- A gold catalyst for carbene-transfer reactions from ethyl diazoacetate
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(Chemical Equation Presented) Approaching El Dorado: A gold catalyst has been discovered that transfers a carbene unit from ethyl diazoacetate to aromatic substrates (see scheme) as well as olefins, amines, and alcohols. The insertion of carbene units into the C-H bonds of the aromatic ring of benzene, toluene, and styrene is a novel reaction. R = H, CH3, CH=CH 2; IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene.
- Fructos, Manuel R.,Belderrain, Tomas R.,De Fremont, Pierre,Scott, Natalie M.,Nolan, Steven P.,Diaz-Requejo, M Mar,Perez, Pedro J.
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p. 5284 - 5288
(2007/10/03)
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- Synthesis and herbicidal evaluation of novel 3-[(α-hydroxy- substituted)benzylidene]pyrrolidine-2,4-diones
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A series of 3-[(α-hydroxy-substituted) benzylidene]pyrrolidine-2,4- dione derivatives were synthesized as candidate herbicides by reacting different aroyl acetates with N-substituted glycine esters. The new compounds were identified by 1H NMR spectroscopy and elemental analyses. Their herbicidal activities were evaluated. Some compounds exhibited excellent herbicidal activities at a dose of 187.5 g/ha. A suitable electron-donating substituent at the 2- and/or 4-position of the phenyl ring was essential for high herbicidal activity, a result that has not been reported before. It was also found that the title compound's structure-activity relationships were different from those of other similar kinds of earlier compounds, a result that may depend on the enol structure difference.
- Zhu, Youquan,Zou, Xiaomao,Hu, Fangzhong,Yao, Changsheng,Liu, Bin,Yang, Huazheng
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p. 9566 - 9570
(2007/10/03)
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- Catalytic insertion of diazo compounds into N-H bonds: The copper alternative
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The complexes TpXCu (TpX = homoscorpionate) catalyse the insertion of diazo compounds into nitrogen-hydrogen bonds of amines and amides, under very mild conditions, with quantitative yields being obtained with equimolar ratios of reactants.
- Morilla, M. Esther,Diaz-Requejo, M. Mar,Belderrain, Tomas R.,Nicasio, M. Carmen,Trofimenko, Swiatoslaw,Perez, Pedro J.
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p. 2998 - 2999
(2007/10/03)
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- Insertion of ethyl diazoacetate into N-H and S-H bonds catalyzed by ruthenium porphyrin complexes
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Ruthenium porphyrin complexes catalyze insertion of ethyl diazoacetate into sulfur-hydrogen and nitrogen-hydrogen bonds under mild conditions and with reasonable to very good yields.
- Galardon, Erwan,Le Maux, Paul,Simonneaux, Gerard
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p. 2455 - 2456
(2007/10/03)
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- Organic reactions catalyzed by methylrhenium trioxide: Reactions of ethyl diazoacetate and organic azides
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Methylrhenium trioxide (CH3ReO3 or MTO) catalyzes several classes of reactions of ethyl diazoacetate, EDA. It is the first high valent oxo complex for carbene transfer. Under mild conditions and in the absence of other substrates, EDA was converted to a 9:1 mixture of diethyl maleate and diethyl fumarate. In the presence of alcohols, α-alkoxy ethyl acetates were obtained in good yield. The yields dropped for the larger and more branched alcohols, the balance of material being diethyl maleate and fumarate. An electron-donating group in the para position of phenols favors the formation of α-phenoxy ethyl acetates. The use of EDA to form α-thio ethyl acetates and N-substituted glycine ethyl esters, on the other hand, is hardly affected by the size or structure of the parent thiol or amine, with all of these reactions proceeding in high yield. MTO-catalyzed cycloaddition reactions occur between EDA and aromatic imines, olefins, and carbonyl compounds. Three-membered ring products are formed: aziridines, cyclopropanes, and epoxides, respectively. The reactions favor the formation of trans products, and provide a convenient route for the preparation of aziridines. Intermediate carbenoid and nitrenoid species have been proposed. In the presence of an oxygen source such as an epoxide, ethyl diazoacetate and azibenzil are converted to an oxalic acid monoethyl ester and tobenzil; at the same time the epoxide was converted to an olefin. These results provide further support for the proposed intermediate, a cyclic species containing Re, O, and CHCO2Et (or, occasionally, CPhC(O)Ph)in a three-membered ring.
- Zhu, Zuolin,Espenson, James H.
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p. 9901 - 9907
(2007/10/03)
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- Synthesis and reactions of 9,10-diazatetracyclo-[6.3.0.0.4,110.5.9]undecanes
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The tandem 1,3-dipolar cycloaddition between sydnones and 1,5-cyclooctadiene provides 9,10-diazatetracyclo[6.3.0.0.4,110.5,9]undecanes (the Weintraub reaction) in modest to good yields.
- Gribble, Gordon W.,Hirth, Bradford H.
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p. 719 - 726
(2007/10/03)
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