- Method for preparing alpha, beta-unsaturated carboxylic acid compound
-
The invention discloses a method for preparing an alpha, beta-unsaturated carboxylic acid compound, which comprises the following steps: 1) in an atmosphere containing carbon dioxide, heating and reacting a mixture containing hydrosilane and a copper catalyst to obtain a system I; and 2) adding a raw material containing alkyne and a nickel catalyst into the system I in the step 1), and heating to react. The method has the advantages of simple, easily available, cheap and stable raw materials, common, easily available and stable catalyst, mild reaction conditions, simple post-treatment, high yield and the like.
- -
-
Paragraph 0103-0104; 0431-0438
(2021/05/05)
-
- A novel phenylalanine ammonia-lyase from Pseudozyma antarctica for stereoselective biotransformations of unnatural amino acids
-
A novel phenylalanine ammonia-lyase of the psychrophilic yeast Pseudozyma antarctica (PzaPAL) was identified by screening microbial genomes against known PAL sequences. PzaPAL has a significantly different substrate binding pocket with an extended loop (26 aa long) connected to the aromatic ring binding region of the active site as compared to the known PALs from eukaryotes. The general properties of recombinant PzaPAL expressed in E. coli were characterized including kinetic features of this novel PAL with L-phenylalanine (S)-1a and further racemic substituted phenylalanines rac-1b-g,k. In most cases, PzaPAL revealed significantly higher turnover numbers than the PAL from Petroselinum crispum (PcPAL). Finally, the biocatalytic performance of PzaPAL and PcPAL was compared in the kinetic resolutions of racemic phenylalanine derivatives (rac-1a-s) by enzymatic ammonia elimination and also in the enantiotope selective ammonia addition reactions to cinnamic acid derivatives (2a-s). The enantiotope selectivity of PzaPAL with o-, m-, p-fluoro-, o-, p-chloro- and o-, m-bromo-substituted cinnamic acids proved to be higher than that of PcPAL.
- Varga, Andrea,Csuka, Pál,Sonesouphap, Orlavanah,Bánóczi, Gergely,To?a, Monica Ioana,Katona, Gabriel,Molnár, Zsófia,Bencze, László Csaba,Poppe, László,Paizs, Csaba
-
p. 185 - 194
(2020/04/28)
-
- Iron-catalyzed domino decarboxylation-oxidation of α,β-unsaturated carboxylic acids enabled aldehyde C-H methylation
-
A practical and general iron-catalyzed domino decarboxylation-oxidation of α,β-unsaturated carboxylic acids enabling aldehyde C-H methylation for the synthesis of methyl ketones has been developed. This mild, operationally simple method uses ambient air as the sole oxidant and tolerates sensitive functional groups for the late-stage functionalization of complex natural-product-derived and polyfunctionalized molecules.
- Gong, Pei-Xue,Xu, Fangning,Cheng, Lu,Gong, Xu,Zhang, Jie,Gu, Wei-Jin,Han, Wei
-
supporting information
p. 5905 - 5908
(2021/06/18)
-
- C–C Cross-Coupling Reactions of Organosilanes with Terminal Alkenes and Allylic Acetates Using PdII Catalyst Supported on Starch Coated Magnetic Nanoparticles
-
Starch coated magnetic nanoparticles supported palladium catalyst has been explored to perform C–C cross coupling reactions, such as oxidative Heck coupling and Tsuji–Trost allylic coupling using organosilicon compounds as one of the coupling partners. The biopolymer coated magnetic catalyst was very easy to recover magnetically and was efficiently recycled in the subsequent batches. All the reactions were performed in air and thus the necessity of air and moisture free reaction condition is avoided. The present protocols show wide substrate scope and good yields of the products.
- Patra, Debabrata,Panja, Subir,Saha, Amit
-
supporting information
p. 878 - 883
(2020/02/13)
-
- Design, synthesis, and evaluation of novel cinnamic acid-tryptamine hybrid for inhibition of acetylcholinesterase and butyrylcholinesterase
-
Background: Acetylcholine deficiencies in hippocampus and cortex, aggregation of β-amyloid, and β-secretase over activity have been introduced as main reasons in pathogenesis of Alzheimer’s disease. Methods: Colorimetric Ellman’s method was used for determination of IC50 value in AChE and BChE inhibitory activity. The kinetic studies, neuroprotective and β-secretase inhibitory activities, evaluation of inhibitory potency on β-amyloid (Aβ) aggregations induced by AChE, and docking study were performed for prediction of the mechanism of action. Result and discussion: A new series of cinnamic acids-tryptamine hybrid was designed, synthesized, and evaluated as dual cholinesterase inhibitors. These compounds demonstrated in-vitro inhibitory activities against acetyl cholinesterase (AChE) and butyryl cholinesterase (BChE). Among of these synthesized compounds, (E)-N-(2-(1H-indol-3-yl)ethyl)-3-(3,4-dimethoxyphenyl)acrylamide (5q) demonstrated the most potent AChE inhibitory activity (IC50 = 11.51?μM) and (E)-N-(2-(1H-indol-3-yl)ethyl)-3-(2-chlorophenyl)acrylamide (5b) were the best anti-BChE (IC50 = 1.95?μM) compounds. In addition, the molecular modeling and kinetic studies depicted 5q and 5b were mixed type inhibitor and bound with both the peripheral anionic site (PAS) and catalytic sites (CAS) of AChE and BChE. Moreover, compound 5q showed mild neuroprotective in PC12 cell line and weak β-secretase inhibitory activities. This compound also inhibited aggregation of β-amyloid (Aβ) in self-induced peptide aggregation test at concentration of 10?μM. Conclusion: It is worth noting that both the kinetic study and the molecular modeling of 5q and 5b depicted that these compounds simultaneously interacted with both the catalytic active site and the peripheral anionic site of AChE and BChE. These findings match with those resulted data from the enzyme inhibition assay. [Figure not available: see fulltext.]
- Ghafary, Shahrzad,Ghobadian, Roshanak,Mahdavi, Mohammad,Nadri, Hamid,Moradi, Alireza,Akbarzadeh, Tahmineh,Najafi, Zahra,Sharifzadeh, Mohammad,Edraki, Najmeh,Moghadam, Farshad Homayouni,Amini, Mohsen
-
p. 463 - 477
(2020/05/25)
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- Co-catalysis over a tri-functional ligand modified Pd-catalyst for hydroxycarbonylation of terminal alkynes towards α,β-unsaturated carboxylic acids
-
An amphiphilic tri-functional ligand (L1) containing a Lewis acidic phosphonium cation, a phosphino-fragment and a hydrophilic sulfonate anion (-SO3-) enabled Pd(OAc)2 to efficiently co-catalyze the hydroxycarbonylation of terminal alkynes towards α,β-unsaturated carboxylic acids. These incorporated functional groups synergistically promoted the reaction, which proved more effective than the ligands lacking -SO3- and/or phosphonium and the mechanical mixtures of the individual functional groups independently. The molecular structure of Pd-L1 indicated that -SO3- in L1 served as a secondary O-donor ligand with reversible coordinating ability, cooperating with the phosphino-fragment to stabilize the Pd-catalyst. The in situ FT-IR analysis verified that the formation and stability of Pd-H active species in charge of hydroxycarbonylation were dramatically facilitated by the presence of L1. It was believed that, over the L1-based Pd-catalyst, H2O was cooperatively activated by the Lewis acidic phosphonium via "acid-base pair" interaction (H2O → P(v)+) and by the hydrophilic SO3-via hydrogen bonding (SO3-?H2O), giving rise to the formation of dimeric and mono-nuclear Pd-H species driven by reversible SO3--coordination. In addition, the L1-based Pd-catalyst could be immobilized in the ionic liquid [Bmim]NTf2 for six-run recycling uses without obvious activity loss and detectable metal leaching.
- Yang, Da,Liu, Huan,Liu, Lei,Guo, Wen-Di,Lu, Yong,Liu, Ye
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p. 5336 - 5344
(2019/10/11)
-
- Oxime-derived palladacycle Immobilized in an Ionic Liquid Brush as an Efficient and Reusable Catalyst for Mozoroki-Heck Reaction in Neat Water
-
An efficient and reusable heterogeneous catalyst with oxime-derived palladacycle immobilized in an ionic liquid brush has been synthesized and an environmentally-friendly procedure have been developed for coupling aryl iodides and bromides with acrylic acid. These reactions were conducted in neat water under aerobic conditions with water-insoluble or even solid aryl halides and they proceeded smoothly and cleanly without any organic co-solvent or other additives. The ionic liquid brush could be easily recovered and reused at least five times without significant loss of activity. The protocol has the advantages of excellent yields, environmental friendliness, and catalyst recyclability.
- Wang, Rong,Li, Shan,Li, Jing,Wei, Junfa
-
-
- Visible-light-enabled denitrative carboxylation of β-nitrostyrenes: A direct photocatalytic approach to cinnamic acids
-
The first workable application of β-nitrostyrenes and CBr4 as coupling partners for a highly stereoselective synthesis of (E)-cinnamic acids under visible light photoredox catalysis is reported. The reaction involves a radical denitrative tribromomethylation/hydrolysis cascade to afford (E)-cinnamic acids in excellent yields at room temperature in a one-pot procedure. Moreover, the implementation of visible light as a clean and inexpensive energy source and CBr4 as the latent source of carboxylic groups makes the protocol reconcilable with the present day scenario of organic synthesis.
- Tripathi, Shubhangi,Yadav, Lal Dhar S.
-
supporting information
p. 3765 - 3769
(2018/03/06)
-
- Palladium-Catalyzed Carbonylative Transformation of Organic Halides with Formic Acid as the Coupling Partner and CO Source: Synthesis of Carboxylic Acids
-
A palladium-catalyzed carbonylative transformation of organic halides with formic acid as the coupling partner to produce carboxylic acids has been developed. With a catalytic amount of DCC as the activator of formic acid, the process can be realized successfully through benzoic formic anhydride as the intermediate. Both vinyl and aryl (pseudo)halides were conveniently transformed into the corresponding acids in good yields.
- Wu, Fu-Peng,Peng, Jin-Bao,Qi, Xinxin,Wu, Xiao-Feng
-
p. 9710 - 9714
(2017/09/23)
-
- Polystyrene supported palladium nanoparticles catalyzed cinnamic acid synthesis using maleic anhydride as a substitute for acrylic acid
-
Maleic anhydride was explored as a substitute for acrylic acid to synthesize cinnamic acids from aryl halides under heterogeneous palladium catalyzed conditions. The combined role of surface and impregnated catalyst together performed an upright engineering to hold in situ generated molecules on the surface and subsequently facilitate their interaction for the desired product synthesis. Overall, a surface mediated approach for cinnamic acid synthesis from maleic anhydride following a major unexplored pathway through catalyst promoted decarboxylation was critically investigated.
- Thakur, Vandna,Kumar, Sandeep,Das, Pralay
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p. 3692 - 3697
(2017/09/07)
-
- Kinetic Resolution of Aromatic β-Amino Acids Using a Combination of Phenylalanine Ammonia Lyase and Aminomutase Biocatalysts
-
An enzymatic strategy for the preparation of (R)-β-arylalanines employing phenylalanine aminomutase and ammonia lyase (PAM and PAL) enzymes has been demonstrated. Candidate PAMs with the desired (S)-selectivity from Streptomyces maritimus (EncP) and Bacillus sp. (PabH) were identified via sequence analysis using a well-studied template sequence. The newly discovered PabH could be linked to the first ever proposed biosynthesis of pyloricidin-like secondary metabolites and was shown to display better β-lyase activity in many cases. In spite of this, a method combining the higher conversion of EncP with a strict α-lyase from Anabaena variabilis (AvPAL) was found to be more amenable, allowing kinetic resolution of five racemic substrates and a preparative-scale reaction with >98% (R) enantiomeric excess. This work represents an improved and enantiocomplementary method to existing biocatalytic strategies, allowing simple product separation and modular telescopic combination with a preceding chemical step using an achiral aldehyde as starting material. (Figure presented.).
- Weise, Nicholas J.,Ahmed, Syed T.,Parmeggiani, Fabio,Turner, Nicholas J.
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p. 1570 - 1576
(2017/05/05)
-
- Carboxylation of styrenes with CBr4 and DMSO via cooperative photoredox and cobalt catalysis
-
Cooperative photoredox and cobalt catalyzed carboxylation of styrenes with CBr4 to afford the corresponding α,β-unsaturated carboxylic acids has been realized through radical addition and Kornblum (DMSO) oxidation. DMSO serves as the oxidant, oxygen source and solvent under these photocatalytic conditions.
- Song, Cai-Xia,Chen, Ping,Tang, Yu
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p. 11233 - 11243
(2017/02/26)
-
- Chiral phosphoric acid catalyzed enantioselective annulation of acyclic enecarbamates to: In situ -generated ortho -quinone methides
-
The first organocatalytic asymmetric reaction of acyclic enecarbamates with o-quinone methides is disclosed. BINOL-based phosphoric acid catalysts were found to be suitable for the annulation reaction. With 10 mol% of the TRIP catalyst, high yields as well as excellent diastereo- and enantioselectivities are achieved for a variety of 2,3,4-trisubstituted chroman products.
- Gharui, Chandan,Singh, Shreya,Pan, Subhas Chandra
-
supporting information
p. 7272 - 7276
(2017/09/25)
-
- Carboxymethylcellulose-supported palladium nanoparticles generated in situ from palladium(II) carboxymethylcellulose as an efficient and reusable catalyst for ligand- and base-free Heck-Matsuda and Suzuki-Miyaura couplings
-
A novel palladium(II) carboxymethylcellulose (CMC-PdII) was prepared from sodium carboxymethylcellulose (CMC-Na) and PdCl2 in aqueous solution. It was employed as precatalyst for Heck-Matsuda and Suzuki-Miyaura couplings. The true catalytic species are active soluble Pd(0) or Pd(0) clusters released from palladium nanoparticles deposited on the CMC molecular skeleton (CMC-Pd0) formed in situ from CMC-PdII in the catalytic process.
- Xiao, Jinlong,Lu, Zhangxiu,Li, Zhipeng,Li, Yiqun
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p. 646 - 652
(2015/09/01)
-
- Magnetic polymer nanocomposite-supported Pd: An efficient and reusable catalyst for the Heck and Suzuki reactions in water
-
A novel type of magnetically responsive polymer nanocomposite Fe3O4@poly(undecylenic acid-co-4-vinyl pyridine-co-sodium acrylate) (Fe3O4@PUVS) was synthesized by the free radical polymerization of 4-vinyl pyridine (4-VP) with sodium acrylate (SAA) and Fe3O4@undecylenic acid. Pd2+ was then immobilized on this magnetic nanocomposite to form the magnetic Fe3O4@PUVS-Pd catalyst. This catalyst exhibited excellent catalytic activity for the Heck and Suzuki coupling reactions in water, and could be simply separated by using a permanent magnet. The supported catalyst could be used consecutively for six runs without significant loss of catalytic activity.
- Wang, Dongfang,Liu, Wendong,Bian, Fengling,Yu, Wei
-
p. 2052 - 2059
(2015/03/18)
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- SULFAMATE DERIVATIVE COMPOUND FOR USE IN PREVENTING OR TREATING EPILEPSY
-
The present invention relates to a pharmaceutical composition for treating or preventing epilepsy containing a sulfamate derivative compound and/or pharmaceutically acceptable salt thereof as an active ingredient. Furthermore, the present invention relates to a method for treatment or prevention epilepsy comprising administering a sulfamate derivative compound in a pharmaceutically effective amount to a subject in need of treatment or prevention of epilepsy.
- -
-
Page/Page column 37; 38
(2015/06/25)
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- Compositions comprising an aryl pyrazole and a substituted imidazole, methods and uses thereof
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This invention relates to compositions for combating parasites in animals, comprising 1-arylpyrazole compounds in combination with substituted imidazole compounds. This invention also provides for an improved methods for eradicating, controlling, and preventing parasite infestation in an animal comprising administering the compositions of the invention to an animal in need thereof.
- -
-
Page/Page column 27; 28
(2015/09/28)
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- Aromatic diacylhydrazine derivatives as a new class of polo-like kinase 1 (PLK1) inhibitors
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A novel class of aromatic diacylhydrazine derivatives was designed as PLK1 inhibitors. All the 19 new synthesized compounds were assayed for antitumor activity against the respective cervical cancer cells. In which, nine compounds with better antitumor activities were further tested for their PLK1 inhibitory activity. Last, we have successfully found that compound 7k showed both the promising antitumor activity with IC50 of 0.17 μM against the cervical cancer cells, and also processed the most potent PLK1 inhibitory activity with IC50 of 0.03 μM. In addition, docking simulation also carried out in this study to give a potent prediction binding mode between the small molecule and PKL1 (PDB code: 1umw) protein.
- Sun, Juan,Lv, Peng-Cheng,Guo, Feng-Jiao,Wang, Xin-Yi,Han, Xiao-,Zhang, Yang,Sheng, Gui-Hua,Qian, Shao-Song,Zhu, Hai-Liang
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p. 420 - 426
(2014/06/09)
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- PHENYLALKYL SULFAMATE COMPOUND AND MUSCLE RELAXANT COMPOSITION COMPRISING THE SAME
-
The present invention relates to novel phenylalkyl sulfamate compounds, a method for preventing or treating a disease associated with muscle spasm. The present invention ensures the enhancement of muscle relaxation activity essential for alleviation of muscle spasm, such that it is promising for preventing or treating various diseases associated with muscle spasm.
- -
-
Page/Page column 20-21; 41
(2014/01/08)
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- CANNABINOID RECEPTOR MODULATORS
-
Compounds of Formula (I) along with processes for their preparation that are useful for treating, managing and/or lessening the diseases, disorders, syndromes or conditions associated with the modulation of cannabinoid (CB) receptors. Methods of treating, managing and/or lessening the diseases, disorders, syndromes or conditions associated with the modulation of cannabinoid (CB) receptors of Formula (I).
- -
-
Paragraph 0173
(2013/07/19)
-
- CANNABINOID RECEPTOR MODULATORS
-
Compounds of Formula (I) along with processes for their preparation that are useful for treating, managing and/or lessening the diseases, disorders, syndromes or conditions associated with the modulation of cannabinoid (CB) receptors. Methods of treating, managing and/or lessening the diseases, disorders, syndromes or conditions associated with the modulation of cannabinoid (CB) receptors of Formula (I).
- -
-
Page/Page column 32
(2013/03/26)
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- COMPOSITIONS COMPRISING AN ARYL PYRAZOLE AND A SUBSTITUTED IMIDAZOLE, METHODS AND USES THEREOF
-
This invention relates to compositions for combating parasites in animals, comprising 1-arylpyrazole compounds in combination with substituted imidazole compounds. This invention also provides for an improved methods for eradicating, controlling, and preventing parasite infestation in an animal comprising administering the compositions of the invention to an animal in need thereof.
- -
-
Page/Page column 39-40
(2013/06/05)
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- Design, synthesis and biological evaluation of cinnamic acyl shikonin derivatives
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Inducing apoptosis is an important and promising therapeutic approach to overcome cancer. Here, we described a series of novel synthesized compounds, cinnamic acyl shikonin derivatives (1b-19b), which were synthesized starting from shikonin and cinnamic acids, which exhibit anticancer activity via inducing apoptosis in vitro. Our flow cytometry results showed that compound 8b((E)-1-(5,8-dihydroxy-1,4-dioxo-1,4-dihydronaphthalen-2-yl)-4-methylpent -3-enyl-3-(3-(trifluoromethyl) phenyl)acrylate) (IC50=0.69, 0.65, 1.62 μm for human SW872-s, A875 and A549 cell lines, respectively) exhibited conspicuous anticancer activities and has low cell toxicity in vitro. Therefore, we considered that compound 8b is potentially to be a candidate of anticancer agent. The proliferation inhibitory effect of compound 8b was associated with its apoptosis-inducing effect by activating caspase-3, caspase-7, caspase-9, and PARP. When the level of cleaved caspase-3, cleaved caspase-7, cleaved caspase-9, and cleaved PARP are rise, apoptosis of cancer cells will be induced.
- Lin, Hong-Yan,Chen, Wei,Shi, Jing,Kong, Wen-Yao,Qi, Jin-Liang,Wang, Xiao-Ming,Yang, Yong-Hua
-
p. 275 - 283
(2013/03/13)
-
- Titanium-catalyzed intermolecular hydroaminoalkylation of conjugated dienes
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Ti me kangaroo down: Conjugated dienes undergo intermolecular hydroaminoalkylation in the presence of Ti catalyst [Ind2TiMe 2] (Ind=η5-indenyl). This new reaction offers a highly atom-efficient approach to homoallylic amines from 1,3-butadienes. Copyright
- Preuss, Till,Saak, Wolfgang,Doye, Sven
-
supporting information
p. 3833 - 3837
(2013/04/24)
-
- Synthesis and antitumor activity of 1,3,4-oxadiazole possessing 1,4-benzodioxan moiety as a novel class of potent methionine aminopeptidase type II inhibitors
-
A series of 1,3,4-oxadiazole derivatives containing 1,4-benzodioxan moiety (7a-7q) have been designed, synthesized and evaluated for their antitumor activity. Most of the synthesized compounds were proved to have potent antitumor activity and low toxicity. Among them, compound 7a showed the most potent biological activity against Human Umbilical Vein Endothelial cells, which was comparable to the positive control. The results of apoptosis and flow cytometry (FCM) demonstrated that compound 7a induce cell apoptosis by the inhibition of MetAP2 pathway. Molecular docking was performed to position compound 7a into MetAP2 binding site in order to explore the potential target.
- Sun, Juan,Li, Ming-Hui,Qian, Shao-Song,Guo, Feng-Jiao,Dang, Xiao-Fang,Wang, Xiao-Ming,Xue, Ya-Rong,Zhu, Hai-Liang
-
supporting information
p. 2876 - 2879
(2013/06/26)
-
- Polypyrrole-palladium nanocomposite-coated latex particles as a heterogeneous catalyst in water
-
Polypyrrole-palladium nanocomposite-coated cross-linked polystyrene latex particles (PS/PPy-Pd) showed an excellent catalytic activity for Suzuki and Heck reactions in aqueous media. The PS/PPy-Pd can be recovered easily and quantitatively through the repeated uses with simple filtration and they maintain their high catalytic activities.
- Ohtaka, Atsushi,Kono, Yuki,Teratani, Takuto,Fujii, Syuji,Matsuzawa, Soichiro,Nakamura, Yoshinobu,Nomura, Ryoki
-
experimental part
p. 1097 - 1103
(2012/06/18)
-
- Aryldiazonium silica sulfates as efficient reagents for Heck-type arylation reactions under mild conditions
-
An efficient and straightforward procedure for Heck-type arylation reactions was studied using aryldiazonium silica sulfates and olefins in the presence of a catalytic amount of Pd(OAc)2. These reactions were carried out in water at room temperature without using a base or additional ligands. The use of a non-toxic solvent, a simple and clean work-up, short reaction times, and good yields are advantages of this method.
- Zarei, Amin,Khazdooz, Leila,Pirisedigh, Azadeh,Hajipour, Abdol R.,Seyedjamali, Hojjat,Aghaei, Hamidreza
-
experimental part
p. 4554 - 4557
(2011/09/20)
-
- Stereochemistry and mechanism of a microbial phenylalanine aminomutase
-
The stereochemistry of a phenylalanine aminomutase (PAM) on the andrimid biosynthetic pathway in Pantoea agglomerans (Pa) is reported. PaPAM is a member of the 4-methylidene-1H-imidazol-5(4H)-one (MIO)-dependent family of catalysts and isomerizes (2S)-α-phenylalanine to (3S)-β-phenylalanine, which is the enantiomer of the product made by the mechanistically similar aminomutase TcPAM from Taxus plants. The NH2 and pro-(3S) hydrogen groups at Cα and Cβ, respectively, of the substrate are removed and interchanged completely intramolecularly with inversion of configuration at the migration centers to form β-phenylalanine. This is a contrast to the retention of configuration mechanism followed by TcPAM.
- Ratnayake, Nishanka Dilini,Wanninayake, Udayanga,Geiger, James H.,Walker, Kevin D.
-
supporting information; experimental part
p. 8531 - 8533
(2011/07/29)
-
- Tandem reduction + cyclization of ortho-substituted cinnamic esters
-
Conjugate reduction of ortho-substituted cinnamic esters by Stryker's reagent to form copper enolates, followed by intramolecular aldol-type cyclization, successfully generated indane and tetralin rings in one pot efficiently. This tandem reaction is generally diastereoselective and provides good yields.
- Sass, Daiane Cristina,De Lucca Jr., Emílio Carlos,Da Silva Barbosa, Jader,De Oliveira, Kleber Thiago,Constantino, Mauricio Gomes
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scheme or table
p. 5371 - 5374
(2011/10/31)
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- Cinnamoyl inhibitors of tissue transglutaminase
-
(Figure Presented) Transglutaminases (TGases) catalyze the intermolecular cross-linking of certain proteins and tissue TGases (TG2) are involved in diverse biological processes. Unregulated, high TGase activities have been implicated in several physiological disorders, but few reversible inhibitors of TG2 have been reported. Herein, we report the synthesis of a series of novel trans-cinammoyl derivatives, discovered to be potent inhibitors of guinea pig liver transglutaminase. The most effective inhibitors evaluated can be sorted into two subclasses: substituted cinnamoyl benzotriazolyl amides and the 3-(substituted cinnamoyl)pyridines, referred to more commonly as azachalcones. Kinetic evaluation of both of these subclasses revealed that they display reversible inhibition and are competitive with acyl donor TGase substrates at IC50 values as low as 18 μM. An analysis of structure - activity relationships within these series of inhibitors permitted the identification of potentially important binding interactions. Further testing of some of the most potent inhibitors demonstrated their selectivity for TG2 and their potential for further development.
- Pardin, Christophe,Pelletier, Joelle N.,Lubell, William D.,Keillor, Jeffrey W.
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p. 5766 - 5775
(2008/12/22)
-
- Stereoselective hydroxycarbonylation of vinyl bromides to α,β-unsaturated carboxylic acids in the ionic liquid [BMIM]PF 6
-
(E/Z)-Isomers containing vinyl bromides were stereoselectively carbonylated to the corresponding (E)-α,β-ethylenic carboxylic acids in the ionic liquid [BMIM]PF6. Vinyl dibromides also underwent hydroxycarbonylation to give monoacids. The products are pure by proton NMR spectroscopic determination without purification by silica gel column chromatograghy or recrystallization.
- Zhao, Xiaodan,Alper, Howard,Yu, Zhengkun
-
p. 3988 - 3990
(2007/10/03)
-
- Efficient Aqueous-Phase Heck and Suzuki Couplings of Aryl Bromides Using Tri(4,6-dimethyl-3-sulfonatophenyl)phosphine Trisodium Salt (TXPTS)
-
(Matrix presented) Sterically demanding, sulfonated arylphosphines TXPTS and TMAPTS have been applied to the aqueous-phase Heck and Suzuki coupling of aryl bromides. TXPTS provides good yields of Heck coupling products from aryl bromides at 80°C, while both TMAPTS and TPPTS gave significantly less active catalysts. TXPTS is the first ligand to promote the aqueous-phase Heck coupling under such mild conditions. Both TXPTS and TMAPTS provide active catalysts for Suzuki couplings of aryl bromides at 50°C.
- Moore, Lucas R.,Shaughnessy, Kevin H.
-
p. 225 - 228
(2007/10/03)
-
- Aqueous-phase, palladium-catalyzed cross-coupling of aryl bromides under mild conditions, using water-soluble, sterically demanding alkylphosphines
-
Sterically demanding, water-soluble alkylphosphines have been used in combination with various palladium salts in Suzuki, Sonogashira, and Heck couplings of aryl bromides under mild conditions in aqueous solvents. The tert-butyl-substituted ligands 2-(di-tert-butylphosphino)ethyltrimethylammonium chloride (t-Bu-Amphos) and 4-(di-tert-butylphosphino)-N,N-dimethylpiperidinium chloride (t-Bu-Pip-phos) in combination with palladium(II) salts were found to give catalysts that were significantly more active than catalysts derived from tri(3-sulfonatophenyl)phosphine trisodium (TPPTS). Suzuki couplings of unactivated aryl bromides occurred efficiently at room temperature in water/acetonitrile and water/toluene biphasic mixtures or in neat water. Notably, Suzuki couplings of hydrophilic aryl bromides gave high yields without using organic solvents for the reaction or purification. This methodology has been applied to a highly efficient synthesis of diflunisal. The catalyst derived from t-Bu-Amphos was recycled three times in Suzuki couplings in water/toluene before catalyst activity began to significantly drop. The average yield of four cycles was >80% per cycle. Heck and Sonogashira couplings were carried out under mild conditions (50 and 80°C, respectively) with unactivated aryl bromides to give coupled products in high yield.
- DeVasher, Rebecca B.,Moore, Lucas R.,Shaughnessy, Kevin H.
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p. 7919 - 7927
(2007/10/03)
-
- Mizoroki-Heck arylation of α,β-unsaturated acids with a hybrid fluorous ether, F-626: Facile filtrative separation of products and efficient recycling of a reaction medium containing a catalyst
-
The Mizoroki-Heck reaction was carried out using a fluorous ether F-626 as the solvent and a fluorous Pd carbene complex as the catalyst. When carboxylic acids are the products, separation of both the F-626 and the Pd catalyst from the products can be conveniently carried out by simple filtration. The F-626 filtrates containing the Pd catalyst can be recycled.
- Fukuyama, Takahide,Arai, Masashi,Matsubara, Hiroshi,Ryu, Ilhyong
-
p. 8105 - 8107
(2007/10/03)
-
- Heck reaction in water with amphiphilic resin-supported palladium-phosphine complexes
-
The Heck reaction of various aryl halides and alkenes took place in water in the presence of an amphiphilic polystyrene-poly(ethylene glycol) resin-supported palladium-phosphine complex to give the corresponding styrene derivatives in quantitative yields.
- Uozumi, Yasuhiro,Kimura, Tsutomu
-
p. 2045 - 2048
(2007/10/03)
-
- A one-pot synthesis of 3-amino-3-arylpropionic acids
-
3-Aminopropionic acids (β-amino acids) are biologically active compounds of interest in medicinal and pharmaceutical chemistry. Twenty-one 3-amino-3-arylpropionic acids were synthesized via a facile one-pot synthesis. In addition, a series of mechanistic studies have been performed to optimize the production of these β-amino acids. The reaction mechanism of this one-pot synthesis of β-amino acids, as well as the electronic effect of para-substitution and the influence of solvent polarity on the proposed reaction mechanism are discussed.
- Tan,Weaver
-
p. 7449 - 7461
(2007/10/03)
-
- Novel titanium(IV) chloride catalyzed olefination of aldehydes: A simple and convenient synthesis of trans-cinnamic acids
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A variety of aromatic aldehydes were stereoselectively transformed into (E)-cinnamic acids via the reaction with ethyl bromoacetate and triphenylphosphine in the presence of catalytic amount of titanium tetrachloride, followed by hydrolysis and crystallization.
- Basavaiah, Deevi,Jaganmohan Rao, Anumolu
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p. 195 - 201
(2007/10/03)
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- Structure-activity relationship on the human EP3 prostanoid receptor by use of solid-support chemistry
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Potent and selective EP3 receptor ligands were found by making a library using solid-support chemistry. These compounds can be obtained by a Suzuki coupling reaction of a solid-supported benzyl bromide using various boronic acids. The yields obtained for this reaction were in the range of 24-95% of arylmethyl cinnamic acid I after cleavage from the Wang resin,
- Juteau, Helene,Gareau, Yves,Labelle, Marc,Lamontagne, Sonia,Tremblay, Nathalie,Carriere, Marie-Claude,Sawyer, Nicole,Denis, Danielle,Metters, Kathleen M.
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p. 747 - 749
(2007/10/03)
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- Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 10. Generation of 2-methylstyrylalkynes and their thermal cyclisation to 2-alkenylnaphthalenes
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A series of nine 2-methylcinnamoyl phosphorus ylides 7 have been prepared and are found upon FVP at 500°C to undergo loss of Ph3PO to afford the corresponding styrylalkynes 8 whose fully assigned 13C NMR spectra are presented. FVP of the ylides at 900°C leads to cyclisation to give substituted naphthalenes 9-18; the mechanism of these reactions may proceed either by initial hydrogen atom loss or an initial [1,7]hydrogen shift, but an alternative route involving an initial [1,3]hydrogen shift has been ruled out by examination of a deuterium labelled analogue. For the α-phenyl ylides 7d and 7i a further cyclisation leads to benzo[c]fluorene derivatives and this process has been extended to a thiophene analogue to give fluoreno[3,4-b]thiophene. The formation of 2-ethylnaphthalene as the main product from the α-methoxycarbonyl ylide 7e is due to a secondary thermal reaction of methyl 2-naphthylacetate which may involve a radical chain reaction featuring, as the propagation step, an unusual homolytic substitution at a methoxy carbon by a 2-naphthylmethyl radical.
- Aitken, R. Alan,Boeters, Christine,Morrison, John J.
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p. 2625 - 2631
(2007/10/03)
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- 5-Nitrofuran-2-ylmethyl group as a potential bioreductively activated pro-drug system
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5-Substituted isoquinolin-1-ones have been synthesised by one-pot Curtius rearrangement of the corresponding substituted 3-phenylpropenoyl azides and cyclisation. Arylmethylation of the anions of the isoquinolinones with benzyl halides [4-methoxybenzyl chloride, 2-(chloromethyl)furan and 5-nitro-2-(tosyloxymethyl)furan] takes place exclusively at nitrogen. Nitration of 2-(furan-2-ylmethyl)isoquinolin-1-one in strongly acidic medium gives 2-(5-nitrofuran-2-ylmethyl)isoquinolin-1-one, whereas weaker acidic conditions lead to dinitration. Curtius rearrangement of 3-carboranylbutanoyl azide and trapping with 5-nitrofuran-2-ylmethanol gives 5-nitrofuran-2-ylmethyl N-(3-carboranylpropyl)carbamate. Biomimetic reduction of these nitrofuranylmethyl derivatives of anticancer drugs triggers release of the parent drugs. Thus, these nitrofurans have potential applications as pro-drugs for selective release of therapeutic drugs in hypoxic solid tumours.
- Berry, Jane M.,Watson, Corrine Y.,Whish, William J. D.,Threadgill, Michael D.
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p. 1147 - 1156
(2007/10/03)
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- Substituted dihydroisoquinolinones and related compounds as potentiators of the lethal effects of radiation and certain chemotherapeutic agents; selected compounds, analogs and process
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The invention is selected, novel, and known analogs of isoquinolinones of the formula and pharmaceutically acceptable salts thereof; novel pharmaceutical compositions; and a method for enhancing the lethal effects for tumor cells to treatment having DNA damaging activity such as ionizing radiation or with chemotherapeutic agents.
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- Phenylethl o-methylcinnamate, a process for preparation and a fragrance composition containing same
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The invention relates to phenylethyl o-methylcinnamate and a process for its preparation. Phenylethyl o-methylcinnamate is prepared by, first, alkylating ethyl acetoacetate with o-methylbenzyl chloride in the presence of a phase transfer catalyst to yield 2-(o-methylbenzyl)-acetoacetate. Thereafter the 2-(o-methylbenzyl)-acetoacetate yielded in the alkylating step is halogenated to yield ethyl 2-halo-2-(o-methylbenzyl)-acetoacetate. This is followed by degarding the ethyl 2-halo-2-(o-methylbenzyl)-acetoacetate acid. Finally the o-methylcinnamic acid obtained in the degarding step is esterified with 2-phenylethanol into phenylethyl o-methylcinnamate. A fragrance composition utilizing phenylethyl o-methylcinnamate is also disclosed.
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- Iodide-promoted Debromination of Vicinal Dibromides. Part-I. In DMF
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The specific rate constants and the activation parameters ΔH*, ΔS* and ΔG*, for the iodide-induced debromination reaction of erythro-2,3-dibromo-3-phenylpropanoic acids (o-Cl, -F, -Br, -NO2, -CH3; m-OCH3, -F, -NO2, -CH3 and p-NO2, -F, -Cl, -CH3) and erythro-2,3-dibromobutanoic acid in dimethylformamide are reported.Ortho-substituted compounds were found to react faster than the unsubstituted ones irrespective of the nature of the substituent.Results indicate that the bromine attached to the α-carbon atom is attacked by I- and the transition state is between non-synchronous nearly E1 type and synchronous E2 type.
- Philip, V. J.,Mathai, I.M.,Raj, D. Joshwa Anthony,Jacob, G. Carol
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p. 350 - 353
(2007/10/02)
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- Synthesis of Substituted 1,2-Dihydroisoquinolines by the Intramolecular 1,3-Dipolar Alkyl Azide-Olefin Cycloaddition
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A general synthesis of substituted 1,2-dihydroisoquinolines based on intramolecular 1,3-dipolar cycloaddition of alkyl azides and olefins is described.Reaction of bromide 4 with sodium azide afforded azide 5, which underwent 1,3-dipolar cycloaddition intramolecularly to give triazoline 6 .Rearrangement of triazoline 6 on silica gel gave diazo compound 7.Treatment of 7 with rhodium acetate afforded substituted 1,2-dihydroisoquinoline 9 in good overall yield.
- Liu, Jia-Ming,Young, Jenn-Jong,Li, Yu-Jang,Sha, Chin-Kang
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p. 1120 - 1123
(2007/10/02)
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- 3aH-Indenes. Part 2. Cycloaddition Reactions of 3-Methoxy- and 3-Trimethylsiloxy-3a-methyl-3aH-indene
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The title 3a-methyl-3aH-indenes (1a) and (1b) have been prepared from indan-1-one via the dienone (5) and the trienone (6), and the preparation of the key intermediates (5) and (6) has been improved.The 3aH-indene (1b) behaves similarly to the methoxy derivative (1a), and rearranges on heating to the 1H-isomer.Cycloaddition reactions of (1a) to N-phenylmaleimide and maleic anhydride give isolable -adducts (12), which rearrange on heating to give the exo- and endo--adducts (13) and (14).In contrast, both 2-chloroacrylonitrile and 2-chloroacryloyl chloride give - adducts with (1a).The 2-chloroacryloyl chloride adducts are readily converted into the tricyclic ketone (23).The trimethylsiloxy 3aH-indene (1b) undergoes cycloaddition reactions with dimethyl acetylenedicarboxylate, 2-chloroacryloyl chloride, and dichloroketene.The trimethylsilyl derivative (1b) offers some advantages over the methoxyindene (1a) in synthetic work.
- McCague, Raymond,Moody, Christopher J.,Rees, Charles W.
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p. 2399 - 2407
(2007/10/02)
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- SYNTHESIS AND SOME TRANSFORMATIONS OF BENZOTHIOPHENE DERIVATIVES
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A number of 3-chloro-2-chlorocarbonylbenzothiophenes with alkyl substituents in various positions of the benzene ring were synthesized by arylation of acrylic acid with the corresponding alkyl-substituted iodobenzenes under the influence of catalytic amounts of palladium acetate and subsequent oxidation of the resulting arylacrylic acids with thionyl chloride.Replacement of the pyridine added in the oxidation reaction by triethylbenzylammonium chloride led to substantial increases in the yields of the desired products.The possibility of conversionof the resulting benzothiophene derivatives to thiophene ring-unsubstituted benzothiophenes was shown in the case of 3-chloro-2-chlorocarbonylbenzothiophene as a result of successive saponification of the 2-chlorocarbonyl group, decarboxylation, and dechlorination.
- Sidorenko, T.N.,Terent'eva, G.A.,Raida, V.S.,Andrienko, O.S.,Savinykh, Yu.V.,Aksenov, V.S.
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p. 1246 - 1250
(2007/10/02)
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