- Copper-Catalyzed Ullmann-Type Coupling and Decarboxylation Cascade of Arylhalides with Malonates to Access α-Aryl Esters
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We have developed a high-efficiency and practical Cu-catalyzed cross-coupling to directly construct versatile α-aryl-esters by utilizing readily available aryl bromides (or chlorides) and malonates. These gram-scale approaches occur with turnovers of up to 1560 and are smoothly conducted by the usage of a low catalyst loading, a new available ligand, and a green solvent. A variety of functional groups are tolerated, and the application occurs with α-aryl-esters to access nonsteroidal anti-inflammatory drugs (NSAIDs) on the gram scale.
- Cheng, Fei,Chen, Tao,Huang, Yin-Qiu,Li, Jia-Wei,Zhou, Chen,Xiao, Xiao,Chen, Fen-Er
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supporting information
p. 115 - 120
(2022/01/04)
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- Coupling of Reformatsky Reagents with Aryl Chlorides Enabled by Ylide-Functionalized Phosphine Ligands
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The coupling of aryl chlorides with Reformatsky reagents is a desirable strategy for the construction of α-aryl esters but has so far been substantially limited in the substrate scope due to many challenges posed by various possible side reactions. This limitation has now been overcome by the tailoring of ylide-functionalized phosphines to fit the requirements of Negishi couplings. Record-setting activities were achieved in palladium-catalyzed arylations of organozinc reagents with aryl electrophiles using a cyclohexyl-YPhos ligand bearing an ortho-tolyl-substituent in the backbone. This highly electron-rich, bulky ligand enables the use of aryl chlorides in room temperature couplings of Reformatsky reagents. The reaction scope covers diversely functionalized arylacetic and arylpropionic acid derivatives. Aryl bromides and chlorides can be converted selectively over triflate electrophiles, which permits consecutive coupling strategies.
- Hu, Zhiyong,Wei, Xiao-Jing,Handelmann, Jens,Seitz, Ann-Katrin,Rodstein, Ilja,Gessner, Viktoria H.,Goo?en, Lukas J.
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supporting information
p. 6778 - 6783
(2021/02/01)
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- Chlorotrimethylsilane and Sodium Iodide: A Useful Combination for the Regioselective Deoxygenation of Arylalkyl-α-Diketones
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An efficient regioselective deoxygenation of arylalkyl-1,2-diketones by the couple trimethylsilylchloride/sodium iodide has been reported. In all cases, the deoxygenation takes place on the carbonyl group (Cα=O) proximal to the aromatic ring in methylene chloride at room temperature in good yields, furnishing a series of variously functionalized alkylbenzylketones. A large range of functional groups were well tolerated on the ortho-, meta- and para-positions by this mild process regardless of their electronic effects, demonstrating the general character of the present methodology. The trimethylsilylchloride/sodium iodide reducing process was also successfully applied to reduce α-ketoacid and α-ketoester substrates. (Figure presented.).
- Yuan, Ling-Zhi,Zhao, Guangkuan,Hamze, Abdallah,Alami, Mouad,Provot, Olivier
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p. 2682 - 2691
(2017/08/16)
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- Preparation method of 4-methylthio phenylacetic acid
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The invention provides a preparation method of 4-methylthio phenylacetic acid. According to the preparation method, p-halogenated phenylacetic acid and phenylacetic acid derivatives thereof are taken as the primary raw materials. The preparation method is characterized in that p-halogenated phenylacetic acid and phenylacetic acid derivatives thereof and sodium methyl mercaptide carry out catalytic reactions in the presence of cuprous ions and DMF, and 4-methylthio phenylacetic acid is obtained after the post treatment. The Willgerodt-kindler reactions will generate hydrogen sulfide, which is pollutant to the environment, the provided method does not have Willgerodt-kindler reactions, and thus the environmental pollution is avoided. Moreover, the operation is simple, and the method is environment-friendly and is suitable for large-scale industrial production.
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Paragraph 0011
(2016/11/14)
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- MULTIPLE KINASE PATHWAY INHIBITORS
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Kinase with inhibitory activity against kinases disposed in multiple signaling pathways and their therapeutic uses.
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Page/Page column 267-269; 277
(2014/04/17)
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- PROCESS FOR PREPARING ARYL- AND HETEROARYLACETIC ACID DERIVATIVES
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The invention relates to a process for preparing aryl- and heteroarylacetic acids and derivatives thereof by reaction of aryl or heteroaryl halides with malonic diesters in the presence of a palladium catalyst, of one or more bases and optionally of a phase transfer catalyst. This process enables the preparation of a multitude of functionalized aryl- and heteroarylacetic acids and derivatives thereof, especially also the preparation of arylacetic acids with sterically demanding substituents.
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Paragraph 0075; 0076; 0081; 0082
(2014/06/23)
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- Pd-catalyzed decarboxylative cross-couplings of potassium malonate monoesters with aryl halides
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An efficient catalytic protocol for Pd-catalyzed decarboxylative cross-coupling of potassium malonate monoesters and derivatives with aryl bromides and chlorides are described. Because of its broad applicability, this new catalytic system provides an alternative method for the preparation of diverse aryl acetic acids and derivatives.
- Feng, Yi-Si,Wu, Wei,Xu, Zhong-Qiu,Li, Yan,Li, Ming,Xu, Hua-Jian
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experimental part
p. 2113 - 2120
(2012/03/26)
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- Three-component reaction: Synthesis, characterization, and biological study of some fused bridgehead nitrogen heterocyclic systems containing 4-methylthiophenyl moiety
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Several substituted thiazolo-[3,2-b]-1,2,4-triazole derivatives 4 were synthesized by a one-pot, three-component reaction of 3-(4-methylthiobenzyl)-1, 2,4-triazole-5-thiol 3, substituted 5-aryl-furan-2-carboxaldehydes/substituted aromatic aldehydes, and monochloroacetic acid in acetic acid using acetic anhydride and anhydrous sodium acetate. Compound 3 was obtained from 4-methylthiophenyl acetic acid by esterification followed by hydrazinolysis. All structures of the newly synthesized compounds were elucidated by elemental analysis and spectral data. The newly synthesized compounds were also screened for their antimicrobial and anti-inflammatory activities. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. Copyright Taylor & Francis Group, LLC.
- Manjunatha,Poojary, Boja,Lobo, Prajwal L.,Kumari, N. Suchetha,Anoop
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scheme or table
p. 526 - 532
(2011/05/15)
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- Practical synthesis of 2-arylacetic acid esters via palladium-catalyzed dealkoxycarbonylative coupling of malonates with aryl halides
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A new palladium-based system was developed that catalyzes the coupling of aryl halides with diethyl malonates in the presence of mild bases. In the course of the reaction, the intermediately formed diethyl arylmalonate is directly converted into the arylacetic acid ester via liberation of carbon dioxide and an alkanol. This cross-coupling/dealkoxycarbonylation process provides an efficient and high-yielding synthetic entry to diversely functionalized arylacetic acid esters. Two complementary protocols were developed, one of which is optimal for electron-rich, the other for electron-poor aryl halides. Both make use of low loadings of palladium(0) bis(dibenzylideneacetone) (0.5 mol%)/tri-tert-butylphosphonium tetrafluoroborate (1.1 mol%) as the catalyst and diethyl malonate as the reaction solvent. The new procedures are particularly effective for sterically hindered substrates. Copyright
- Song, Bingrui,Rudolphi, Felix,Himmler, Thomas,Goossen, Lukas J.
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supporting information; experimental part
p. 1565 - 1574
(2011/08/03)
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- Synthesis and biological evaluation of some 1,3,4-oxadiazole derivatives
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The acid hydrazides (2) derived from ibuprofen and 4-methylthiophenyl acetic acids have been subjected to cyclization with carbon disulphide under basic conditions to yield 1,3,4-oxadiazol-2-thiones (3) which on aminomethylation with formaldehyde and secondary amines afforded a series of Mannich bases (4 and 5). Purity of the compounds has been confirmed by TLC. Structures of these compounds were established on the basis of elemental analyses and spectral studies. The newly synthesized compounds were evaluated for their anti-inflammatory, analgesic, ulcerogenic and antimicrobial activities.
- Manjunatha,Poojary, Boja,Lobo, Prajwal L.,Fernandes, Jennifer,Kumari, N. Suchetha
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scheme or table
p. 5225 - 5233
(2011/01/04)
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- NAPHTHALENONE COMPOUNDS EXHIBITING PROLYL HYDROXYLASE INHIBITORY ACTIVITY, COMPOSITIONS, AND USES THEREOF
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Compounds of Formula (I) and Formula (II) are useful as inhibitors of HIF prolyl hydroxylases. Compounds of Formula(I) and Formula (II) have the following structures, where the definitions of the variables are provided herein.
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Page/Page column 117
(2008/12/06)
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- Synthesis of 4,5-Diaryl-1H-pyrazole-3-ol derivatives as potential COX-2 inhibitors
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4,5-Diaryl-1H-pyrazole-3-ol was utilized as a versatile template to synthesize several classes of compounds such as pyrazolo-oxazines 7, pyrazolo-benzooxazines 9, pyrazolo-oxazoles 10, and its analogues 11a-c as potential COX-2 inhibitors. Compounds 11b,c were successfully synthesized with use of pyridinium p-toluenesulfonate mediated cyclization of the ketal intermediate. Diarylpyrazolo-benzooxazepine analogues were synthesized by using Cu-mediated cyclization of the O-alkylated arylbromide intermediate. Arylsulfonamides were synthesized efficiently on a large scale with 4-[4-(4-fluorophenyl)-5-hydroxy-2H-pyrazol-3-yl]benzenesulfonamide 31 template readily synthesized from commercially available 4-sulfamoyl benzoic acid 29. The structure of a representative compound from each class was confirmed by X-ray crystallography. Selected compounds tested for inhibitory activity against COX-1 and COX-2 enzymes showed good selectivity for COX-2 versus COX-1 enzyme.
- Patel, Meena V.,Bell, Randy,Majest, Sandra,Henry, Rodger,Kolasa, Teodozyj
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p. 7058 - 7065
(2007/10/03)
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- SULFONYLPHENYLPYRAZOLE COMPOUNDS USEFUL AS COX-2 INHIBITORS
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The present invention encompasses novel sulfonylphenylpyrazole compounds useful in the treatment of cyclooxygenase-2 mediated diseases.
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- Sulfonylphenylpyrazole compounds useful as COX-2 inhibitors
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The present invention encompasses novel sulfonylphenylpyrazole compounds useful in the treatment of cyclooxygenase-2 mediated diseases.
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- Synthesis and immunosuppressive activity of 2-substituted 2- aminopropane-1,3-diols and 2-aminoethanols
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A series of 2-substituted 2-aminopropane-1,3-diols was synthesized and evaluated for their lymphocyte-decreasing effect and immunosuppressive effect on rat skin allograft. A phenyl ring was introduced into the alkyl chain of the lead compound 3, which is an immunosuppressive agent structurally simplified from myriocin (1, ISP-I) via compound 2. The potency of the various compounds was dependent upon the position of the phenyl ring within the alkyl side chain. The most suitable length between the quaternary carbon atom and the phenyl ring was two carbon atoms. 2-Substituted 2-aminoethanols were successively synthesized and evaluated for their T-cell-decreasing effect and immunosuppressive effect using a popliteal lymph node gain assay in rats. The absolute configuration at the quaternary carbon affected the activity, and the (pro-S)-hydroxymethyl group of compound 6 was essential for potent immunosuppressive activity. Favorable substituents for the (pro-R)- hydroxymethyl group of 6 were hydroxyalkyl (hydroxyethyl and hydroxypropyl) or lower alkyl (methyl and ethyl) groups. 2-Amino-2-[2-(4- octylphenyl)ethyl]propane-1,3-diol hydrochloride (6, FTY720) was found to possess considerable activity and is expected to be useful as an immunosuppressive drug for organ transplantation.
- Kiuchi, Masatoshi,Adachi, Kunitomo,Kohara, Toshiyuki,Minoguchi, Masanori,Hanano, Tokushi,Aoki, Yoshiyuki,Mishina, Tadashi,Arita, Masafumi,Nakao, Noriyoshi,Ohtsuki, Makio,Hoshino, Yukio,Teshima, Koji,Chiba, Kenji,Sasaki, Shigeo,Fujita, Tetsuro
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p. 2946 - 2961
(2007/10/03)
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- Sulfonamides and uses
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Sulfonamides of formula I, in which the symbols R1 -R6, X, Y and n have the significance given in the description and which are in part novel compounds, and salts thereof, which can be used as active ingredients for the manufacture of medicaments for the treatment of circulatory disorders, especially hypertension, ischemia, vasospasms and angina pectoris, are described.
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- SYNTHESE UND UV/VIS-SPEKTROSKOPISCHE EIGENSCHAFTEN SOLVATOCHROMER UND HALOCHROMER METHANSULFONYL-SUBSTITUIERTER PYRIDINIUM-N-PHENOLAT-BETAINFARBSTOFFE
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Synthese und UV/Vis-spektroskopische Eigenschaften der negativ solvatochromen, methansulfonyl-substituierten Betainfarbstoffe Ic-Ie werden beschrieben.Die lineare Korrelation zwischen den ET-Werten des wasserloeslichen Betains Ic und den ET(30)-Werten des Standardbetains Ia erlaubt eine Erweiterung der empirischen ET(30)-Polaritaetsskala auf waessrige Elektrolytloesungen.Die Betaine Ic-Ie weisen eine negative Halochromie (Halo-Solvatochromie) auf.Eine neue Definition der Halochromie (Halo-Solvatochromie) wird gegeben.
- Reichardt, Christian,Schaefer, Gerhard,Milart, Piotr
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