- HCl-mediated cascade cyclocondensation of oxygenated arylacetic acids with arylaldehydes: one-pot synthesis of 1-arylisoquinolines
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In this paper, a concise, open-vessel synthesis of 1-arylisoquinolines is describedviaHCl-mediated intermolecular cyclocondensation of oxygenated arylacetic acids with arylaldehydes in the presence of NH2OH and alcoholic solvents under mild and one-pot reaction conditions. A plausible mechanism is proposed and discussed herein. In the overall reaction process, only water was generated as the byproduct. Various environmentally friendly reaction conditions are investigated for convenient transformationviathe (4C + 1C + 1N) annulation. This protocol provides a highly effective ring closureviathe formations of one carbon-carbon (C-C) bond, two carbon-nitrogen (C-N) bonds and one carbon-oxygen (C-O) bond.
- Hsueh, Nai-Chen,Chen, Shin-Mei,Lin, Chun-Yi,Chang, Meng-Yang
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p. 1047 - 1059
(2021/02/16)
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- Arylboronic Acid-Catalyzed C-Allylation of Unprotected Oximes: Total Synthesis of N-Me-Euphococcine
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O-Unprotected keto-and aldoximes are readily C-allylated with allyl diisopropyl boronate in the presence of arylboronic acid catalysts to yield highly substituted N-α-secondary and tertiary homoallylic hydroxylamines. The method was used in the total synthesis of the trace alkaloid N-Me-Euphococcine.
- Kürti, László,Kattamuri, Padmanabha V.,Siitonen, Juha H.,Yousufuddin, Muhammed
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supporting information
(2020/03/24)
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- SO2F2-Mediated one-pot cascade process for transformation of aldehydes (RCHO) to cyanamides (RNHCN)
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A simple, mild and practical cascade process for the direct conversion of aldehydes to cyanamides was developed featuring a wide substrate scope and great functional group tolerability. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable cyanamides in a pot, atom, and step-economical manner with a green nitrogen source. This protocol will serve as a robust tool for the installation of the cyanamide moiety in various complicated molecules.
- Ding, Chengrong,Ge, Shuting,Wei, Junjie,Zhang, Guofu,Zhao, Yiyong
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p. 17288 - 17292
(2020/05/18)
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- Unusual Reactivity of 4-Vinyl Isoxazoles in the Copper-Mediated Synthesis of Pyridines, Employing DMSO as a One-Carbon Surrogate
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An efficient protocol for the synthesis of nicotinate derivatives and tetrasubstituted pyridines through a copper-mediated cleavage of isoxazoles has been developed. The highlight of the work is the observation of an unusual reactivity of 4-vinyl isoxazoles under the reaction conditions. DMSO serves as a one-carbon surrogate generating an active methylene group during the reaction to form two C-C bonds. This protocol provides a facile and an expeditious approach for the assembly of densely substituted N-heterocyclic compounds.
- Kumar, Pravin,Kapur, Manmohan
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supporting information
p. 5855 - 5860
(2020/07/30)
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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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- 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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- Cascade Process for Direct Transformation of Aldehydes (RCHO) to Nitriles (RCN) Using Inorganic Reagents NH2OH/Na2CO3/SO2F2 in DMSO
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A simple, mild, and practical process for direct conversion of aldehydes to nitriles was developed feathering a wide substrate scope and great functional group tolerability (52 examples, over 90% yield in most cases) using inorganic reagents (NH2OH/Na2CO3/SO2F2) in DMSO. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable nitriles in a pot, atom, and step-economical manner without transition metals. This protocol will serve as a robust tool for the installation of cyano-moieties to complicated molecules.
- Fang, Wan-Yin,Qin, Hua-Li
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p. 5803 - 5812
(2019/05/14)
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- SO 2 F 2 -Promoted Dehydration of Aldoximes: A Rapid and Simple Access to Nitriles
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A rapid, simple and mild process for the dehydration of aldoximes to give the corresponding nitriles, which utilizes SO 2 F 2 as an efficient reagent, has been developed. A variety of (hetero)arene, alkene, alkyne and aliphatic aldoximes proceeded with high efficiency to afford nitriles in excellent to quantitative yields with great functional group compatibilities in acetonitrile under ambient conditions. Furthermore, an eco-friendly synthetic protocol to access nitriles from aldehydes with ortho -, meta - and para -nitrile groups was also described in aqueous methanol by using inorganic base Na 2 CO 3, and a one-pot synthetic strategy to generate nitriles from aldehydes was proved to be feasible.
- Ding, Chengrong,Mei, Guangyao,Wang, Haibo,Zhang, Guofu,Zhao, Yiyong
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supporting information
p. 1484 - 1488
(2019/07/15)
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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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- Design, synthesis and structure-based optimization of novel isoxazole-containing benzamide derivatives as FtsZ modulators
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Antibiotic resistance among clinically significant bacterial pathogens is becoming a prevalent threat to public health, and new antibacterial agents with novel mechanisms of action hence are in an urgent need. Utilizing computational docking method and structure-based optimization strategy, we rationally designed and synthesized two series of isoxazol-3-yl- and isoxazol-5-yl-containing benzamide derivatives that targeted the bacterial cell division protein FtsZ. Evaluation of their activity against a panel of Gram-positive and -negative pathogens revealed that compounds B14 and B16 that possessed the isoxazol-5-yl group showed strong antibacterial activity against various testing strains, including methicillin-resistant Staphylococcus aureus and penicillin-resistant S. aureus. Further molecular biological studies and docking analyses proved that the compound functioned as an effective inhibitor to alter the dynamics of FtsZ self-polymerization via a stimulatory mechanism, which finally terminated the cell division and caused cell death. Taken together, these results could suggest a promising chemotype for development of new FtsZ-targeting bactericidal agent.
- Bi, Fangchao,Song, Di,Zhang, Nan,Liu, Zhiyang,Gu, Xinjie,Hu, Chaoyu,Cai, Xiaokang,Venter, Henrietta,Ma, Shutao
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- Novel Pyrimidine-4-Carboxylic Acid Derivatives Having Anti-tumor Activity
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The present invention relates to a novel pyrimidine-4-carboxylic acid derivative having anticancer activity. The compound of the present invention can be useful as a medicine for treating and preventing oncologic disorders. The compound of the present inv
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Paragraph 0094-0097
(2017/05/16)
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- Catalytic Enantioselective [3 + 2] Cycloaddition of α-Keto Ester Enolates and Nitrile Oxides
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An enantioselective [3 + 2] cycloaddition reaction between nitrile oxides and transiently generated enolates of α-keto esters has been developed. The catalyst system was found to be compatible with in situ nitrile oxide-generation conditions. A versatile array of nitrile oxides and α-keto esters could participate in the cycloaddition, providing novel 5-hydroxy-2-isoxazolines in high chemical yield with high levels of diastereo- and enantioselectivity. Notably, the optimal reaction conditions circumvented concurrent reactions via O-imidoylation and hetero-[3 + 2] pathways.
- Bartlett, Samuel L.,Sohtome, Yoshihiro,Hashizume, Daisuke,White, Peter S.,Sawamura, Miki,Johnson, Jeffrey S.,Sodeoka, Mikiko
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supporting information
p. 8661 - 8666
(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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- Lanthanide and asymmetric catalyzed syntheses of sterically hindered 4-isoxazolyl-1,4-dihydropyridines and 4-isoxazolyl-quinolones
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The Ytterbium (III) triflate catalyzed Hantzsch synthesis allows for the preparation of sterically hindered 4-isoxazolyl-1,4-dihydropyridines in moderate to good yields. Asymmetric organocatalysis with (R)-4-Oxo-2,6-bis-(2,4,6-triisopropyl-phenyl)-3,5-dioxa-4l5-phospha-cyclohepta[2,1-a;3,4-a']dinaphthalen-4-ol (R-TRIP) produces moderate yields of chiral 4-isoxazolyl-quinolones with high enantioselectivity.
- Steiger, Scott A.,Li, Chun,Campana, Charles F.,Natale, Nicholas R.
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p. 423 - 425
(2016/01/12)
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- Biphenyl derivatives containing trimethylsilyl benzyl ether or oxime groups as probes for NO2 detection
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Four probes based in the use of a biphenyl moiety and functionalized with trimethylsilyl benzyl ether (P1 and P3) and oxime (P2 and P4) groups have been prepared and tested as optical probes for the detection of NO2. Reaction of NO2 with acetonitrile solutions of P2-P4 resulted in the formation of aldehydes 7 and 8 with a concomitant redshift of the absorption bands. Probe P2 displayed a bathochromic shift of 45 nm upon reaction with NO2 and was able to detect this poisonous gas at concentrations as low as 0.02 ppm. P2 was highly selective against NO2 and other gases (i.e. NO, CO2, H2S, SO2) and vapours of organic solvents (i.e. acetone, hexane, chloroform, acetonitrile or toluene) had no effect in the optical properties of the probe.
- Juárez, L. Alberto,Costero, Ana M.,Parra, Margarita,Gil, Salvador,Ródenas, Javier,Sancenón, Félix,Martínez-Má?ez, Ramón
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p. 43719 - 43723
(2016/05/24)
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- Alkyl Nitrites: Novel Reagents for One-Pot Synthesis of 3,5-Disubstituted Isoxazoles from Aldoximes and Alkynes
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An efficient, one-pot approach has been described for the synthesis of 3,5-disubstituted isoxazoles from substituted aldoximes (mixture of E and Z) and alkynes, using alkyl nitrites under conventional heating conditions. The key nitrile oxide intermediates that are required for the synthesis of isoxazoles are formed by treatment of substituted aldoxime with either tert-butyl nitrite or isoamyl nitrite. The generated nitrile oxides underwent in situ [3+2] dipolar cycloaddition to the substituted alkynes to give 3,5-disubstituted isoxazoles regioselectively in high to excellent yields. The developed synthetic methodology was applied for the synthesis of a previously reported potent hDGAT1 inhibitor.
- Kadam, Kishorkumar S.,Gandhi, Thirumanavelan,Gupte, Amol,Gangopadhyay,Sharma, Rajiv
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p. 3996 - 4008
(2016/11/11)
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- (Thiolan-2-yl)diphenylmethyl benzyl ether/N,N′-diarylurea cocatalyzed asymmetric aziridination of cinnamyl bromide and aryl aldimine
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A dual catalyst system using THT-based chiral sulfide 2a and H-bond donor 10a was developed for the asymmetric imino Corey-Chaykovsky reaction. Under the optimum reaction conditions, cinnamyl bromide reacted with a wide scope of N-diphenylphosphinic aldim
- Wang, Shang-Hua,Chein, Rong-Jie
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supporting information
p. 2607 - 2615
(2016/05/11)
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- Enantioselective synthesis of diaryl aziridines using tetrahydrothiophene- based chiral sulfides as organocatalysts
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This work describes catalytic and asymmetric aziridinations (15 examples, 95-98% ee) of benzyl bromide and imines via the imino Corey-Chaykovsky reaction using (thiolan-2-yl)diarylmethanol benzyl ether as an organocatalyst. The catalyst and analogues thereof were prepared through an expeditious and efficient synthetic route featuring a double nucleophilic substitution and Shi epoxidation as key steps.
- Huang, Meng-Ting,Wu, Hsin-Yi,Chein, Rong-Jie
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supporting information
p. 1101 - 1103
(2014/01/17)
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- Metabolism and metabolites of dithiocarbamates in the plant pathogenic fungus leptosphaeria maculans
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Synthetic compounds containing a dithiocarbamate group are known to have a variety of biological effects and applications including antifungal, herbicidal, and insecticidal application. Leptosphaeria maculans is a fungal pathogen of crucifers able to detoxify efficiently the only plant natural product containing a dithiocarbamate group, the phytoalexin brassinin. To evaluate the effects of dithiocarbamates on L. maculans, a number of structurally diverse S-methyl dithiocarbamates containing indolyl, biphenyl, and benzimidazolyl moieties were synthesized, and their antifungal activities and metabolism by L. maculans were investigated. All dithiocarbamates were transformed by L. maculans through hydrolysis to the corresponding amines, which were less antifungal than the parent compounds. Two dithiocarbonates were shown to be much less antifungal than the corresponding dithiocarbamates. Results of this investigation indicate that S-methyl dithiocarbamates are not useful inhibitors of L. maculans and that their rates of transformation by L. maculans did not correlate with the antifungal activity of the particular compound.
- Pedras, M. Soledade C.,Sarma-Mamillapalle, Vijay K.
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experimental part
p. 7792 - 7798
(2012/10/08)
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- Stereospecific synthesis of syn -α-oximinoamides by a three-component reaction of isocyanides, syn -chlorooximes, and carboxylic acids
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A stereospecific multicomponent reaction among isocyanides, syn-chlorooximes, and carboxylic acids provides an efficient synthesis of biologically relevant syn-α-oximinoamides.
- Pirali, Tracey,Mossetti, Riccardo,Galli, Simona,Tron, Gian Cesare
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supporting information; experimental part
p. 3734 - 3737
(2011/09/15)
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- Design, synthesis, and evaluation of non-steroidal farnesoid X receptor (FXR) antagonist
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A series of substituted-isoxazole derivatives was prepared as candidate farnesoid X receptor (FXR) antagonists, based on our previously proposed ligand superfamily concept. Structure-activity relationship studies indicated that the shape and the structura
- Kainuma, Masahiko,Makishima, Makoto,Hashimoto, Yuichi,Miyachi, Hiroyuki
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p. 2587 - 2600
(2007/10/03)
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- Δ2-isoxazoline derivatives as antimicrobials
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The inhibitory effect of newly synthesized C- (anthranyl and biphenyl)-5-substituted-δ2-isoxazolines were characterized by IR, 1H NMR, 13C NMR and CHN analysis and evaluated for their antimicrobial activity against differe
- Priya,Basappa,Rangappa
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- Reduction of aldehydes and oximes to their corresponding alcohols and amines by catalytic hydrogenation method
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The reduction of aldehydes such as 2-butyl-5-chloro-3H-imidazole-5- carbaldehyde and veratraldehyde, which are pharmaceutical key intermediates, have been reduced to alcohols by catalytic hydrogenation method in the presence of magnesium and also oximes are reduced to primary amines successively by magnesium/ammonium formate system, is a large scale feasible and cheaper method. The crystal structure of the product, (2-butyl-5-chloro-3H-imidazole-4-yl)- methanol 1 is reported.
- Basappa,Doreswamy,Mahendra,Mantelingu,Sridhar,Prasad, J. Shashidhara,Rangappa
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p. 148 - 151
(2007/10/03)
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- Discovery of 3-amino-4-chlorophenyl P1 as a novel and potent benzamidine mimic via solid-phase synthesis of an isoxazoline library
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In an effort to identify orally bioavailable factor Xa inhibitors, two isoxazolines libraries were prepared to scan for novel P1 ligands. From this work, 4-chloro-3-aniline was identified as a novel and potent benzamidine mimic.
- Lam, Patrick Y. S.,Adams, Jessica J.,Clark, Charles G.,Calhoun, W. Jason,Luettgen, Joseph M.,Knabb, Robert M.,Wexler, Ruth R.
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p. 1795 - 1799
(2007/10/03)
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- β-Cyclodextrin as a scaffold for supramolecular chemistry, to reverse the regioselectivity of nitrile oxide cycloadditions
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β-Cyclodextrin has been used as a molecular scaffold, whereby tethering dipolarophiles to the cyclodextrin and then allowing preassociation of the modified cyclodextrins with aromatic nitrile oxides, as host-guest complexes, controls the relative orientations of the dipoles and the dipolarophiles in their cycloadditions. In this manner it has been possible to reverse the usual regioselectivity of cycloadditions of nitrile oxides, as illustrated by reactions with a terminal alkene, a terminal alkyne, and a 1,2-disubstituted alkene. For example, in aqueous solution, 4-tertbutylbenzonitrile oxide reacted with 6(A)-deoxy-6(A)-propynamido-β-cyclodextrin to give the corresponding 4- and 5-substituted isoxazoles, in a 15:1 ratio. With DMF as the solvent, to reduce the extent of host-guest complexation, the product ratio was 1:1.5. The role of complexation in these reactions is also demonstrated by contrasting these results with that of the reaction of the nitrile oxide with methyl propynoate, which afforded only the 5-substituted cycloaddition product. Molecular recognition by the cyclodextrin scaffolds was demonstrated through treatment of 4-tertbutylbenzonitrile oxide with an equimolar mixture of 6(A)-deoxy-6(A)-propynamido-β-cyclodextrin and methyl propynoate, in aqueous solution, which gave only the cycloadducts from reaction of the cyclodextrin dipolarophile.
- Meyer, Adam G.,Easton, Christopher J.,Lincoln, Stephen F.,Simpson, Gregory W.
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p. 9069 - 9075
(2007/10/03)
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