- Nickel-Catalyzed NO Group Transfer Coupled with NOxConversion
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Nitrogen oxide (NOx) conversion is an important process for balancing the global nitrogen cycle. Distinct from the biological NOx transformation, we have devised a synthetic approach to this issue by utilizing a bifunctional metal catalyst for producing value-added products from NOx. Here, we present a novel catalysis based on a Ni pincer system, effectively converting Ni-NOx to Ni-NO via deoxygenation with CO(g). This is followed by transfer of the in situ generated nitroso group to organic substrates, which favorably occurs at the flattened Ni(I)-NO site via its nucleophilic reaction. Successful catalytic production of oximes from benzyl halides using NaNO2 is presented with a turnover number of >200 under mild conditions. In a key step of the catalysis, a nickel(I)-?NO species effectively activates alkyl halides, which is carefully evaluated by both experimental and theoretical methods. Our nickel catalyst effectively fulfills a dual purpose, namely, deoxygenating NOx anions and catalyzing C-N coupling.
- Padmanaban, Sudakar,Choi, Jonghoon,Vazquez-Lima, Hugo,Ko, Donghwi,Yoo, Dagyum,Gwak, Jinseong,Cho, Kyung-Bin,Lee, Yunho
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supporting information
p. 4585 - 4593
(2022/03/02)
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- Cyanide-Free Cyanation of Aryl Iodides with Nitromethane by Using an Amphiphilic Polymer-Supported Palladium Catalyst
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A cyanide-free aromatic cyanation was developed that uses nitromethane as a cyanide source in water with an amphiphilic polystyrene poly(ethylene glycol) resin-supported palladium catalyst and an alkyl halide (1-iodobutane). The cyanation proceeds through the palladium-catalyzed cross-coupling of an aryl halide with nitromethane, followed by transformation of the resultant (nitromethyl)arene intermediate into a nitrile by 1-iodobutane.
- Niimi, Ryoko,Suzuka, Toshimasa,Uozumi, Yasuhiro
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- Visible-light mediated stereospecific C(sp2)-H difluoroalkylation of (Z)-aldoximes
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A visible light mediated stereospecific C(sp2)-H difluoroalkylation of (Z)-aldoximes to (E)-difluoroalkylated ketoximes has been described. In this reaction, (hetero)-aromatic and aliphatic difluoroalkylated ketoximes could be obtained with the retention of the configuration of the starting aldoximes. A preliminary mechanism study showed that a difluoromethyl radicalviaan SET pathway was involved.
- Chen, Hua,Deng, Hongmei,Gong, Haiying,Hao, Jian,Li, Mingjie,Peng, Yi,Wan, Wen,Wang, Qian,Zhang, Yifang
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supporting information
p. 7867 - 7874
(2021/09/28)
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- Novel oxime derivative and application thereof in agriculture
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The present invention relates to a novel oxime derivative and application thereof in agriculture. The novel oxime derivative has a structure represented by formula (I), wherein R, R, R, R and R are each independently hydrogen, fluorine, chlorine or the like, A is shown as the specification, wherein R and R are each independently hydrogen, C1-4 alkyl group, phenyl group or the like, R is C1-4 alkoxy group or the like, and R is hydrogen or C1-4 alkyl group. The novel oxime derivative disclosed by the invention is novel in structure and simple in synthesis process, and has an excellent control effect on plant diseases, particularly cucumber downy mildew.
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Paragraph 0143-0144
(2021/04/10)
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- Visible-Light-Mediated Strategies for the Preparation of Oxime Ethers Derived from O-H Insertions of Oximes into Aryldiazoacetates
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Two visible-light-mediated O-H insertion protocols involving oximes and aryldiazoacetates leading to different products depending on the solvent employed are reported. In DCM, direct O-H insertion takes place. In THF, there is the additional incorporation of the ring-opened form of this solvent into the structure of the product. These metal-free protocols are mild and tolerant to air and moisture. The preparation of an acaricide has been developed as an example of synthetic application.
- Duarte, Marcelo,Jurberg, Igor D.,Le?o, Luiz Paulo M. O.,Saito, Felipe A.,Stivanin, Mateus L.
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supporting information
p. 17528 - 17532
(2021/12/02)
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- On the mixed oxides-supported niobium catalyst towards benzylamine oxidation
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A series of mixed oxides-supported niobium-based catalysts has been synthesized and applied towards oxidation reactions of benzylamine derivatives. Under the optimized reaction conditions, the selectivity to oxime enhanced, leading to the main product with up to 72 %. Moreover, even α-substituted benzylamines were well tolerated and led to oximes in good isolated yields. It is important to mention; four equivalents of the harmless and inexpensive hydrogen peroxide were employed as oxidizing agent. Mechanism hypothesis suggested that the reaction proceed to selective benzylamine oxidation into nitroso intermediate, following by formation of the corresponding oxime tautomer mediated by an unstable water produced by NbOx supported catalyst. This consists the first mixed oxides-supported niobium-based catalyst for selective oxidation of benzylamines to oximes.
- Granato, álisson Silva,de Carvalho, Gustavo S. Gon?alves,Fonseca, Carla G.,Adrio, Javier,Leit?o, Alexandre A.,Amarante, Giovanni Wilson
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p. 118 - 125
(2020/09/11)
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- Synthesis and Biological Activity of 2-(2-Amino-2-phenylethyl)-5-oxotetrahydrofuran-2-carboxylic Acid: A Microwave-Assisted 1,3-Dipolar Cycloaddition Approach
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The microwave-assisted 1,3-dipolar cycloaddition of furanyl and benzyl oximes and several methyl acrylates effectively provided several isoxazoline when mediated by diacetoxyiodobenzene. The selected isoxazoline, methyl-5-(3-methoxy-3-oxopropyl)-3-phenyl-4,5-dihydro isoxazole-5-carboxylate, was rapidly transformed to the γ-lactone carboxylic acid, 2-(2-amino-2-phenylethyl)-5-oxotetrahydrofuran-2-carboxylic acid, in reasonable yield. The biological activity of this γ-lactone carboxylic acid increased the growth of E. coli organisms by about 44% and has a potential significance in stem cell research.
- Urquilla, Andromeda,Merrer, Dina C.,Sumner, Ryan,Denton, Richard W.
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supporting information
p. 1735 - 1740
(2021/08/27)
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- Design, synthesis, and biological evaluation of N-(4-substituted)-3-phenylisoxazolo[5,4–d]pyrimidin-4-amine derivatives as apoptosis-inducing cytotoxic agents
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A library of new 3-phenylisoxazolo[5,4–d]pyrimidines (8–10) was designed based on a scaffold hybridization technique incorporating the important pharmacophoric features of 4-aminopyrimidine and phenyl isoxazole scaffold which is renowned for its BET inhib
- Bansod, Sapana,Gaikwad, Nikhil Baliram,Garise, Ramana,Godugu, Chandraiah,Mara, Alekhya,Srinivas, Nanduri,Yaddanapudi, Venkata Madhavi
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supporting information
(2021/08/05)
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- Poly(N-vinylimidazole): A biocompatible and biodegradable functional polymer, metal-free, and highly recyclable heterogeneous catalyst for the mechanochemical synthesis of oximes
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The catalytic activity of poly(N-vinylimidazole), a biocompatible and biodegradable synthetic functional polymer, was investigated for the synthesis of oximes as an efficient, halogen-free, and reusable heterogeneous catalyst. The corresponding oximes were afforded in high to excellent yields at room temperature and in short times using the planetary ball mill technique. Some merits, such as the short reaction times and good yields for poorly active carbonyl compounds, and avoiding toxic, expensive, metal-containing catalysts, and hazardous and flammable solvents, can be mentioned for the current catalytic synthesis of the oximes. Furthermore, the heterogeneous organocatalyst could be easily separated after the reaction, and the regenerated catalyst was reused several times with no significant loss of its catalytic activity.
- Fahim, Hoda,Ghaffari Khaligh, Nader,Gorjian, Hayedeh
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p. 2007 - 2012
(2022/01/08)
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- Design, synthesis and biological evaluation of novel indanone containing spiroisoxazoline derivatives with selective COX-2 inhibition as anticancer agents
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Objective: A new family of 3′-(Mono, di or tri-substituted phenyl)-4′-(4-(methylsulfonyl) phenyl) spiroisoxazoline derivatives containing indanone spirobridge was designed, synthesized, and evaluated for their selective COX-2 inhibitory potency and cytotoxicity on different cell lines. Methods: A synthetic reaction based on 1,3-dipolar cycloaddition mechanism was applied for the regiospecific formation of various spiroisoxazolines. The activity of the newly synthesized compounds was determined using in vitro cyclooxygenase inhibition assay. The toxicity of the compounds was evaluated by MTT assay. In addition, induction of apoptosis, and expression levels of Bax, Bcl-2 and caspase-3 mRNA in MCF-7 cells were evaluated following exposure to compound 9f. The docking calculations and molecular dynamics simulation were performed to study the most probable modes of interactions of compound 9f upon binding to COX-2 enzyme. Results: The docking results showed that the synthesized compounds were able to form hydrogen bonds with COX-2 involving methyl sulfonyl, spiroisoxazoline, meta-methoxy and fluoro functional groups. Spiroisoxazoline derivatives containing methoxy group at the C-3′ phenyl ring meta position (9f and 9g) showed superior selectivity with higher potency of inhibiting COX-2 enzyme. Furthermore, compound 9f, which possesses 3,4-dimethoxyphenyl on C-3′ carbon atom of isoxazoline ring, exhibited the highest COX-2 inhibitory activity, and also displayed the most potent cytotoxicity on MCF-7 cells with an IC50 value of 0.03 ± 0.01 μM, comparable with that of doxorubicin (IC50 of 0.062 ± 0.012 μM). The results indicated that compound 9f could promote apoptosis. Also, compared to the control group, the mRNA expression of Bax and caspase-3 significantly increased, while that of Bcl-2 significantly decreased upon exposure to compound 9f which may propose the activation of mitochondrial-associated pathway as the mechanism of observed apoptosis. Conclusion: In vitro biological evaluations accompanied with in silico studies revealed that indanone tricyclic spiroisoxazoline derivatives are good candidates for the development of new anti-inflammatory and anticancer (colorectal and breast) agents.
- Abolhasani, Hoda,Zarghi, Afshin,Komeili Movahhed, Tahereh,Abolhasani, Ahmad,Daraei, Bahram,Dastmalchi, Siavoush
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- SO2F2-mediated oxidation of primary and tertiary amines with 30% aqueous H2O2 solution
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A highly efficient and selective oxidation of primary and tertiary amines employing SO2F2/H2O2/base system was described. Anilines were converted to the corresponding azoxybenzenes, while primary benzylamines were transformed into nitriles and secondary benzylamines were rearranged to amides. For tertiary amine substrates quinolines, isoquinolines and pyridines, their oxidation products were the corresponding N-oxides. The reaction conditions are very mild and just involve SO2F2, amines, 30% aqueous H2O2 solution, and inorganic base at room temperature. One unique advantage is that this oxidation system is just composed of inexpensive inorganic compounds without the use of any metal and organic compounds.
- Liao, Xudong,Zhou, Yi,Ai, Chengmei,Ye, Cuijiao,Chen, Guanghui,Yan, Zhaohua,Lin, Sen
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supporting information
(2021/11/01)
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- Synergistic Nanostructured MnOx/TiO2 Catalyst for Highly Selective Synthesis of Aromatic Imines
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This work reports the development of a synergistic nanostructured MnOx/TiO2 catalyst, with highly dispersed MnOx nanoparticles (4.5±1 nm) on shape-controlled TiO2 nanotubes (8–11 nm width and 120–280 nm length), for selective synthesis of valuable aromatic imines at industrially important conditions. Pristine TiO2 nanotubes exhibited 97 % imine selectivity at a 38.3 % benzylamine conversion, whereas very low imine selectivity was obtained over commercial TiO2 materials, indicating the catalytic significance of shape-controlled TiO2 nanotubes. The MnOx nanoparticle/TiO2 nanotube (10 wt% Mn) catalyst calcined at 400 °C showed the best activity with 95.6 % benzylamine conversion and 99.9 % imine selectivity. This catalyst exhibited good recyclability for four times and is effective for converting numerous benzylamines into higher yields of imines. The high catalytic performance of MnOx/TiO2 nanotubes was attributed to higher number of redox sites (Mn3+), high dispersion of Mn species, and shape-controlled structure of TiO2, indicating that this catalyst could be a promising candidate for selective oxidation reactions.
- Sudarsanam, Putla,K?ckritz, Angela,Atia, Hanan,Amin, Mohamad Hassan,Brückner, Angelika
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p. 1990 - 1997
(2021/02/27)
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- Dioxido-vanadium(V) complex catalyzed oxidation of alcohols and tandem synthesis of oximes: a simple catalytic protocol for C–N bond formation
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We report the synthesis of a vanadium(V) complex characterized by FT-IR and 1H NMR spectroscopy. The structure of the complex was established by single crystal X-ray crystallography. We also carried out the catalytic oxidation of benzyl alcohol, hetero-aryl alcohols and propargylic alcohols. Tandem synthesis of oximes from alcohols were also carried out using our vanadium(V) complex. The newly synthesized complex acts as a catalyst for oxidation reactions and tandem synthesis of oxime from alcohols.
- Kurbah, Sunshine Dominic
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p. 905 - 918
(2021/02/03)
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- Selective Carbon-Carbon Bond Amination with Redox-Active Aminating Reagents: A Direct Approach to Anilines?
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Amines are among the most fundamental motifs in chemical synthesis, and the introduction of amine building blocks via selective C—C bond cleavage allows the construction of nitrogen compounds from simple hydrocarbons through direct skeleton modification. Herein, we report a novel method for the preparation of anilines from alkylarenes via Schmidt-type rearrangement using redox-active amination reagents, which are easily prepared from hydroxylamine. Primary amines and secondary amines were prepared from corresponding alkylarenes or benzyl alcohols under mild conditions. Good compatibility and valuable applications of the transformation were also displayed.
- Qiu, Xu,Wang, Yachong,Su, Lingyu,Jin, Rui,Song, Song,Qin, Qixue,Li, Junhua,Zong, Baoning,Jiao, Ning
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supporting information
p. 3011 - 3016
(2021/09/13)
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- Visible-Light-Induced Photoaddition of N-Nitrosoalkylamines to Alkenes: One-Pot Tandem Approach to 1,2-Diamination of Alkenes from Secondary Amines
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The generation of aminium radical cation species from N-nitrosoamines is disclosed for the first time through visible-light excitation at 453 nm. The developed visible-light-promoted photoaddition reaction of N-nitrosoamines to alkenes was combined with the o-NQ-catalyzed aerobic oxidation protocol of amines to telescope the direct handling of harmful N-nitroso compounds, where the desired α-amino oxime derivatives were obtained in a one-pot tandem N-nitrosation and photoaddition sequence.
- Patil, Dilip V.,Si, Tengda,Kim, Hun Young,Oh, Kyungsoo
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supporting information
p. 3105 - 3109
(2021/05/05)
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- Identification of morpholine based hydroxylamine analogues: Selective inhibitors of MARK4/Par-1d causing cancer cell death through apoptosis
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Microtubule affinity-regulating kinase 4 (MARK4) is a serine/threonine kinase involved in the phosphorylation of MAP proteins that regulates microtubule dynamics and abets tumor progression by participating in oncogenic signaling pathways. It is overexpressed in multiple human malignancies and no drug is available for this potential therapeutic target at present. Therefore, using the structure based drug design strategy, a library of hydroxylamine derivatives of morpholine were designed and synthesized as small molecule inhibitors of MARK4. Compound 32 having the CF3 group at the ortho position of the phenyl ring tethered with the >CNOH core and the hinge binder morpholine component was found to be a potent and selective inhibitor of MARK4 over thirty other serine-threonine kinases. Study of cell viability and compound induced morphological changes in MCF-7 cancer cells discovered that molecule 32 caused death of cancerous cells through the mechanism of apoptosis. Compound 32 may be transported and delivered to the target site through the blood stream, and has promising antioxidant potential. Such bio-active molecules could serve as optimized lead candidates in drug discovery for cancer treatment through MARK4 inhibition.
- Avecilla, Fernando,Azam, Amir,Gaur, Aysha,Hassan, Md. Imtaiyaz,Khan, Nashrah Sharif,Khan, Parvez,Peerzada, Mudasir Nabi
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supporting information
p. 16626 - 16637
(2020/10/14)
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- Acetic Anhydride-Acetic Acid as a New Dehydrating Agent of Aldoximes for the Preparation of Nitriles: Preparation of 2-Cyanoglycals
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Glycals, 1,2-unsatrated carbohydrates, are versatile building blocks for the synthesis of various scaffolds. Despite their potential to serve as suitable precursors in diversity-oriented synthesis, 2-cyanoglycals are less explored in terms of their synthesis and derivatization. Herein, we report a combination of Ac 2 O and AcOH as new and efficient dehydrating agent of aldoximes for the synthesis of 2-cyanoglycals. In comparison to the conventional dehydrating system of Ac 2 O-base (such as NaOH, NaOAc and K 2 CO 3), the current protocol provides superior yields and faster reaction rates. The scope and limitations of the dehydrating system are investigated.
- Kinfe, Henok H.,Mabasa, Jackie,Mabasa, Tommy F.,Makhubela, Banothile C. E.,Simelane, Mthokozisi,Vatsha, Banele
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supporting information
p. 991 - 996
(2020/06/10)
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- Annulation of Oxime-Ether Tethered Donor–Acceptor Cyclopropanes
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Novel oxime-ether tethered cyclopropanes, when exposed to Yb(OTf)3 and heat, annulate to generate hydropyrrolo-oxazines products that can be taken to their respective pyrrolidines via hydrogenative N?O bond cleavage. The hydropyrrolo-oxazines are generated in a diastereoselective manner isolating the cis or trans product based on the temperature of the reaction. 20 examples of selective cis and trans hydropyrrolo-oxazines were generated in high yields by temperature control.
- Irwin, Lauren C.,Allen, Meredith A.,Vriesen, Matthew R.,Kerr, Michael A.
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supporting information
p. 171 - 175
(2019/12/24)
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- Site-specific catalytic activities to facilitate solvent-free aerobic oxidation of cyclohexylamine to cyclohexanone oxime over highly efficient Nb-modified SBA-15 catalysts
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The development of highly active and selective heterogeneous catalysts for efficient oxidation of cyclohexylamine to cyclohexanone oxime is a challenge associated with the highly sensitive nitrogen center of cyclohexylamine. In this work, dispersed Nb oxide supported on SBA-15 catalysts are disclosed to efficiently catalyze the selective oxidation of cyclohexylamine with high conversion (>75%) and selectivity (>84%) to cyclohexanone oxime by O2without any addition of solvent (TOF = 469.8 h?1, based on the molar amount of Nb sites). The role of the active-site structure identity in dictating the site-specific catalytic activities is probed with the help of different reaction and control conditions and multiple spectroscopy methods. Complementary to the experimental results, further poisoning tests (with KSCN or dehydroxylation reagents) and DFT computational studies clearly unveil that the surface exposed active centers toward activation of the reactants are quite different: the surface -OH groups can catch the NH2group from cyclohexylamine by forming a hydrogen bond and lead to a more facile cyclohexylamine oxidation to desired products, while the monomeric or oligomeric Nb sites with a highly distorted structure play a key role in the dissociation of O2molecules beneficial for insertion of active oxygen species into cyclohexylamine. These catalysts exhibit not only satisfactory recyclability for cyclohexylamine oxidation but also efficiently catalyze the aerobic oxidation of a wide range of amines under solvent-free conditions.
- Ding, Wei,Mao, Liqiu,Peng, Haoyu,Yin, Dulin,Zhong, Wenzhou
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p. 3409 - 3422
(2020/06/09)
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- Adhesive functionalized ascorbic acid on CoFe2O4: A core-shell nanomagnetic heterostructure for the synthesis of aldoximes and amines
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This paper reports on the simple synthesis of novel green magnetic nanoparticles (MNPs) with effective catalytic properties and reusability. These heterogeneous nanocatalysts were prepared by the anchoring of Co and V on the surface of CoFe2O4 nanoparticles coated with ascorbic acid (AA) as a green linker. The prepared nanocatalysts have been identified by scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray atomic mapping, thermogravimetric analysis, X-ray powder diffraction, vibrating sample magnetometer analysis, coupled plasma optical emission spectrometry and Fourier transform infrared spectroscopy. The impact of CoFe2O4@AA-M (Co, V) was carefully examined for NH2OH·HCl oximation of aldehyde derivatives first and then for the reduction of diverse nitro compounds with sodium borohydride (NaBH4) to the corresponding amines under green conditions. The catalytic efficiency of magnetic CoFe2O4@AA-M (Co, V) nanocatalysts was investigated in production of different aldoximes and amines with high turnover numbers (TON) and turnover frequencies (TOF) through oximation and reduction reactions respectively. Furthermore, the developed environment-friendly method offers a number of advantages such as high turnover frequency, mild reaction conditions, high activity, simple procedure, low cost and easy isolation of the products from the reaction mixture by an external magnetic field and the catalyst can be reused for several consecutive runs without any remarkable decrease in catalytic efficiency.
- Sorkhabi, Serve,Ghadermazi, Mohammad,Mozafari, Roya
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p. 41336 - 41352
(2020/11/30)
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- Design and Structural Optimization of Dual FXR/PPARδActivators
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Nonalcoholic steatohepatitis (NASH) is considered as severe hepatic manifestation of the metabolic syndrome and has alarming global prevalence. The ligand-activated transcription factors farnesoid X receptor (FXR) and peroxisome proliferator-activated receptor (PPAR) δhave been validated as molecular targets to counter NASH. To achieve robust therapeutic efficacy in this multifactorial pathology, combined peripheral PPAR?-mediated activity and hepatic effects of FXR activation appear as a promising multitarget approach. We have designed a minimal dual FXR/PPARδactivator scaffold by rational fusion of pharmacophores derived from selective agonists. Our dual agonist lead compound exhibited weak agonism on FXR and PPARδand was structurally refined to a potent and balanced FXR/PPARδactivator in a computer-aided fashion. The resulting dual FXR/PPARδmodulator comprises high selectivity over related nuclear receptors and activates the two target transcription factors in native cellular settings.
- Schierle, Simone,Neumann, Sebastian,Heitel, Pascal,Willems, Sabine,Kaiser, Astrid,Pollinger, Julius,Merk, Daniel
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supporting information
p. 8369 - 8379
(2020/08/12)
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- Microwave synthesis method of benzaldoxime compounds
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The invention discloses a microwave synthesis method of benzaldoxime compounds. The method comprises the following steps: dissolving a substituted benzaldehyde, hydroxylamine hydrochloride and an alkaline compound in an organic solvent, placing the formed solution in a microwave reaction kettle for a reaction, spin-drying the solvent after the reaction is finished, conducting mixed extraction withethyl acetate and water, separating an organic phase, carrying out drying with anhydrous sodium sulfate, and successively performing filtering and desolventizing to obtain a benzaldoxime compound. Based on the structure of the substituted benzaldehyde, the substituted benzaldoxime compound is obtained by reacting the aldehyde with hydroxylamine hydrochloride in the microwave reaction kettle. Themethod is simple in process, convenient to operate, short in reaction time and high in yield, meets the requirement for environment friendliness and improves economic benefits.
- -
-
Paragraph 0023-0026
(2020/12/08)
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- A Synergic Activity of Urea/Butyl Imidazolium Ionic Liquid Supported on UiO-66-NH2 Metal–Organic Framework for Synthesis of Oximes
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An efficient supported ionic liquid catalyst is designed for condensation reaction of aldehydes and ketones. The Zr-based metal–organic framework (MOF), UiO-66-NH2, was initially functionalized with N,N′-dibutyl imidazolium ionic liquid (UiO-66-NH2-ILBr–), and then urea was attached to the ionic liquid (IL) to form a task-specific IL. Bromide was exchanged with tetrafluoroborate and the catalyst exhibits excellent performance for the synthesis of oximes. The ionic liquid/urea coupling showed a synergistic effect on the efficiency of the reaction. The supported catalyst system was recycled simply by filtration and reused for five times without significant decrease in its activity. The catalyst was characterized with PXRD, FTIR, TGA, XPS, BET, FE-SEM, EDS, elemental mapping and elemental analysis (CHN). Graphic Abstract: MOF/IL/urea catalytic system was used for the synthesis of oximes[Figure not available: see fulltext.].
- Askari, Saeed,Jafarzadeh, Mohammad,Christensen, David Benjamin,Kegn?s, S?ren
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p. 3159 - 3173
(2020/04/21)
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- Potassium Poly(Heptazine Imide): Transition Metal-Free Solid-State Triplet Sensitizer in Cascade Energy Transfer and [3+2]-cycloadditions
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Polymeric carbon nitride materials have been used in numerous light-to-energy conversion applications ranging from photocatalysis to optoelectronics. For a new application and modelling, we first refined the crystal structure of potassium poly(heptazine imide) (K-PHI)—a benchmark carbon nitride material in photocatalysis—by means of X-ray powder diffraction and transmission electron microscopy. Using the crystal structure of K-PHI, periodic DFT calculations were performed to calculate the density-of-states (DOS) and localize intra band states (IBS). IBS were found to be responsible for the enhanced K-PHI absorption in the near IR region, to serve as electron traps, and to be useful in energy transfer reactions. Once excited with visible light, carbon nitrides, in addition to the direct recombination, can also undergo singlet–triplet intersystem crossing. We utilized the K-PHI centered triplet excited states to trigger a cascade of energy transfer reactions and, in turn, to sensitize, for example, singlet oxygen (1O2) as a starting point to synthesis up to 25 different N-rich heterocycles.
- Antonietti, Markus,Guldi, Dirk M.,Hussain, Tanveer,Karton, Amir,Markushyna, Yevheniia,Mazzanti, Stefano,Oschatz, Martin,Sánchez Vadillo, José Manuel,Savateev, Aleksandr,Strauss, Volker,Tarakina, Nadezda V.,Tyutyunnik, Alexander P.,Walczak, Ralf,ten Brummelhuis, Katharina
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supporting information
p. 15061 - 15068
(2020/06/17)
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- 1,3-Dipolar Cycloaddition, HPLC Enantioseparation, and Docking Studies of Saccharin/Isoxazole and Saccharin/Isoxazoline Derivatives as Selective Carbonic Anhydrase IX and XII Inhibitors
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Two series of saccharin/isoxazole and saccharin/isoxazoline hybrids were synthesized by 1,3-dipolar cycloaddition. The new compounds showed to be endowed with potent and selective inhibitory activity against the cancer-related human carbonic anhydrase (hCA) IX and XII isoforms in the nanomolar range, while no affinity was encountered for off-targets, such as hCA I and II. Successive enantioseparation on a milligram scale of the most representative compounds led to the discovery that (S)-isomers were more potent than their corresponding (R)-enantiomers. Lastly, molecular modeling studies were conducted to define those structural requirements that were responsible for the discrimination among selected human isoforms of carbonic anhydrases. Two nanomolar hCA IX and XII inhibitors were also screened for their selective toxicity against non tumoral primary cells (fibroblasts) and against a breast adenocarcinoma cell line (MCF7) in hypoxic environment. The efficacious combination of these compounds with doxorubicin on MCF7 cells was demonstrated after 72 h of treatment.
- D'Ascenzio, Melissa,Secci, Daniela,Carradori, Simone,Zara, Susi,Guglielmi, Paolo,Cirilli, Roberto,Pierini, Marco,Poli, Giulio,Tuccinardi, Tiziano,Angeli, Andrea,Supuran, Claudiu T.
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p. 2470 - 2488
(2020/03/31)
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- Nickel-Catalyzed Transformation of Alkene-Tethered Oxime Ethers to Nitriles by a Traceless Directing Group Strategy
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Nickel-catalyzed transformation of alkene-tethered oxime ethers to nitriles using a traceless directing group strategy has been developed. A series of alkene-tethered oxime ethers derived from benzaldehyde and cinnamyl aldehyde derivatives were converted into the corresponding benzonitriles and cinnamonitriles in 46-98% yields using the nickel catalyst system. Control experiments showed that the alkene group tethered to an oxygen atom on the oximes via one methylene unit plays a key role as a traceless directing group during the catalysis.
- Takahashi, Yoshiyuki,Tsuji, Hiroaki,Kawatsura, Motoi
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p. 2654 - 2665
(2020/02/04)
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- Synthesis and SAR study of simple aryl oximes and nitrofuranyl derivatives with potent activity against Mycobacterium tuberculosis
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Background: Oximes and nitrofuranyl derivatives are particularly important compounds in medicinal chemistry. Thus, many researchers have been reported to possess antibacterial, antiparasitic, insecticidal and fungicidal activities. Methods: In this work, we report the synthesis and the biological activity against Mycobacterium tuberculosis H37RV of a series of fifty aryl oximes, ArCH=N-OH, I, and eight nitrofuranyl compounds, 2-nitrofuranyl-X, II. Results: Among the oximes, I: Ar = 2-OH-4-OH, 42, and I: Ar = 5-nitrofuranyl, 46, possessed the best activity at 3.74 and 32.0 μM, respectively. Also, 46, the nitrofuran compounds, II; X = MeO, 55, and II: X = NHCH2Ph, 58, (14.6 and 12.6 μM, respectively), exhibited excellent biological activities and were non-cytotoxic. Conclusion: The compound 55 showed a selectivity index of 9.85. Further antibacterial tests were performed with compound 55 which was inactive against Enterococcus faecalis, Klebisiella pneumonae, Pseudomonas aeruginosa, Staphylococcus aureus, Salmonella typhymurium and Shigel-la flexneri. This study adds important information to the rational design of new lead anti-TB drugs. Structure-activity Relationship (SAR) is reported.
- Calixto, Stephane Lima,Carvalho, Guilherme da Silva Louren?o,Coimbra, Elaine Soares,Granato, Juliana da Trindade,Louren?o, Maria Cristina da Silva,Wardell, James,da Costa, Cristiane Fran?a,de Souza, Marcus Vinicius Nora
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- Photochemical Flow Oximation of Alkanes
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The nitrosation of several alkanes using tert-butyl nitrite has been performed in flow showing a remarkable reduction in the reaction time compared with batch processing. Due to the necessity for large excesses of the alkane component a continuous recycling process was devised for the preparation of larger quantities of material.
- Griffiths, Oliver M.,Ruggeri, Michele,Baxendale, Ian R.
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supporting information
p. 1907 - 1912
(2020/10/06)
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- Uncommon overoxidative catalytic activity in a new halo-tolerant alcohol dehydrogenase
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Alcohol dehydrogenases (ADH) are versatile and useful enzymes employed as biocatalysts, especially for the selective oxidation of primary and secondary alcohols, and for the reduction of carbonyl moieties. A new alcohol dehydrogenase (HeADH-II) has been identified from the genome of the halo-adapted bacterium Halomonas elongata, which proved stable in the presence of polar organic solvents and salt exposure. Unusual for this class of enzymes, HeADH-II lacks enantiopreference and is capable of oxidizing both alcohols and aldehydes, enabling a direct overoxidation of primary alcohols to carboxylic acids. HeADH-II was coupled with a NADH-oxidase from Lactobacillus pentosus (LpNOX) to increase the process yields and allowing recycling of the cofactor. The enzymatic oxidation of primary alcohols was also paired with in situ condensation of the intermediate aldehydes with hydroxylamine to prepare the corresponding aldoximes, with particular attention to perillartine (a powerful sweetener), whose enzymatic synthesis starting from natural sources, leads to an equally natural product.
- Contente, Martina L.,Fiore, Noemi,Cannazza, Pietro,Roura Padrosa, David,Molinari, Francesco,Gourlay, Louise,Paradisi, Francesca
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supporting information
p. 5679 - 5685
(2020/09/17)
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- Iron-Promoted Decarboxylation of Arylacetic Acids for the Synthesis of Aromatic Nitriles with Sodium Nitrite as the Nitrogen Source
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A new and effective method was developed for the synthesis of aromatic nitriles from arylacetic acids by using NaNO 2as the nitrogen source and Fe(OTf) 3as the promoter at 50 °C. A series of arylacetic acids underwent this transformation to give the targeted products in yields of 51-90%. Because of the mild conditions, the reaction is compatible with a broad range of functional groups, including ester, carboxy, hydroxy, acetamido, halo, nitro, cyano, methoxy, and even highly reactive formyl groups.
- Shen, Zhenpeng,Liu, Wenbo,Tian, Xinzhe,Zhao, Zhe,Ren, Yun-Lai
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supporting information
p. 1805 - 1808
(2020/11/02)
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- BICYCLIC KETONE COMPOUNDS AND METHODS OF USE THEREOF
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The invention provides novel compounds having the general formula (I): (I) wherein R1, the A ring and the B ring are as described herein, pharmaceutical compositions including the compounds, and methods of using the compounds.
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Page/Page column 48; 49; 93; 94
(2019/02/02)
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- Cp?-Free Cobalt-Catalyzed C-H Activation/Annulations by Traceless N, O-Bidentate Directing Group: Access to Isoquinolines
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N,O-Bidentate directing-enabled, traceless heterocycle synthesis is described via Cp?-free cobalt-catalyzed C-H activation/annulation. The weakly coordinating nature of the carboxylic acid was employed for the preparation of isoquinolines. Meanwhile, the N-O bond of the α-imino-oxy acid can serve as an internal oxidant. Terminal as well as internal alkynes can be efficiently applied to the catalytic system. This operationally simple approach shows a broad substrate scope with the products obtained in good to excellent yields.
- Li, Xiao-Cai,Du, Cong,Zhang, He,Niu, Jun-Long,Song, Mao-Ping
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supporting information
p. 2863 - 2866
(2019/04/17)
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- The Bioorthogonal Isonitrile-Chlorooxime Ligation
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Bioorthogonal reactions are valuable tools for the selective labeling and imaging of natural products and proteins. Here, we present the reaction between isonitriles and chlorooximes as a ligation that proceeds quickly (k ≈ 1 M-1 s-1
- Li, Mao,Monaco, Mattia R.,Rivera-Fuentes, Pablo,Sch?fer, Rebecca J. B.,Tirla, Alina,Wennemers, Helma
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supporting information
p. 18644 - 18648
(2019/11/28)
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- Quinazoline derivatives preparation method and use thereof
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The invention discloses a quinazoline derivative shown in formula (I) which is described in the specification and a salt thereof. In the formula, Z represents -NH- and -O-, R1 and R2 represent C1-3 alkoxy groups or hydrogen, R3 is selected from the group consisting of 4-fluoro-, 4-chloro-, 2-chloro-, 4-bromo-, 2, 4-dichloro-, 4-methyl, 4-methoxy, hydrogen, 4-trifluoromethyl and 2,4-dimethoxy. The invention relates to a preparation method and application of the compound shown in the formula (I) and the salt thereof. The compound or the salt thereof has strong inhibitory activity on colorectal cancer cell strains HCT-116, human lung cancer cell strains A549 and breast cancer cell strains MCF-7. The compound has wide spectrum antitumor activity and can be used as a drug or lead compound for treatment of diseases like tumors and cancers.
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Paragraph 0075; 0077-0079
(2019/04/02)
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- Synthesis method of parecoxib sodium isomeric impurities
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The invention provides a synthesis method of parecoxib sodium isomeric impurities. Structures of the parecoxib sodium isomeric impurities are shown in formulae I and II in the description. The synthesis method comprises the following steps: the compound as shown in the formula I is subjected to reaction with the compound as shown in formula II or the compound as shown in formula III under the action of alkali, and a compound as shown in formula IV is generated; the corresponding parecoxib sodium isomeric impurities are generated by reduction reaction, diazotization, sulfonylation, amino substitution reaction and acylation reaction; the total reaction yield is higher than 22%, and purity of a target product is higher than 99%.
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Paragraph 0041; 0049-0055
(2019/01/23)
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- C-N Bond Activation of N, N′-Dialkylacylhydrazines Mediated by β-Fragmentation of Nitrogen-Centered Radical
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In the presence of tert-butylnitrite and dioxygen, the C-N bond activation of N,N′-dialkylacylhydrazines was realized, providing a series of N-nitrosoacylhydrazines in high yields. Different from transition-metal and other radical catalysis, this reaction is mediated by a nitrogen-centered radical of the corresponding N,N′-dialkylacylhydrazine and further β-fragmentation, which was supported by the mechanistic study.
- Zhang, Yuxian,Zhang, Shuwei,Sun, Zheng,He, Kaixuan,Chen, Qian,Yuan, Yu,Jia, Xiaodong
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p. 14202 - 14208
(2019/10/16)
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- Fe3O4@SiO2@Im[Cl]Mn(III)-complex as a highly efficient magnetically recoverable nanocatalyst for selective oxidation of alcohol to imine and oxime
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An efficient and environmentally friendly oxidation process for the one-pot preparation of oxime, imine and carbonyl compounds through alcohol oxidation in the presence of H2O2 and/or O2 have been developed by a melamine-Mn(III) Schiff base complex supported on Fe3O4@SiO2–Cl nanoparticles, named as Fe3O4@SiO2@Im[Cl]Mn(III)-complex nanocomposite, at room temperature. Direct oxidation of alcohol to carboxylic acid was performed using the catalyst in the presence of molecular O2 at room temperature in a different approach. The oxidation products were obtained with excellent yields and high TOFs. The properties of the catalyst were characterized by Fourier transform infrared spectroscopy (FTIR), elemental analysis (C, H, N), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), dynamic light scattering (DLS), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), inductive coupled plasma (ICP), cyclic voltammetry (CV), nuclear magnetic resonance (1H & 13C NMR), vibration sample magnetometer (VSM), Brunauer– Emmett–Teller (BET) and differential pulse voltammetry (DPV) analyses. The mechanism of the oxidation processes was investigated for the both H2O2 and O2 oxidants. The role of the imidazolium moiety in the catalyst as a secondary functionality was investigated. Chemoselectivity behavior of the catalyst was studied by some combinations. The catalyst could be recycled from the reaction mixture by a simple external magnet and reused for several times without any considerable reactivity loss.
- Kazemnejadi, Milad,Alavi, Seyyedeh Ameneh,Rezazadeh, Zinat,Nasseri, Mohammad Ali,Allahresani, Ali,Esmaeilpour, Mohsen
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p. 230 - 249
(2019/03/28)
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- A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
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A new transition-metal-free one-pot cascade process for the direct conversion of alcohols to nitriles was developed without introducing an “additional carbon atom”. This protocol allows transformations of readily available, inexpensive, and abundant alcohols to highly valuable nitriles.
- Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
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p. 3190 - 3194
(2019/05/21)
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- Facile One-Pot Transformation of Primary Alcohols into 3-Aryl- and 3-Alkyl-isoxazoles and -pyrazoles
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Various primary alcohols were smoothly transformed into 3-aryl- and 3-alkylisoxazoles in good yields in one pot by successive treatment with PhI(OAc) 2 in the presence of TEMPO, NH 2 OH, and then NCS, followed by reaction with alkynes in the presence of Et 3 N. Similarly, various primary alcohols were smoothly transformed into 3-aryl- and 3-alkylpyrazoles in good yields in one pot by successive treatment with PhI(OAc) 2 in the presence of TEMPO, PhNHNH 2, and then NCS and decyl methyl sulfide, followed by reaction with alkynes in the presence of Et 3 N. Thus, both 3-aryl- and 3-alkylisoxazoles, and 3-aryl- and 3-alkylpyrazoles could be prepared from readily available primary alcohols in one pot under transition-metal-free conditions.
- Kobayashi, Eiji,Togo, Hideo
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p. 3723 - 3735
(2019/09/30)
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- Synthesis and SAR of new isoxazole-triazole bis-heterocyclic compounds as analogues of natural lignans with antiparasitic activity
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Despite the impressive scientific and technological advances of recent decades, no effective treatment is currently available for Chagas disease. Our research group has been studying the design and synthesis of analogues of natural lignans aiming to identify compounds with antiparasitic activity. This article reports the synthesis of 42 novel bis-heterocyclic derivatives and the structure-activity relationship study conducted based on results of biological assays against Trypanosoma cruzi amastigotes. Thirty-seven compounds were active, and eight of them had GI50 values lower than 100 μM (GI50 88.4–12.2 μM). A qualitative structure activity relationship study using three dimensional descriptors was carried out and showed a correlation between growth inhibitory potency and the presence of bulky hydrophobic groups located at rings A and D of the compounds. Compound 3-(3,4-dimethoxyphenyl)-5-((4-(4-pentylphenyl)-1H-1,2,3-triazol-1-yl)methyl)isoxazole (31) was the most active in the series (GI50 12.2 μM), showing, in vitro, low toxicity and potency similar to benznidazole (GI50 10.2 μM). These results suggest that this compound can be a promising scaffold for the design of new trypanocidal compounds.
- Zimmermann, Lara A.,de Moraes, Milene H.,da Rosa, Rafael,de Melo, Eduardo B.,Paula, Fávero R.,Schenkel, Eloir P.,Steindel, Mario,Bernardes, Lílian S.C.
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p. 4850 - 4862
(2018/09/11)
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- Selective and facile synthesis of α,β-unsaturated nitriles and amides with N-hydroxyphthalimide as the nitrogen source
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The direct conversion of α,β-unsaturated aldehydes to corresponding nitriles promoted by Pd(OAc)2 and phthalic acid which was hydrolyzed from N-hydroxyphthalimide (NHPI) has been disclosed. Additionally, it was found that when water was used as the solvent, α,β-unsaturated amides was obtained as the main products in good to excellent yields. It was first reported that NHPI was utilized as the nitrogen source to synthesize α,β-unsaturated nitriles and amides from aldehydes. Control experiment demonstrated that aldehydes undergo a process of oximation and dehydration to form nitriles and amides.
- Yan, Yiyan,Xu, Xiaohe,Jie, Xiaokang,Cheng, Jingya,Bai, Renren,Shuai, Qi,Xie, Yuanyuan
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p. 2793 - 2796
(2018/06/25)
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- A mild system for synthesis of aldoximes and ketoximes in the presence of N-hydroxyphthalimide in aqueous system
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An efficient method for synthesis of oximes from aldehydes or ketones with N-hydroxyphthalimide or N-hydroxysuccinimide in water has been described. It is the first time to utilize NHPI as an oximation reagent to synthesize aldoximes and ketoximes from the corresponding organic carbonyl compounds without other reagents. The reaction tolerates various functional groups and affords the corresponding oximes in 76%–98% yields. The by-product phthalic acid can be recycled from the system. In addition, this method has been successfully applied to the synthesis of the precursor of some pharmacologically active amide molecules.
- Jiang, Xiaoying,Xu, Xiaohe,Lin, Yuyan,Yan, Yiyan,Li, Pingping,Bai, Renren,Xie, Yuanyuan
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supporting information
p. 5879 - 5885
(2018/09/06)
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- Depsipeptides Featuring a Neutral P1 Are Potent Inhibitors of Kallikrein-Related Peptidase 6 with On-Target Cellular Activity
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Kallikrein-related peptidase 6 (KLK6) is a secreted serine protease that belongs to the family of tissue kallikreins (KLKs). Many KLKs are investigated as potential biomarkers for cancer as well as therapeutic drug targets for a number of pathologies. KLK6, in particular, has been implicated in neurodegenerative diseases and cancer, but target validation has been hampered by a lack of selective inhibitors. This work introduces a class of depsipeptidic KLK6 inhibitors, discovered via high-throughput screening, which were found to function as substrate mimics that transiently acylate the catalytic serine of KLK6. Detailed structure-activity relationship studies, aided by in silico modeling, uncovered strict structural requirements for potency, stability, and acyl-enzyme complex half-life. An optimized scaffold, DKFZ-251, demonstrated good selectivity for KLK6 compared to other KLKs, and on-target activity in a cellular assay. Moreover, DKFZ-633, an inhibitor-derived activity-based probe, could be used to pull down active endogenous KLK6.
- De Vita, Elena,Schüler, Peter,Lovell, Scott,Lohbeck, Jasmin,Kullmann, Sven,Rabinovich, Eitan,Sananes, Amiram,He?ling, Bernd,Hamon, Veronique,Papo, Niv,Hess, Jochen,Tate, Edward W.,Gunkel, Nikolas,Miller, Aubry K.
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supporting information
p. 8859 - 8874
(2018/10/09)
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- INHIBITORS OF RIP1 KINASE AND METHODS OF USE THEREOF
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The invention provides novel compounds having RIP1 kinase inhibitory activity, pharmaceutical compositions including the compounds and methods of using the compounds.
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Paragraph 0518; 0519
(2018/07/04)
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- BICYCLIC AMIDE COMPOUNDS AND METHODS OF USE THEREOF
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The invention provides novel compounds having the general formula I: wherein R1, R2, the A ring and the B ring are as described herein, pharmaceutical compositions including the compounds and methods of using the compounds.
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Paragraph 0178-0179
(2018/06/15)
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- Indazole compounds and application thereof to preparation of IDO inhibitors
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The invention discloses indazole compounds as shown in a formula (i) or (II) which is described in the specification, and a preparation method thereof, and application of the compounds as IDO inhibitors. The compounds provided by the invention can be used for preventing and/or treating a plurality of diseases, such as Alzheimer's disease, cataract, infections related to cellular immune activation,autoimmune diseases, AIDS, cancers, depression, the metabolic disorder of tryptophan or the like.
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Paragraph 0210; 0212; 0213; 0214
(2018/11/04)
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- ISOXAZOLYL-CARBONYLOXY AZABICYCLO[3.2.1]OCTANYL COMPOUNDS AS FXR ACTIVATORS
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The disclosure relates to activators of FXR useful in the treatment of autoimmune disorders, liver disease, intestinal disease, kidney disease, cancer, and other diseases in which FXR plays a role, having the Formula (I): wherein L1, L2, A, B, R1, R2, R3, and R4 are described herein.
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Paragraph 00373
(2018/09/25)
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- Cycloaddition Reactions of Benzonorbornadiene and Homonorbornadiene: New Isoxazoline and Pyridazine Derivatives
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Ten new isoxazoline derivatives were synthesized from the reactions of benzonorbornadiene and homonorbornadiene derivatives with nitrile oxides formed from benzaldehyde and 4-substituted benzaldehyde. Two new pyridazine derivatives were also synthesized from the reaction of the homonorbornadiene derivatives with 3,6-di (2-pyridyl)-s-tetrazine. It was seen that all cycloaddition reactions were realized as exo selectivity. Finally, γ-Gauche effect in the isoxazoline derivatives was discussed.
- Adilo?lu, Yadigar,?ahin, Ertan,Tutar, Ahmet,Menzek, Abdullah
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supporting information
p. 1917 - 1925
(2018/07/31)
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- Facile one-pot preparation of 5-aryltetrazoles and 3-arylisoxazoles from aryl bromides
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The successive treatment of aryl bromides with n-BuLi, DMF, hydroxylamine hydrochloride, and finally diphenylphosphoryl azide provided efficiently the corresponding 5-aryltetrazoles in good to moderate yields. Similarly, the successive treatment of aryl bromides with n-BuLi, DMF, hydroxylamine hydrochloride, and finally diethyl acetylenedicarboxylate and Oxone provided efficiently the corresponding diethyl 3-arylisoxazole-4,5-dicarboxylates in good to moderate yields. Aromatic aldoximes are the key intermediates in both reactions, and 5-aryltetrazoles and 3-arylisoxazoles could be obtained from aryl bromides in one pot under transition-metal-free conditions.
- Kobayashi, Eiji,Togo, Hideo
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p. 4226 - 4235
(2018/07/06)
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- Oxidation Catalysis by an Aerobically Generated Dess–Martin Periodinane Analogue
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Hypervalent iodine(V) reagents, such as Dess–Martin periodinane (DMP) and 2-iodoxybenzoic acid (IBX), are broadly useful oxidants in chemical synthesis. Development of strategies to generate these reagents from dioxygen (O2) would immediately enable use of O2 as a terminal oxidant in a broad array of substrate oxidation reactions. Recently we disclosed the aerobic synthesis of I(III) reagents by intercepting reactive oxidants generated during aldehyde autoxidation. In this work, aerobic oxidation of iodobenzenes is coupled with disproportionation of the initially generated I(III) compounds to generate I(V) reagents. The aerobically generated I(V) reagents exhibit substrate oxidation chemistry analogous to that of DMP. The developed aerobic generation of I(V) has enabled the first application of I(V) intermediates in aerobic oxidation catalysis.
- Maity, Asim,Hyun, Sung-Min,Wortman, Alan K.,Powers, David C.
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supporting information
p. 7205 - 7209
(2018/05/29)
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