- Growth, crystalline perfection and characterization of benzophenone oxime crystal
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Single crystals of benzophenone oxime (BPO) have been grown by slow evaporation solution growth technique from ethanol at room temperature. The single crystal X-ray diffraction study reveals that the crystal belongs to monoclinic system and cell parameter
- Rajasekar,Muthu,Meenatchi,Bhagavannarayana,Mahadevan,Meenakshisundaram
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Read Online
- Three oxime ether derivatives: Synthesis, crystallographic study, electronic structure and molecular electrostatic potential calculation
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Three oxime ether derivatives, (E)-3-methoxy-4-(prop-2-ynyloxy)-benzaldehyde-O-prop-2-ynyl-oxime (C14H13NO3) (2), benzophenone-O-prop-2-ynyl-oxime (C16H13NO) (3) and (E)-2-chloro-6-methylquinoline-3-c
- Dey, Tanusri,Praveena, Koduru Sri Shanthi,Pal, Sarbani,Mukherjee, Alok Kumar
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- Scale-up of microdroplet reactions by heated ultrasonic nebulization
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Dramatically higher rates for a variety of chemical reactions have been reported in microdroplets compared with those in the liquid bulk phase. However, the scale-up of microdroplet chemical synthesis has remained a major challenge to the practical applic
- Liu, Chengyuan,Li, Jia,Chen, Hao,Zare, Richard N.
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- 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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- 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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- Beckmann rearrangement of ketoximes promoted by cyanuric chloride and dimethyl sulfoxide under a mild condition
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Synthesis of amides via Beckmann rearrangement of ketoximes promoted by cyanuric chloride (TCT)/DMSO under mild conditions has been reported. Conditions of the Beckmann rearrangement, e.g., solvents, the ratios of TCT/DMSO, and the temperature, were investigated using diphenylmethanone oxime as a substrate. The optimized conditions were adopted to afford fourteen amides with yields ranging from 20% to 99%. A plausible mechanism involving an active dimethyl alkoxysulfonium intermediate was proposed according to the mass spectrometry analysis. To our best knowledge, this is the first case of study on Beckmann rearrangement of ketoximes promoted by TCT/DMSO under a mild condition to afford amides efficiently.
- Ma, Ruonan,Chen, Xueyuan,Xiao, Zhiyin,Natarajan, Mookan,Lu, Chunxin,Jiang, Xiujuan,Zhong, Wei,Liu, Xiaoming
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supporting information
(2021/01/06)
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- Dehydrative Beckmann rearrangement and the following cascade reactions
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The Beckmann rearrangement has been predominantly studied for the synthesis of amide and lactam. By strategically using the in situ generated Appel's salt or Mitsunobu's zwitterionic adduct as the dehydrating agent, a series of Beckmann rearrangement and following cascade reactions have been developed herein. The protocol allows the conversion of various ketoximes into amide, thioamide, tetrazole and imide products in modular procedures. The generality and tolerance of functionalities of this method have been demonstrated.
- Liu, Yinghui,Wei, Yongjiao,Xie, Lan-Gui
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supporting information
(2021/11/16)
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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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- Synthesis of hydroxyethyl methyl morpholinium azide (HEM Morph)N3: A highly efficient new task specific azide-based ionic liquid and its dual application as an azide source and media for synthesis of some novel aromatic O-oxime ethers-1,2,3-triazole conjugates as a potential antihistaminic agents
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The synthesis, characterization and application of hydroxyethyl methyl morpholinium azide (HEM Morph)N3 as a new azide-based ionic liquid (ABIL) has been described. (HEM Morph)N3 is used as a source of azide and reaction media for three components ‘Click’ Huisgen cycloaddition reaction between O-propargyl oxime ether and alkyl bromide to acquire novel aromatic O-oxime ethers-1,2,3-triazole conjugates as potential antihistaminic agents in good yields. The influence of parameters like temperature, amount of IL, type of azide-based ionic liquids and its reusability is investigated. The (HEM Morph)N3 is proved to be an efficient, thermally stable, inexpensive and recyclable azide-based ionic liquid which can be easily synthesized and used as both azide's source and reaction media for ‘Click’ Huisgen cycloaddition reaction.
- Rad, Mohammad Navid Soltani,Behrouz, Somayeh,Saremi, Hossein,Mohammadtaghi-Nezhad, Javad
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- Chlorotropylium Promoted Conversions of Oximes to Amides and Nitriles
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Chlorotropylium chloride as a catalyst for the transformations of oximes, ketones, and aldehydes to their corresponding amides and nitriles in excellent yields (up to 99 %) and in short reaction times (mostly 10–15 min). Oximes were electrophilically attacked on the hydroxyl oxygen by chlorotropylium. The produced tropylium oxime ethers were the key intermediates, of which the ketoxime ether led to amide through Beckmann rearrangement, and the aldoxime ether led to nitrile by nitrogen base DBU assisted formal dehydration. This chlorotropylium activation protocol offered general, mild, and efficient avenues bifurcately from oximes to both amides and nitriles by one organocatalyst.
- Xu, Jiaxi,Gao, Yu,Li, Zhenjiang,Liu, Jingjing,Guo, Tianfo,Zhang, Lei,Wang, Haixin,Zhang, Zhihao,Guo, Kai
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p. 311 - 315
(2020/01/25)
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- Transition-Metal-Free Coupling of 1,3-Dipoles and Boronic Acids as a Sustainable Approach to C?C Bond Formation
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The need for alternative, complementary approaches to enable C?C bond formation within organic chemistry is an on-going challenge in the area. Of particular relevance are transformations that proceed in the absence of transition-metal reagents. In the current study, we report a comprehensive investigation of the coupling of nitrile imines and aryl boronic acids as an approach towards sustainable C?C bond formation. In situ generation of the highly reactive 1,3-dipole facilitates a Petasis–Mannich-type coupling via a nucleophilic boronate complex. The introduction of hydrazonyl chlorides as a complementary nitrile imine source to the 2,5-tetrazoles previously reported by our laboratory further broadens the scope of the approach. Additionally, we exemplify for the first time the extension of this protocol into another 1,3-dipole, through the synthesis of aryl ketone oximes from aryl boronic acids and nitrile N-oxides.
- Livingstone, Keith,Bertrand, Sophie,Kennedy, Alan R.,Jamieson, Craig
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p. 10591 - 10597
(2020/07/25)
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- Copper-catalyzed synthesis of oxime ethers from iminoxy radical (C[dbnd]N–O[rad]) and maleimides via radical addition
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An efficient Cu(II)-catalyzed radical addition of maleimides has been achieved. The identified copper catalyst enables the formation of oxime radicals (N–O[rad]) by cleaving the O–H bond in ketoximes, followed by the radical addition to N-substituted male
- Han, Ziwei,Shen, Subo,Zheng, Feng,Hu, Han,Zhang, Jianmin,Zhu, Shizheng
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supporting information
(2019/09/30)
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- Microdroplets as Microreactors for Fast Synthesis of Ketoximes and Amides
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The formation of amide bonds is one of the most valuable transformations in organic synthesis. Beckmann rearrangement is a well-known method for producing secondary amides from ketoximes. This study demonstrates the rapid synthesis of ketoximes and amides in microdroplets. Many factors are found to affect the yield, such as microdroplet generation devices, temperature, catalysts, and concentrations of reactants. In particular, the temperature has a great influence on the synthesis of amide, which is demonstrated by a sharp ascendance to the yield when the temperature was increased to 45 °C. The best amide yield (93.3%) can be obtained by using coaxial flowing devices, a sulfonyl chloride compound as a catalyst, and heating to 55 °C in microdroplets. The yields can reach 78.7-91.3% for benzoylaniline and 87.2-93.4% for benzophenone oximes in several seconds in microdroplets compared to 10.1-66.1% and 82.5-93.3% in several hours in the bulk phase. Apart from the dramatically decreased reaction time and enhanced reaction yields, the microdroplet synthesis is also free of severe reaction environments (anhydrous and anaerobic conditions). In addition, the synthesis in microdroplets also saves reactants and solvents and reduces the waste amounts. All of these merits indicate that the microdroplet synthesis is a high-efficiency green methodology.
- Zhang, Wenwen,Yang, Shiwei,Lin, Qiuyu,Cheng, Heyong,Liu, Jinhua
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p. 851 - 859
(2019/01/24)
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- SO2F2-Activated Efficient Beckmann Rearrangement of Ketoximes for Accessing Amides and Lactams
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A novel, mild and practical protocol for the efficient activation of the Beckmann rearrangement utilizing the readily available and economical sulfuryl fluoride (SO2F2 gas) has been developed. The substrate scope of the operationally simple methodology has been demonstrated by 37 examples with good to nearly quantitative isolated yields (over 90 % yield in most cases) in a short time, including B(OH)2, COOH, NH2, and OH substituted substrates. A tentative mechanism was proposed involving formation and elimination of key intermediate, sulfonyl ester.
- Zhang, Guofu,Zhao, Yiyong,Xuan, Lidi,Ding, Chengrong
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supporting information
p. 4911 - 4915
(2019/07/31)
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- Vilsmeier-Haack reagent mediated synthetic transformations with an immobilized iridium complex photoredox catalyst
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An immobilized iridium complex photocatalyst Ir(ppy)2(PDVB-py) was synthesized by immobilization of the iridium complex onto the nanoporous vinylpyridine-divinylbenzene copolymer (PDVB-py). Its application for the synthesis of amides, nitriles, and anhydrides was reported via reactions under the action of the visible-light-driven in situ generated Vilsmeier-Haack reagent from CBr4 in DMF. The results showed that this heterogeneous photocatalyst has extremely high activity and excellent stability to be recycled five times.
- Zhi, Peng,Xi, Zi-Wei,Wang, Dan-Yan,Wang, Wei,Liang, Xue-Zheng,Tao, Fei-Fei,Shen, Run-Pu,Shen, Yong-Miao
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supporting information
p. 709 - 717
(2019/01/10)
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- Rhodium(III)-Catalyzed Annulation of Acetophenone O-Acetyl Oximes with Allenoates through Arene C-H Activation: An Access to Isoquinolines
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Rhodium(III)-catalyzed annulation of acetophenone O-acetyl oximes with allenoates was achieved, affording isoquinolines in good to excellent yields with high regioselectivities under redox-neutral conditions. Allenoates acted as the C2 synthons in the annulation reaction. The present synthetic methodology features good functional group tolerance and avoids metal salts as the external oxidants. The proposed mechanism suggests that the reaction proceeds through arene C-H activation, allene insertion, and C-N coupling.
- Wang, Quannan,Lou, Jiang,Huang, Zilong,Yu, Zhengkun
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p. 2083 - 2092
(2019/02/19)
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- Visible Light-Promoted Beckmann Rearrangements: Separating Sequential Photochemical and Thermal Phenomena in a Continuous Flow Reactor
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The Beckmann rearrangement of oximes to amides typically requires strong acids or highly reactive, hazardous electrophiles and/or elevated temperatures to proceed. A very attractive alternative is the in situ generation of Vilsmeier–Haack reagents, by means of photoredox catalysis, as promoters for the thermal Beckmann rearrangement. Investigation of the reaction parameters for this light-induced method using a one-pot strategy has shown that the reaction is limited by the different temperatures required for each of the two sequential steps. Using a continuous flow reactor, the photochemical and thermal processes have been separated by integrating a flow photoreactor unit at low temperature for the electrophile generation with a second reactor unit, at high temperature, where the rearrangement takes place. This strategy has enabled excellent conversions and yields for a diverse set of oximes, minimizing the formation of side products obtained with the original one-pot method.
- Chen, Yuesu,Cantillo, David,Kappe, C. Oliver
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supporting information
p. 2163 - 2171
(2019/03/14)
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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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- o-Phthalic Anhydride/Zn(OTf)2 co-catalyzed Beckmann rearrangement under mild conditions
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o-Phthalic anhydride/Zn(OTf)2 co-catalyzed Beckmann rearrangement was developed, producing the corresponding amide in up to 99% yield with acid-sensitive functionalities tolerated well, and the scale of the reaction could be enlarged to 77 mmol and the excellent yield was maintained. A successive procedure was developed. Moreover, the reaction was carried out at rt under nearly neutral conditions, and the workup was concise. These features illustrated the potential of the protocol in amide synthesis.
- Xu, Ze-Feng,Zhang, Teng,Hong, Wenjun
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supporting information
p. 3113 - 3117
(2019/05/08)
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- Stereospecific synthesis of 1,5-disubstituted tetrazoles from ketoximes via a Beckmann rearrangement facilitated by diphenyl phosphorazidate
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A novel method for the stereospecific synthesis of 1,5-disubstituted tetrazoles from ketoximes via the Beckmann rearrangement was developed using diphenyl phosphorazidate (DPPA) as both the oxime activator and azide source. Various ketoximes were transformed into the corresponding 1,5-disubstituted tetrazoles with exclusive trans-group migration and no E-Z isomerization of the ketoxime. This method enables the preparation of 1,5-disubstituted tetrazoles without using toxic or explosive azidation reagents.
- Ishihara, Kotaro,Shioiri, Takayuki,Matsugi, Masato
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supporting information
p. 1295 - 1298
(2019/04/13)
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- Pt-catalyzed O-silylation of oximes by tri-substituted organosilanes
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Silylated derivatives of oximes are important intermediates in organic synthesis, and have found application in the preparation of various nitrogen containing compounds including nitriles, amines, nitrones, and hydroxylamines. An efficient method for the
- Bhatt, Shreeja V.,Bhatt, Shreya V.,Fotie, Jean
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supporting information
p. 1636 - 1639
(2019/06/04)
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- Visible-Light-Photosensitized Aryl and Alkyl Decarboxylative Functionalization Reactions
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Despite significant progress in aliphatic decarboxylation, an efficient and general protocol for radical aromatic decarboxylation has lagged far behind. Herein, we describe a general strategy for rapid access to both aryl and alkyl radicals by photosensitized decarboxylation of the corresponding carboxylic acids esters followed by their successive use in divergent carbon–heteroatom and carbon–carbon bond-forming reactions. Identification of a suitable activator for carboxylic acids is the key to bypass a competing single-electron-transfer mechanism and “switch on” an energy-transfer-mediated homolysis of unsymmetrical σ-bonds for a concerted fragmentation/decarboxylation process.
- Patra, Tuhin,Mukherjee, Satobhisha,Ma, Jiajia,Strieth-Kalthoff, Felix,Glorius, Frank
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supporting information
p. 10514 - 10520
(2019/07/12)
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- Scope and mechanism of a true organocatalytic beckmann rearrangement with a boronic acid/perfluoropinacol system under ambient conditions
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Catalytic activation of hydroxyl functionalities is of great interest for the production of pharmaceuticals and commodity chemicals. Here, 2-alkoxycarbonyl- and 2-phenoxycarbonyl-phenylboronic acid were identified as efficient catalysts for the direct and chemoselective activation of oxime N-OH bonds in the Beckmann rearrangement. This classical organic reaction provides a unique approach to prepare functionalized amide products that may be difficult to access using traditional amide coupling between carboxylic acids and amines. Using only 5 mol % of boronic acid catalyst and perfluoropinacol as an additive in a polar solvent mixture, the operationally simple protocol features mild conditions, a broad substrate scope, and a high functional group tolerance. A wide variety of diaryl, aryl-alkyl, heteroaryl-alkyl, and dialkyl oximes react under ambient conditions to afford high yields of amide products. Free alcohols, amides, carboxyesters, and many other functionalities are compatible with the reaction conditions. Investigations of the catalytic cycle revealed a novel boron-induced oxime transesterification providing an acyl oxime intermediate involved in a fully catalytic nonself-propagating Beckmann rearrangement mechanism. The acyl oxime intermediate was prepared independently and was subjected to the reaction conditions. It was found to be self-sufficient; it reacts rapidly, unimolecularly without the need for free oxime. A series of control experiments and 18O labeling studies support a true catalytic pathway involving an ionic transition structure with an active and essential role for the boronyl moiety in both steps of transesterification and rearrangement. According to 11B NMR spectroscopic studies, the additive perfluoropinacol provides a transient, electrophilic boronic ester that is thought to serve as an internal Lewis acid to activate the ortho-carboxyester and accelerate the initial, rate-limiting step of transesterification between the precatalyst and the oxime substrate.
- Mo, Xiaobin,Morgan, Timothy D. R.,Ang, Hwee Ting,Hall, Dennis G.
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supporting information
p. 5264 - 5271
(2018/04/24)
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- Direct Transformation of Arylamines to Aryl Halides via Sodium Nitrite and N-Halosuccinimide
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A one-pot universal approach for transforming arylamines to aryl halides via reaction with sodium nitrite (NaNO2) and N-halosuccinimide (NXS) in DMF at room temperature under metal- and acid-free condition is described. This new protocol that is complementary to the Sandmeyer reaction, is suggested to involve the in situ generation of nitryl halide induce nitrosylation of aryl amine to form the diazo intermediate which is halogenated to furnish the aryl halide.
- Mukhopadhyay, Sushobhan,Batra, Sanjay
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supporting information
p. 14622 - 14626
(2018/09/21)
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- Dichloroimidazolidinedione-Activated Beckmann Rearrangement of Ketoximes for Accessing Amides and Lactams
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A novel protocol for the activation of the Beckmann rearrangement utilizing the readily available and economical geminal dichloroimidazolidinediones (DCIDs) on a substoichiometric scale (10 mol %) has been developed. A unique self-propagating mechanism for the substoichiometric dichloroimidazolidinedione-activated transformation was proposed and validated. The substrate scope of the developed protocol has been demonstrated by 23 examples with good to excellent yields (mostly 90-98%) in a short time (mostly 10-30 min), including a substrate for synthesizing the monomer of nylon-12 and a complicated steroidal substrate on a preparative scale. This research not only unveils for the first time the synthetic potential of substoichiometric amounts of dichloroimidazolidinediones in promoting chemical transformation but also offers yet another important illustration of the self-propagating cycle in the context of the Beckmann rearrangement activated by a structurally novel organic promoter.
- Gao, Yu,Liu, Jingjing,Li, Zhenjiang,Guo, Tianfo,Xu, Songquan,Zhu, Hui,Wei, Fulan,Chen, Siming,Gebru, Hailemariam,Guo, Kai
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p. 2040 - 2049
(2018/02/23)
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- Preparation method of ketoxime
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The invention belongs to the technical field of ketoxime and specifically relates to a preparation method of ketoxime. The preparation method comprises the following steps: (1) sufficiently mixing ketone and hydroxylamine hydrochloride, adding absolute ethyl alcohol, and stirring till total dissolution to obtain mixed liquid 1; (2) adding imidazolyl anion functionalized ionic liquid into the mixedliquid 1, and heating till ethanol reflux, wherein reaction liquid is obtained after the reaction; (3) removing ethanol in the reaction liquid, adding deionized water and stirring to separate out solid, and performing suction filtration and washing to obtain white solid ketoxime. According to the preparation method provided by the invention, by taking the imidazolyl anion functionalized ionic liquid as a catalyst, a reaction between ketone and hydroxylamine hydrochloride can be efficiently catalyzed, and the preparation method has the advantages of mild reaction conditions, high product yieldand purity and the like.
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Paragraph 0027-0028; 0029-0031
(2018/07/30)
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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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- Beckmann rearrangement of ketoxime catalyzed by N-methyl-imidazolium hydrosulfate
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Beckmann rearrangement of ketoxime catalyzed by acidic ionic liquid-N-methyl-imidazolium hydrosulfate was studied. Rearrangement of benzophenone oxime gave the desirable product with 45% yield at 90 ?C. When co-catalyst P2O5 was added, the yield could be improved to 91%. The catalyst could be reused three cycles with the same efficiency. Finally, reactions of other ketoximes were also investigated.
- Hu, Hongyu,Cai, Xuting,Xu, Zhuying,Yan, Xiaoyang,Zhao, Shengxian
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- Fe(NO3)3·9H2O-catalyzed aerobic oxidative deoximation of ketoximes and aldoximes under mild conditions
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A mild, simple process for the effective aerobic oxidative deoximation of a wide range of ketoximes and aldoximes has been developed that utilizes Fe(NO3)3·9H2O as the single catalyst and molecular oxygen as the green oxidant. The environmentally benign protocol provides moderate to excellent yield and broad functional groups tolerance and is a valuable synthetic method for practical applications. According the relevant verification experiment, a plausible mechanism has been proposed.
- Li, Yongshu,Xu, Nizhou,Mei, Guangyao,Zhao, Yun,Zhao, Yiyong,Lyu, Jinghui,Zhang, Guofu,Ding, Chengrong
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supporting information
p. 810 - 814
(2018/08/09)
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- PRODUCTION METHOD OF KETOXIME COMPOUND
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PROBLEM TO BE SOLVED: To provide a new catalytic production method of a ketoxime that does not directly use hydroxyamine, nor require severe reaction conditions. SOLUTION: A production method of a ketoxime compound includes a step for transoximizing a ketone compound and ethyl acetohydroxamate in the presence of an organic solvent and a trifluoromethanesulfonic acid metal salt. The trifluoromethanesulfonic acid metal salt is preferably scandium (III) trifluoromethanesulfonate. The organic solvent is preferably methylene chloride, methanol, ethanol, n-propanol, or n-butanol. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0022-0024
(2017/10/11)
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- Iron-Catalyzed Synthesis of 2H-Imidazoles from Oxime Acetates and Vinyl Azides under Redox-Neutral Conditions
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A novel and versatile method for the synthesis of 2H-imidazoles via iron-catalyzed [3 + 2] annulation from readily available oxime acetates with vinyl azides has been developed. This denitrogenative process involved N-O/N-N bond cleavages and two C-N bond formations to furnish 2,4-substituted 2H-imidazoles. This protocol was performed under mild reaction conditions and needed no additives or ligands. Furthermore, this is a green reaction involving oxime acetate as internal oxidant, acetic acid, and nitrogen as byproducts.
- Zhu, Zhongzhi,Tang, Xiaodong,Li, Jianxiao,Li, Xianwei,Wu, Wanqing,Deng, Guohua,Jiang, Huanfeng
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supporting information
p. 1370 - 1373
(2017/03/23)
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- ANTIVIRAL OXIME PHOSPHORAMIDE COMPOUNDS
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Compounds of Formula I: I and their pharmaceutically acceptable salts are useful for the inhibition of HIV reverse transcriptase. The compounds may also be useful for the prophylaxis or treatment of infection by HIV and in the prophylaxis, delay in the onset or progression, and treatment of AIDS. The compounds and their salts can be employed as ingredients in pharmaceutical compositions, optionally in combination with other antiviral agents, immunomodulators, antibiotics or vaccines.
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Page/Page column 30
(2017/07/06)
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- Asymmetric Nitrone Synthesis via Ligand-Enabled Copper-Catalyzed Cope-Type Hydroamination of Cyclopropene with Oxime
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We report realization of the first enantioselective Cope-type hydroamination of oximes for asymmetric nitrone synthesis. The ligand promoted asymmetric cyclopropene "hydronitronylation" process employs a Cu-based catalytic system and readily available starting materials, operates under mild conditions and displays broad scope and exceptionally high enantio- and diastereocontrol. Preliminary mechanistic studies corroborate a CuI-catalytic profile featuring an olefin metalla-retro-Cope aminocupration process as the key C-N bond forming event. This conceptually novel reactivity enables the first example of highly enantioselective catalytic nitrone formation process and will likely spur further developments that may significantly expedite chiral nitrone synthesis.
- Li, Zhanyu,Zhao, Jinbo,Sun, Baozhen,Zhou, Tingting,Liu, Mingzhu,Liu, Shuang,Zhang, Mengru,Zhang, Qian
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supporting information
p. 11702 - 11705
(2017/09/07)
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- One-pot conversion of cyclohexanol to ?-caprolactam using a multifunctional Na2WO4-acidic ionic liquid catalytic system
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Na2WO4-acidic ionic liquid was used as a simple, ecofriendly, recyclable and efficient catalytic system for the one-pot conversion of cyclohexanol to ?-caprolactam. The effect of the structure of the ionic liquid on the catalytic activity of this system was investigated, and the results revealed that sulfonic acid-functionalized ionic liquids with HSO4?as an anion gave the best results. The highly efficient performance of this catalyst system was attributed to the phase-transfer behavior of the cation of the ionic liquid, the improved coordination of the substrate to bisperoxotungstate during the oxidation reaction, and the stabilization of the intermediate formed during the Beckmann rearrangement.
- Wang, Hefang,Jia, Liyuan,Hu, Rongbin,Gao, Meidan,Wang, Yanji
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- Ir(III)-Catalyzed Synthesis of Isoquinoline N-Oxides from Aryloxime and α-Diazocarbonyl Compounds
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An efficient Ir(III)-catalyzed C-H activation and annulations of aryloxime with α-diazocarbonyl compounds has been developed for the synthesis of substituted isoquinoline N-oxides. The reaction proceeds under mild atmospheric conditions, without any external oxidants and releases N2 and H2O as the byproducts. In addition, synthetic applications of the N-oxide products have been established by performing further functionalization. An interesting dimeric iridacyclic complex allied through a bis-silver carboxylate bridge has been isolated that efficiently catalyzed the reaction.
- Phatake, Ravindra S.,Patel, Pitambar,Ramana, Chepuri V.
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supporting information
p. 292 - 295
(2016/02/03)
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- Lewis acid-assisted N-fluorobenzenesulfonimide-based electrophilic fluorine catalysis in Beckmann rearrangement
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A microwave-assisted N-fluorobenzenesulfonimide (NFSI)/Lewis acid-catalyzed Beckmann rearrangement was developed. The remarkable promotion to the electrophilicity of NFSI by Lewis acids was illustrated utilizing a series of readily available oxime substrates. The action model between NFSI and Lewis acids was probed by control experiments and theoretical calculations.
- Xie, Fukai,Du, Chuan,Pang, Yadong,Lian, Xu,Xue, Chentao,Chen, Yanyu,Wang, Xuefei,Cheng, Maosheng,Guo, Chun,Lin, Bin,Liu, Yongxiang
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supporting information
p. 5820 - 5824
(2016/12/06)
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- Synthesis and structural analysis of halogen substituted fibril formation inhibitors of Human Transthyretin (TTR)
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Transthyretin (TTR), a β-sheet-rich tetrameric protein, in equilibrium with an unstable amyloidogenic monomeric form is responsible for extracellular deposition of amyloid fibrils, is associated with the onset of neurodegenerative diseases, such as senile
- Ciccone, Lidia,Nencetti, Susanna,Rossello, Armando,Stura, Enrico Adriano,Orlandini, Elisabetta
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- Laccase-catalysed biotransformation of collismycin derivatives. A novel enzymatic approach for the cleavage of oximes
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Analogues of the natural product collismycin bearing a carboxylic acid moiety has been efficiently synthesised from several collismycin precursors through a laccase-catalysed oxidation under mild conditions with TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl) as a mediator and aerial O2 as an oxidant in aqueous medium. The biotransformations proceeded with excellent yields (85-95%) and involved, depending on the precursor, the oxidation of a benzylic hydroxyl group or the bioconversion of an aldoxime group into carboxylic acid. Since the latter is herein reported for the first time, we explored the potential of this novel oxime cleavage with several synthetic aldo- and ketoximes. Thus, the laccase/TEMPO system proved to be an efficient and green alternative for the deprotection of both aromatic and aliphatic ketoximes into the corresponding ketones. On the other hand, the reaction with aldoximes leads to dimeric species generated by coupling reactions.
- González-Sabín, Javier,Ríos-Lombardía, Nicolás,García, Ignacio,Vior, Natalia M.,Bra?a, Alfredo F.,Méndez, Carmen,Salas, José A.,Morís, Francisco
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supporting information
p. 989 - 994
(2016/02/27)
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- Palladium-Catalyzed C-H Functionalization of Aromatic Oximes: A Strategy for the Synthesis of Isoquinolines
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An efficient strategy for synthesis of isoquinolines via Pd(II)-catalyzed cyclization reaction of oximes with vinyl azides or homocoupling of oximes is reported. Oximes could serve as a directing group and an internal oxidant in the transformation. This reaction features good functional group tolerance and provides a useful protocol for the synthesis of different kinds of isoquinolines under mild conditions. Some control experiments and 15N isotope labeling experiments were conducted for the mechanistic research. (Chemical Equation Presented).
- Zhu, Zhongzhi,Tang, Xiaodong,Li, Xianwei,Wu, Wanqing,Deng, Guohua,Jiang, Huanfeng
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p. 1401 - 1409
(2016/03/01)
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- Easy Access to 1-Amino and 1-Carbon Substituted Isoquinolines via Cobalt-Catalyzed C - H/N - O Bond Activation
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A green atom-economical method for the synthesis of highly functionalized 1-amino and 1-carbon substituted isoquinolines from the reaction of N′-hydroxybenzimidamides and aryl ketoximes, respectively, with alkynes via pentamethylcyclopentadienylcobalt(III)-catalyzed C - H/N - O bond activation is described. The external oxidant-free annulation reaction uses the =NOH moiety in N′-hydroxybenzimidamides or N-aromatic ketone oximes as the directing group and internal oxidant. This first row transition metal-catalyzed annulation serves as an efficient alternative for the synthesis of isoquinolines, as water is the only by-product and expensive noble metals such as rhodium(III), iridium(III), palladium(II), and ruthenium(II) are not required. The reaction proceeds via C - H activation, alkyne insertion, reductive elimination, and N - O activation.
- Muralirajan, Krishnamoorthy,Kuppusamy, Ramajayam,Prakash, Sekar,Cheng, Chien-Hong
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supporting information
p. 774 - 783
(2016/03/09)
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- Br?nsted acid catalyzed transoximation reaction: Synthesis of aldoximes and ketoximes without use of hydroxylamine salts
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The transoximation reaction enables the transfer of an oxime to a carbonyl compound and is catalyzed by transoximase in the pupae of the silkworm. Inspired by this bio-synthetic pathway, we achieved the transoximation of oximes to aldehydes and ketones catalyzed by a Br?nsted acid under mild conditions. Hydroxylamine salt, which necessitates a stoichiometric amount of base, was not required. NMR analysis clarified that this reaction proceeded through hydroxylamines generated by the successive hydrolysis of the oxime in situ. In addition, an environmentally benign method for catalytic transoximation was demonstrated in aqueous medium on a one hundred gram scale and the reaction filtrate containing the catalyst was recovered and reused over 10 times.
- Hyodo, Kengo,Togashi, Kosuke,Oishi, Naoki,Hasegawa, Genna,Uchida, Kingo
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supporting information
p. 5788 - 5793
(2016/11/06)
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- Enantioselective α-Alkylation of Benzylideneamino tert-Butyl Malonates by Phase-Transfer Catalysis
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A new enantioselective synthetic method for the synthesis of α,α-dialkylmalonates with a quaternary carbon center was developed via α-alkylation of prochiral malonates by phase-transfer catalysis (PTC). Asymmetric α-alkylation of benzylideneamino tert-butyl α-methylmalonates under phase-transfer catalytic conditions in the presence of (S,S)-3,4,5-trifluorophenyl-NAS bromide afforded the corresponding α,α-dialkylmalonates in high yields (up to 97%) with excellent enantioselectivities (up to 98% ee). The products were then selectively hydrolyzed to chiral malonic monoacids under basic, acidic, or catalytic hydrogenation conditions.
- Park, Cheonhyoung,Ha, Min Woo,Kim, Byungsoo,Hong, Suckchang,Kim, Doyoung,Park, Yohan,Kim, Mi-Hyun,Lee, Jae Kyun,Lee, Jeeyeon,Park, Hyeung-Geun
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supporting information
p. 2841 - 2848
(2015/09/28)
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- Oxime carbamates as potential insecticidal agents: Design, synthesis and biological evaluation
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A series of oxime carbamates derivatives were designed and synthesized as a part of our ongoing search for novel high potential agrochemicals. Their structures were confirmed by 1H NMR, 13C NMR and elemental analysis. The bioassays results indicated that some of the obtained compounds exhibited good insecticidal activity against Heliothis armigera and Plutella xylostella.
- Ke, Shaoyong,Yang, Ziwen,Shi, Liqiao,Liu, Manli,Liang, Ying,Wang, Kaimei,Long, Tong,Jiang, Aibing,Zhang, Zhigang
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p. 771 - 777
(2015/10/05)
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- Synthesis of oximes from the corresponding of organic carbonyl compounds with NH2 OH.HCl and oxalic acid
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The oximation of a variety of aldehydes and ketones was carried out with NH2 OH?HCl in the presence of oxalic acid as catalyst under reflux conditions. The reactions were performed in CH3 CN with excellent yields(90-95%) of products in appropriate times (55-90 min).
- Ghozlojeh, Negin Piri,Setamdideh, Davood
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p. 1823 - 1825
(2016/01/25)
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- A copper-mediated oxidative coupling route to 3H- and 1H-indoles from N-aryl-enamines
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A facile copper(II)-mediated C-H bond oxidation and C-C bond formation procedure has been applied to the synthesis of indole derivatives. Intramolecular oxidative coupling of 3,3-disubstituted enamines proceeded using a non-expensive and air-stable copper
- Drouhin, Pauline,Taylor, Richard J. K.
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supporting information
p. 2333 - 2336
(2015/04/22)
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- Tertiary α-diarylmethylamines derived from diarylketimines and organomagnesium reagents
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Organomagnesium reagents enable swift and versatile derivatisation of diarylimines to the corresponding α-substituted diarylmethylamines in excellent yields, through fast and clean reactions. Where it occurs, 1,2-reduction can be circumvented using readily accessible dialkylmagnesium reagents. This journal is
- Desmarchelier, Alaric,Ortiz, Pablo,Harutyunyan, Syuzanna R.
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supporting information
p. 703 - 706
(2015/01/09)
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- AIEE active perylene bisimide supported mercury nanoparticles for synthesis of amides via aldoximes/ketoximes rearrangement
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Aggregates of perylene bisimide (PBI) derivative 3 serve as reactors and stabilizers for the preparation of mercury nanoparticles (HgNPs) which exhibit excellent catalytic efficiency in the conversion of aldoximes/ketoximes into primary/secondary amides via Beckmann rearrangement. This journal is
- Kaur, Sandeep,Kumar, Manoj,Bhalla, Vandana
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supporting information
p. 4085 - 4088
(2015/03/18)
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- Ruthenium Trichloride Catalyzed Highly Efficient Deoximation of Oximes to the Carbonyl Compounds and Nitriles without Acceptors
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An acceptor-free catalysis protocol for the deoximation of ketoximes and aldoximes using RuCl3 as the catalyst has been developed. Under the optimized conditions, various oximes were converted to ketones and nitriles with excellent isolated yields. An acceptor-free catalysis protocol for the deoximation of ketoximes and aldoximes using RuCl3 as the catalyst has been developed. Under the optimized conditions, various oximes were converted to ketones and nitriles with excellent isolated yields.
- Liu, Yuxiao,Yang, Na,Chu, Changhu,Liu, Renhua
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supporting information
p. 1011 - 1014
(2015/09/28)
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- Synthesis and fungicidal activity of 2-(diphenylmethyl)-3-arylisoxazolidine-5-carboxamides
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A series of new 2-(diphenylmethyl)-3-arylisoxazolidine-5-carboxamides have been prepared from aldehydes. A key step was an uncatalyzed stereoselective and regioselective 1,3-dipolar cycloaddition reaction of N-benzylidene-N-diphenylmethyl nitrones with et
- Zelechowski, Krzysztof,Golbiewski, W. Marek,Krawczyk, Maria
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p. 1895 - 1905
(2015/10/29)
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- Cobalt(III)-Catalyzed Dehydrative [4+2] Annulation of Oxime with Alkyne by C-H and N-OH Activation
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Efficient, scalable cobalt-catalyzed redox-neutral [4+2] annulation of readily available oximes and alkyne is reported. The developed synthetic methodology is widely applicable and tolerates various functional groups including heterocycles. A stable CpCoIII neutral complex is employed as the catalyst for this redox-neutral [4+2] annulation reaction, which progresses smoothly by way of a reversible cyclometallation without any external oxidizing agent, and produces only water as the side product.
- Sen, Malay,Kalsi, Deepti,Sundararaju, Basker
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supporting information
p. 15529 - 15533
(2015/11/03)
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- APPLICATIONS OF N6-SUBSTITUTED ADENOSINE DERIVATIVE AND N6-SUBSTITUTED ADENINE DERIVATIVE TO CALMING, HYPNOSES, CONVULSION RESISTANCE, EPILEPTIC RESISTANCE, PARKINSON DISEASE RESISTANCE, AND DEMENTIA PREVENTION AND TREATMENT
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PROBLEM TO BE SOLVED: To prepare analgesics, hypnotic agents, anticonvulsant agents, antiepileptics, antiparkinson drugs, dementia prophylactics, and health care food. SOLUTION: The present invention relates to an N6-substituted adenosine derivative and an N6-substituted adenine derivative selected from the group consisting of specific compounds. The present invention also relates to a pharmaceutical composition at least comprising a therapeutically effective amount of the compounds and a pharmaceutically acceptable carrier. The invention further relates to the compounds used in preparation of analgesics, hypnotic agents, anticonvulsant agents, antiepileptics, antiparkinson drugs, dementia prophylactics, and health care food. COPYRIGHT: (C)2016,JPO&INPIT
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Paragraph 0187
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