- Nickel-catalyzed deallylation of aryl allyl ethers with hydrosilanes
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An efficient and mild catalytic deallylation method of aryl allyl ethers is developed, with commercially available Ni(COD)2 as catalyst precursor, simple substituted bipyridine as ligand and air-stable hydrosilanes. The process is compatible with a variety of functional groups and the desired phenol products can be obtained with excellent yields and selectivity. Besides, by detection or isolation of key intermediates, mechanism studies confirm that the deallylation undergoes η3-allylnickel intermediate pathway.
- Ding, Guangni,Fan, Sijie,Wang, Jingyang,Wang, Yu,Wu, Xiaoyu,Xie, Xiaomin,Yang, Liqun,Zhang, Zhaoguo
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supporting information
(2021/09/28)
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- Exploring the Electronic Properties of Extended Benzofuran-Cyanovinyl Derivatives Obtained from Lignocellulosic and Carbohydrate Platforms Raw Materials
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Two series of linear extended benzofuran derivatives associating cyanovinyl unit and phenyl or furan moieties obtained from benzaldehyde-lignocellulosic (Be series) or furaldehyde –saccharide (Fu series) platforms were prepared in order to investigate their emission and electrochemical properties. For the fluorescence in solution and solid states, contrasting results between the two series were demonstrated. For Be series a net aggregation induced emission effect was observed with high fluorescence quantum yield for the solid state. A [2+2] cycloaddition under irradiation at 350 nm was also revealed for one derivative of Be series. In contrast, for Fu series the fluorescence in solution is higher than in the solid state. The X-ray crystallography studies for the compounds reveal the formation of strong π-π stacking for the derivatives without emissive property in the solid state and the presence of essentially lateral contacts for emissive compounds. Taking advantage of the propensity to develop 2D π-stacking mode for the more extended derivative with a central furan cycle, organic field effect transistors presenting hole mobility have been made.
- Ibrahim, Nagham,Moussallem, Chady,Allain, Magali,Segut, Olivier,Gohier, Frédéric,Frère, Pierre
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p. 475 - 482
(2021/03/31)
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- Highly Efficient Oxidative Cyanation of Aldehydes to Nitriles over Se,S,N-tri-Doped Hierarchically Porous Carbon Nanosheets
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Oxidative cyanation of aldehydes provides a promising strategy for the cyanide-free synthesis of organic nitriles. Design of robust and cost-effective catalysts is the key for this route. Herein, we designed a series of Se,S,N-tri-doped carbon nanosheets with a hierarchical porous structure (denoted as Se,S,N-CNs-x, x represents the pyrolysis temperature). It was found that the obtained Se,S,N-CNs-1000 was very selective and efficient for oxidative cyanation of various aldehydes including those containing other oxidizable groups into the corresponding nitriles using ammonia as the nitrogen resource below 100 °C. Detailed investigations revealed that the excellent performance of Se,S,N-CNs-1000 originated mainly from the graphitic-N species with lower electron density and synergistic effect between the Se, S, N, and C in the catalyst. Besides, the hierarchically porous structure could also promote the reaction. Notably, the unique feature of this metal-free catalyst is that it tolerated other oxidizable groups, and showed no activity on further reaction of the products, thereby resulting in high selectivity. As far as we know, this is the first work for the synthesis of nitriles via oxidative cyanation of aldehydes over heterogeneous metal-free catalysts.
- Hua, Manli,Song, Jinliang,Huang, Xin,Liu, Huizhen,Fan, Honglei,Wang, Weitao,He, Zhenhong,Liu, Zhaotie,Han, Buxing
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supporting information
p. 21479 - 21485
(2021/08/23)
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- Metabolically stable 5-HMF derivatives for the treatment of hypoxia
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5-HMF derivative compounds that bind covalently with hemoglobin are provided. Methods of treating sickle cell disease and other hypoxia-related disorders by administering such compounds are also provided.
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- Direct synthesis of secondary amides from ketones through Beckmann rearrangement using O-(mesitylsulfonyl)hydroxylamine
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The Beckmann rearrangement is a versatile method for the preparation of secondary amides from ketones via oxime intermediates and has been widely used in the synthesis of bioactive natural products and pharmaceuticals. Herein, we have developed a highly efficient direct method for the preparation of secondary amides and lactams from ketones using O-(mesitylsulfonyl)hydroxylamine (MSH). The reactions proceed rapidly at room temperature under mild condition without requiring any additive, and tolerate multiple functional groups. A simple aqueous work-up often furnished the products in excellent yield with high purity.
- Chandra, Dinesh,Verma, Saumya,Pandey, Chandra Bhan,Yadav, Ajay K.,Kumar, Puneet,Tiwari, Bhoopendra,Jat, Jawahar L.
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supporting information
(2020/03/23)
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- Zinc(II)-Catalyzed Synthesis of Secondary Amides from Ketones via Beckmann Rearrangement Using Hydroxylamine-O-sulfonic Acid in Aqueous Media
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A zinc(II)-catalyzed single-step protocol for the Beckmann rearrangement using hydroxylamine-O-sulfonic acid (HOSA) as the nitrogen source in water was developed. This direct method efficiently produces secondary amides under open atmosphere in a pure form after basic aqueous workup. It isenvironmentally benign and operationally simple.
- Verma, Saumya,Kumar, Puneet,Khatana, Anil K.,Chandra, Dinesh,Yadav, Ajay K.,Tiwari, Bhoopendra,Jat, Jawahar L.
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p. 3272 - 3276
(2020/11/02)
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- CHEMICAL COMPOUNDS
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The invention is directed to substituted salicylamide derivatives. Specifically, the invention is directed to compounds according to FormμLa (I): wherein R, R1,P, X, Y, and Z are as defined herein; or a pharmaceutically acceptable salt thereof. The compounds of the invention are inhibitors of CD73 and can be usefμL in the treatment of cancer, pre-cancerous syndromes and diseases associated with CD73 inhibition, such as AIDS, the treatment of HIV, autoimmune diseases, infections, atherosclerosis, and ischemia–reperfusion injury. Accordingly, the invention is further directed to pharmaceutical compositions comprising a compound of the invention. The invention is still further directed to methods of inhibiting CD73 activity and treatment of disorders associated therewith using a compound of the invention or a pharmaceutical composition comprising a compound of the invention.
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Page/Page column 119
(2019/04/11)
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- Copper-Catalyzed 1,2-Bistrifluoromethylation of Terminal Alkenes
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Many efficient catalytic methods for the introduction of trifluoromethyl group (CF3) have been reported. Among them, the addition of CF3 and other components to alkenes is well known, and many components such as azides, cyanides, amines, and halides have been inserted into alkenes with CF3. However, to date the double catalytic insertion of CF3 into an alkene is unknown. Herein, we report the catalytic 1,2-bistrifluoromethylations of alkenes catalyzed by Copper (Cu). We used two CF3 sources, namely Umemoto's reagent and (trifluoromethyl)trimethylsilane (TMSCF3). Each reagent plays a unique role during this transformation; Umemoto's reagent generates CF3 radicals, while TMSCF3 is used to form CF3 anions. Copper (I) bromide (CuBr) exhibited the best catalytic activity for this reaction. We believe that CuBr oxidizes the alkyl radical, which is produced by the addition of the CF3 radical to the alkene, to the corresponding alkyl cation, which then reacts with the CF3 anion from TMSCF3 to produce the desired product. This reaction tolerates a diverse set of substrates bearing functional groups such as amides, esters, ethers, ketones, protected amines, tertiary amines, and phthalimides; hence this transformation is widely applicable to a wide variety of substrates. (Figure presented.).
- Oh, Hyunseok,Park, Areum,Jeong, Kyu-Sung,Han, Soo Bong,Lee, Hyuk
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supporting information
p. 2136 - 2140
(2019/03/13)
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- Cu(OTf) 2 -Catalyzed Beckmann Rearrangement of Ketones Using Hydroxylamine- O -sulfonic Acid (HOSA)
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The Beckmann rearrangement (BKR) of ketones to secondary amides often requires harsh reaction conditions that limit its practicality and scope. Herein, the Cu(OTf) 2 -catalyzed BKR of ketones under mild reaction conditions using hydroxylamine- O -sulfonic acid (HOSA), a commercial water soluble aminating agent, is described. This method is compatible with most functional groups and directly provides the desired amides in good to excellent yields.
- Anugu, Raghunath Reddy,Chandra, Dinesh,Falck, John R.,Jat, Jawahar L.,Munnuri, Sailu,Verma, Saumya
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p. 3709 - 3714
(2019/09/30)
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- Method for preparing 5-hydroxymethyl-2-furannitrile through catalytic ammoxidation
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The invention belongs to the organic synthesis field and particularly relates to a method for preparing 5-hydroxymethyl-2-furannitrile through catalytic ammoxidation. The method comprises the steps ofcarrying out ammoxidation reaction under the effect of a catalyst by taking 5-hydroxymethyl furfural as the raw material, one or two of oxygen or air as an oxidant and one or at least two of liquid ammonia, ammonia water or ammonia salt as a nitrogen source, carrying out centrifugation so as to remove the catalyst, carrying out rotary evaporation so as to remove a solvent, and carrying out purification by virtue of a column chromatography, so as to obtain a 5-hydroxymethyl-2-furannitrile product. The product of the method is high in yield and easy to separate and has very good application prospects.
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Paragraph 0026-0053
(2018/05/16)
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- Synthesis of Phenylpropanoids via Matsuda-Heck Coupling of Arene Diazonium Salts
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The Pd-catalyzed Heck-type coupling (Matsuda-Heck reaction) of electron rich arene diazonium salts with electron deficient olefins has been exploited for the synthesis of phenylpropanoid natural products. Examples described herein are the naturally occurring benzofurans methyl wutaifuranate, wutaifuranol, wutaifuranal, their 7-methoxy derivatives, and the O-prenylated natural products boropinols A and C.
- Schmidt, Bernd,Wolf, Felix
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p. 4386 - 4395
(2017/04/28)
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- Visible-light-induced thiotrifluoromethylation of terminal alkenes with sodium triflinate and benzenesulfonothioates
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An unconventional reductive quenching cycle was developed to realize the visible-light-induced thiotrifluoromethylation of terminal alkenes. CF3SO2Na was used as an easy to handle CF3 radical source to afford the desired products in moderate to good yields. Mild reaction conditions and a broad substrate scope feature in this transformation.
- Kong, Weiguang,An, Hejun,Song, Qiuling
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supporting information
p. 8968 - 8971
(2017/08/15)
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- Catalytic Amidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxamide over Alkali Manganese Oxides
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2,5-Furandicarboxamide was firstly synthesized in yield of 85% via catalytic oxidative amidation of 5-hydroxymethylfurfural with aqueous NH3 over alkali manganese oxides of α-MnO2/NaxMnO2. The intermediates of 5-hydroxymethyl-furonitrile, 2,5-dicyanofuran, and 5-cyano-2-furancarboxamide were verified and their reactivities were further examined. The kinetic analysis results showed that the transformation of intermediate product of 5-cyano-2-furancarboxamide to 2,5-furan-dicarboxamide is a slower step, which is closely relative to the reaction temperature and basicity of catalyst.
- Li, Xiaofang,Jia, Xiuquan,Ma, Jiping,Xu, Yongming,Huang, Yizheng,Xu, Jie
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p. 984 - 990
(2017/06/27)
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- Catalytic conversion of 5-hydroxymethylfurfural into 2,5-furandiamidine dihydrochloride
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Via implantation of nitrogen from aq. NH3 into hydroxymethylfurfural (HMF), dimethyl furan-2,5-dicarboximidate was synthesized over a manganese oxide catalyst. It was realized by the ammoxidation of HMF followed by methanol addition under mild reaction conditions. The imidate prepared in situ was further transformed into 2,5-furandiamidine dihydrochloride by reaction with ammonium chloride.
- Jia, Xiuquan,Ma, Jiping,Wang, Min,Ma, Hong,Chen, Chen,Xu, Jie
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supporting information
p. 974 - 978
(2016/02/27)
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- Copper-promoted sandmeyer difluoromethylthiolation of aryl and heteroaryl diazonium salts
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An efficient copper-promoted difluoromethylthiolation of aryl and heteroaryl diazonium salts is described. The reaction is conducted under mild reaction conditions and various functional groups were compatible. In addition, reactions of heteroaryl diazonium salts such as pyridyl, quinolinyl, benzothiazolyl, thiophenyl, carbazolyl, and pyrazolyl diazonium salts occurred smoothly to afford the medicinally important difluoromethylthiolated heteroarenes. Furthermore, a more practical one-pot direct diazotization and difluoromethylthiolation protocol was developed, and it converts the aniline derivatives into difluoromethylthiolated arenes. The utility of the method is demonstrated by difluoromethylthiolation of a number of natural products and drug molecules. A dose of salt: The title reaction is conducted under mild reaction conditions and various functional groups are compatible. (Hetero)aryl diazonium salts reacted smoothly to afford the medicinally important difluoromethylthiolated (hetero)arenes. A practical one-pot direct diazotization and difluoromethylthiolation protocol was developed for aniline derivatives to generate difluoromethylthiolated arenes.
- Wu, Jiang,Gu, Yang,Leng, Xuebing,Shen, Qilong
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supporting information
p. 7648 - 7652
(2015/06/25)
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- Stannous chloride dihydrate-mediated efficient access to secondary and primary amides from oximes
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Highly selective, efficient and expeditious Beckmann rearrangement of a wide range of ketoximes to secondary amides (20 examples) has been accomplished using stoichiometric amount of stannous chloride dihydrate in the presence of nucleophilic additive, tetra-n-butylammonium iodide (TBAI) (10 moI%) and 4 ? MS in dry acetonitrile at reflux temperature. Aldoximes delivered primary amides through intermediacy of nitriles upon heating with an equimolar amount of SnCl2·2H2O and DBU in dry toluene at reflux in good to acceptable yields (12 examples). Utilization of mild Lewis acid, inexpensive rack reagents and procedural simplicity including easy isolation of products are key advantageous features of the protocol.
- Ganguly, Nemai C.,Nayek, Subhasis,Chandra, Sumanta
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p. 1695 - 1702
(2014/01/17)
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- Synthesis and SAR studies of 3-allyl-4-prenyloxyaniline amides as potent 15-lipoxygenase inhibitors
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15-Lipoxygenases are one of the nonheme iron-containing proteins with ability of unsaturated lipid peroxidation in animals and plants. The critical role of the enzymes in formation of inflammations, sensitivities and some of cancers has been demonstrated in mammalians. Importance of the 15-lipoxygenases leads to development of mechanistic studies, products analysis and synthesis of their inhibitors. In this work new series of the 3-allyl-4-allyoxyaniline amides and 3-allyl-4-prenyloxyaniline amides were designed, synthesized and their inhibitory potency against soybean 15-lipoxygenase were determined. Among the synthetic amides, 3-allyl-4-(farnesyloxy)-adamantanilide showed the most potent inhibitory activity by IC50 value of 0.69 μM. SAR studies showed that in spite of prenyl length increases, the effects of the amide size and its electronic properties on the inhibitory potency became predominant. The SAR studies was also showed that the orientation of allyl and prenyloxy moieties toward Fe core of the SLO active site pocket is the most suitable location for enzyme inhibition.
- Jabbari, Atena,Davoodnejad, Mahdieh,Alimardani, Maliheh,Assadieskandar, Amir,Sadeghian, Ali,Safdari, Hadi,Movaffagh, Jebraeel,Sadeghian, Hamid
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p. 5518 - 5526
(2012/10/30)
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- Efficient iodine-mediated beckmann rearrangement of ketoximes to amides under mild neutral conditions
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Aryl ketoximes readily underwent Beckmann rearrangement to give N-substituted amides in excellent yields on electrophilic activation by elemental iodine in anhydrous acetonitrile under reflux. The main advantages of this environmentally friendly protocol include a high selectivity as a result of the absence of any accompanying deprotection to form the parent ketones as byproducts, mild neutral conditions, procedural simplicity, and particularly ease of isolation of the products.
- Ganguly, Nemai C.,Mondal, Pallab
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experimental part
p. 3705 - 3709
(2011/01/03)
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- Asymmetric synthesis of aryloxypropanolamines via OsO4-catalyzed asymmetric dihydroxylation
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A simple and effective procedure for the enantioselective synthesis of several β-adrenergic blocking agents incorporating the first asymmetric synthesis of celiprolol, is described. The key steps are (i) sharpless asymmetric dihydroxylation of aryl allyl ethers to introduce chirality into the molecules and (ii) conversion of cyclic sulfates into the corresponding epoxides using a three-step procedure.
- Sayyed, Iliyas A.,Thakur, Vinay V.,Nikalje, Milind D.,Dewkar, Gajanan K.,Kotkar,Sudalai
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p. 2831 - 2838
(2007/10/03)
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- Design and synthesis of a series of melamine-based nitroheterocycles with activity against trypanosomatid parasites
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The parasites that give rise to human African trypanosomiasis (HAT) are auxotrophs for various nutrients from the human host, including purines. They have specialist nucleoside transporters to import these metabolites. In addition to uptake of purine nucleobases and purine nucleosides, one of these transporters, the P2 transporter, can carry melamine derivatives; these derivatives are not substrates for the corresponding mammalian transporters. In this paper, we report the coupling of the melamine moiety to selected nitro heterocycles with the aim of selectively delivering these compounds to the parasites. Some compounds prepared have similar in vitro trypanocidal activities as melarsoprol, the principal drug used against late-stage HAT, with 50% growth inhibitory concentrations in the submicromolar range. Selected compounds were also evaluated in vivo in rodent models infected with Trypanosoma brucei brucei and T. brucei rhodesiense and showed pronounced activity and in two cases were curative without overt signs of toxicity. Compounds were also tested against other trypanosomatid pathogens, Leishmania donovani and Trypanosoma cruzi, and significant activity in vitro was noted for T. cruzi against which various nitro heterocycles are already registered for use.
- Baliani, Alessandro,Bueno, Gorka Jimenez,Stewart, Mhairi L.,Yardley, Vanessa,Brun, Reto,Barrett, Michael P.,Gilbert, Ian H.
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p. 5570 - 5579
(2007/10/03)
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- Designer ligands. Part 12.1 Synthesis and evaluation of novel palladium(II)-selective ligand systems
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Sulfur-containing, PGM-selective, diamide ligands, developed for solvent extraction applications or use in the construction of molecularly imprinted polymers (MIPs), have been shown to exhibit significant selectivity for palladium(II) over copper(II), nickel(II) and cobalt(II).
- Gxoyiya, Babalwa S.B.,Hagemann, Justin P.,Kaye, Perry T.
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p. 252 - 256
(2007/10/03)
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- Efficacious and orally bioavailable thrombin inhibitors based on a 2,5-thienylamidine at the P1 position: Discovery of N-carboxymethyl-D-diphenylalanyl-L-prolyl[(5-amidino-2- thienyl)methyllamide
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Thrombin, a crucial enzyme in the blood coagulation, has been a target for antithrombotic therapy. Orally active thrombin inhibitors would provide effective and safe prophylaxis for venous and arterial thrombosis. We conducted optimization of a highly efficacious benzamidine-based thrombin inhibitor LB30812 (3, Ki = 3 pM) to improve oral bioavailability. Of a variety of arylamidines investigated at the P1 position, 2,5-thienylamidine effectively replaced the benzamidine without compromising the thrombin inhibitory potency and oral absorption. The sulfamide and sulfonamide derivatization at the N-terminal position in general afforded highly potent thrombin inhibitors but with moderate oral absorption, while the well-absorbable N-carbamate derivatives exhibited limited metabolic stability in S9 fractions. The present work culminated in the discovery of the N-carboxymethyl- and 2,5-thienylamidine-containing compound 22 that exhibits the most favorable profiles of anticoagulant and antithrombotic activities as well as oral bioavilability (Ki = 15 pM; F = 43%, 42%, and 15% in rats, dogs, and monkeys, respectively). This compound on a gravimetric basis was shown to be more effective than a low molecular weight heparin, enoxaparin, in the venous thrombosis models of rat and rabbit. Compound 22 (LB30870) was therefore selected for further preclinical and clinical development.
- Lee, Koo,Park, Cheol Won,Jung, Won-Hyuk,Park, Hee Dong,Lee, Sun Hwa,Chung, Kyung Ha,Park, Su Kyung,Kwon, O. Hwan,Kang, Myunggyun,Park, Doo-Hee,Lee, Sang Koo,Kim, Eunice E.,Yoon, Suk Kyoon,Kim, Aeri
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p. 3612 - 3622
(2007/10/03)
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- INHIBITORS OF FARNESYL-PROTEIN TRANSFERASE
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The present invention is directed to compounds which inhibit farnesyl-protein transferase (FTase) and the farnesylation of the oncogene protein Ras. The invention is further directed to chemotherapeutic compositions containing the compounds of this invention and methods for inhibiting farnesyl-protein transferase and the farnesylation of the oncogene protein Ras.
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- Pyrethroid esters
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A compound in all possible stereoisomeric forms and mixtures thereof of the formula STR1 wherein the substituents are defined as in the specification having pesticidal properties.
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- Comparative Structure-Activity Relationships of Antifolate Triazines Inhibiting Murine Tumor Cells Sensitive and Resistant to Methotrexate
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The inhibitory effect of 108 4,6-diamino-1,2-dihydro-2,2-dimethyl-1-(substituted-phenyl)-s-triazines on murine L5178Y tumor cells, resistant and sensitive to methotrexate (MTX), has been studied.From the pI50 values, quantitative structure-activity relationships have been formulated which show that the lipophilic triazines are much more inhibitory against resistant cells than methotrexate or hydrophilic triazines.The results are compared with the behavior of other antifolate drugs that have been used in chemotherapy, as well as with eight antitumor drugs that are notantifolates.The acquired resistance of these cells toward hydrophilic antifolates may be attributed to the combined effect of an impaired active-transport system, a change in the conformation of dihydrofolate reductase in the resistant cells, and an amplified production of dihydrofolate reductase in the resistant cells.
- Selassie, Cynthia Dias,Hansch, Corwin,Khwaja, Tasneem A.,Dias, Cecilia B.,Pentecost, Stephanie
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p. 347 - 357
(2007/10/02)
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