- Preparation of 2-(3-hydroxy-1-adamantyl)-2-oxoacetic acid: A key intermediate for saxagliptin
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An optimized synthetic approach to prepare 2-(3-hydroxy-1-adamantyl)-2- oxoacetic acid has been reported in a good yield under mild experimental conditions. It was synthesized from 1-adamantanecarboxylic acid via successful reaction with thionyl chloride and sodium diethyl malonate to give dimethyl (1-adamantylcarbonyl) malonate, which was subjected to hydrolysis and decarboxylation by a mixture of acetic acid with water and sulfuric acid and then oxidation by potassium permanganate. The synthesized adamantane derivative was utilized to saxagliptin.
- Li, Jingke,Zhang, Shurong,Zhou, Hongrui,Peng, Jun,Feng, Yue,Hu, Xiangnan
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Read Online
- Synthesis of 1-acetyladamantane by reaction of 1-bromoadamantane with vinyl acetate and ethylidene diacetate catalyzed by Mn2(CO)10
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A procedure has been developed for the synthesis of 1-acetyladamantane in 95% yield by reaction of 1-bromoadamantane with vinyl acetate or ethylidene diacetate in the presence of manganese complexes.
- Khusnutdinov,Shchadneva,Mukhametshina
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Read Online
- The Mn(acac)3-RCN-CCl4 system as a new efficient reagent for the oxidation of secondary alcohols into ketones
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The Mn(acac)3-RCN-CCl4 system was found to be efficient for the oxidation of secondary alcohols into the corresponding ketones in 80-93% yields. The oxidation proceeds through the formation of alkyl hypochlorites, which are generated from CCl4 and the alcohols in the presence of the Mn(acac)3-RCN catalytic system (R = Me, Et, and Ph).
- Khusnutdinov,Schadneva,Baiguzina,Dzhemilev
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Read Online
- Selective Nitroxylation of Adamantane Derivatives in the System Nitric Acid–Acetic Anhydride
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Abstract: A number of new nitroxyadamantanes have been synthesized by nitroxylation of the corresponding substrates with nitric acid in acetic anhydride. High electrophilicity and reduced acidity of the system HNO3–Ac2O increases the stability of nitrates and significantly decreases the probability of formation of alcohols. In some cases, nitrolysis and oxidation of functional groups in the substrate are observed.
- Ivleva, E. A.,Klimochkin, Yu. N.,Moiseev, I. K.
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Read Online
- Visible light photoredox catalyzed deprotection of 1,3-oxathiolanes
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An efficient visible light photoredox catalyzed aerobic deprotection of 1,3-oxathiolanes using organic dye Eosin Y as a photocatalyst is disclosed. The deprotection procedure features the use of a metal-free catalyst, mild conditions, a broad range of substrate scope, and good functional group tolerance. 35 examples were tested under the standard conditions and most of them afforded the deprotected products in modest to high yields.
- Yang, Mingyang,Xing, Zhimin,Fang, Bowen,Xie, Xingang,She, Xuegong
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supporting information
p. 288 - 291
(2020/01/13)
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- Nickel/Photoredox-Catalyzed Methylation of (Hetero)aryl Chlorides Using Trimethyl Orthoformate as a Methyl Radical Source
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Methylation of organohalides represents a valuable transformation, but typically requires harsh reaction conditions or reagents. We report a radical approach for the methylation of (hetero)aryl chlorides using nickel/photoredox catalysis wherein trimethyl orthoformate, a common laboratory solvent, serves as a methyl source. This method permits methylation of (hetero)aryl chlorides and acyl chlorides at an early and late stage with broad functional group compatibility. Mechanistic investigations indicate that trimethyl orthoformate serves as a source of methyl radical via β-scission from a tertiary radical generated upon chlorine-mediated hydrogen atom transfer.
- Kariofillis, Stavros K.,Shields, Benjamin J.,Tekle-Smith, Makeda A.,Zacuto, Michael J.,Doyle, Abigail G.
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supporting information
p. 7683 - 7689
(2020/04/22)
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- Aminoxyl-Catalyzed Electrochemical Diazidation of Alkenes Mediated by a Metastable Charge-Transfer Complex
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We report the development of a new aminoxyl radical catalyst, CHAMPO, for the electrochemical diazidation of alkenes. Mediated by an anodically generated charge-transfer complex in the form of CHAMPO-N3, radical diazidation was achieved across a broad scope of alkenes without the need for a transition metal catalyst or a chemical oxidant. Mechanistic data support a dual catalytic role for the aminoxyl serving as both a single-electron oxidant and a radical group transfer agent.
- Siu, Juno C.,Parry, Joseph B.,Lin, Song
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supporting information
p. 2825 - 2831
(2019/02/14)
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- Catalyst-Free Photodriven Reduction of α-Haloketones with Hantzsch Ester
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Catalyst-free dehalogenation of α-haloketones under visible light irradiation is studied. The reactions were carried out in common organic solvent. The outcomes of dechlorination are excellent in yields up to 92%, and it is also applicable to bromides, which give even higher yields. The reaction is tolerable to a broad spectrum of substrates, especially to aromatic ketones, including various aryl and hetaryl groups. There are two examples of aliphatic ketones presented in the paper, although their reactivities are not as high as that of the aromatic ketones.
- Lu, Zheng,Yang, Yong-Qing
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p. 508 - 515
(2019/01/10)
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- A rimantadine Schiff base synthetic method (by machine translation)
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The invention discloses a rimantadine Schiff base synthetic method, including adamantane chloride preparation, adamantane methyl preparation, 1 - adamantane methyl oxime preparation, rimantadine preparation, rimantadine Schiff base preparation, wherein the adamantane methyl preparation steps are as follows: in the flask to join the three trimethylaluminum, formic acid cerium, then dropwise adamantane formyl chloride [...], the adamantane chloride with three methyl aluminum reaction generating adamantane methyl ketone, after the reaction is completed in the reaction liquid into ice water, then filtering, drying, the resulting pale yellow precipitate adamantane methyl ketone. The beneficial effects: the reaction of this invention route changes before the adamantane methyl ketone synthesis route, the use of formic acid cerium auxiliary trimethyl aluminum reaction, mild reaction conditions, few by-products. The invention synthetic method mild condition, the process is simple and feasible, less catalyst levels, environmental protection, high product yield. (by machine translation)
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Page/Page column 3-7
(2019/01/16)
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- Compounding agent of rimantadine hydrochloride and camphor tree essential oil and application thereof
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The invention discloses a compounding agent of rimantadine hydrochloride and camphor tree essential oil and application thereof, wherein the weight ratio of the amantadine hydrochloride to the camphortree essential oil in the compounding agent is 1: 50-50: 1, Adamantanecarbonyl chloride as a raw material, trimethylaluminum as a reagent and cerium formate as an auxiliary agent are reacted to formadamantane methyl ketone, and the rimantadine hydrochloride is prepared by oximation and platinum-carbon hydrogenation reduction of the adamantane methyl ketone; and the camphor tree essential oil isprepared by crushing camphor tree seeds, leaves, bark and the like as raw materials, using sodium glycinate and citric acid to assist breaking of cell walls and using a distillation technique; and thebeneficial effects are that: high purity and high yield of the rimantadine hydrochloride and the camphor tree essential oil. The compound composition of the rimantadine hydrochloride and the camphortree essential oil has synergistic effect, can effectively reduce the application amount of single agents, expands the sterilization spectrum, reduces the phytotoxicity, significantly improves the control effect against pathogens and viruses, alleviates the resistance problem of pathogenic bacteria, and reduces the cost of prevention.
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Page/Page column 5-9
(2019/01/24)
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- A kind of anti-influenza virus preparation
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The present invention discloses an anti-influenza virus preparation, including 1 - bromo adamantane preparation, adamantane formic acid preparation, adamantane chloride preparation, adamantane methyl preparation, 1 - adamantane methyl oxime preparation, hydrochloric acid rimantadine preparation, anti-influenza virus preparation, wherein the adamantane methyl preparation steps are as follows: in the flask to join the three trimethylaluminum, formic acid cerium, then dropwise adamantane formyl chloride [...], the adamantane chloride with three methyl aluminum reaction generating adamantane methyl ketone, after the reaction is completed in the reaction liquid into ice water, then filtering, drying, the resulting pale yellow precipitate adamantane methyl ketone. The beneficial effects: preparation method of this invention mild condition, the process is simple and feasible, high product yield, the system anti- influenza virus preparation can be effective prevention and treatment of type a/b influenza virus infection, also can effectively alleviate the symptoms of the common cold.
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Paragraph 0026; 0031; 0040; 0049
(2019/03/15)
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- Synthesizing method of rimantadine hydrochloride
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The invention discloses a synthesizing method of rimantadine hydrochloride. The synthesizing method comprises the following steps of preparing of 1-bromoadamantane, preparing of adamantane carboxylicacid, preparing of adamantanecarbonyl chloride, preparing of adamantyl methyl ketone, preparing of 1-amantadine methyl ketone oxime, preparing of rimantadine hydrochloride, and preparing of a rimantadine hydrochloride preparation; in the preparing process of adamantyl methyl ketone: adding trimethylaluminum and cerium formate into a flask, then dripping a benzene solution of adamantanecarbonyl chloride, and enabling the adamantanecarbonyl chloride and the trimethylaluminum to react and generate adamantyl methyl ketone; after reaction is finished, pouring a reaction solution into ice water, filtering and drying, so as to obtain a light yellow precipitate, namely the adamantyl methyl ketone. The synthesizing method has the beneficial effects that the conditions are mild, and the technology is simple and feasible; the usage amount of catalyst is small, the environment-friendly effect is realized, and the yield of product is high.
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Paragraph 0022; 0025; 0030
(2019/02/21)
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- Preparation method of rimantadine hydrochloride preparation
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The invention discloses a preparation method of a rimantadine hydrochloride preparation. The preparation method comprises the following steps: preparation of 1-bromoadamantane, preparation of amantadecanoic acid, preparation of adamantanecarbonyl chloride, preparation of adamantyl methy ketone, preparation of 1-amantadine methyl ketone oxime, preparation of rimantadine hydrochloride, and preparation of the rimantadine hydrochloride preparation. The preparation of adamantyl methy ketone comprises the following steps: adding (CH3)3Sb and nickelous formate into a flask; dropwise adding an acetonitrile solution of adamantanecarbonyl chloride, wherein adamantanecarbonyl chloride reacts with (CH3)3Sb to generate adamantyl methy ketone; after reaction, pouring a reaction liquid into ice water; and filtering and drying the mixture to obtain a light yellow precipitate, thereby obtaining the adamantyl methy ketone. The preparation method has the beneficial effects that the preparation method ofrimantadine hydrochloride preparation is good in environmental protection, mild in condition of a synthetic method, simple and feasible in process and high in product yield.
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Paragraph 0026; 0031; 0040; 0049
(2019/02/04)
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- Preparation method of 1-adamantyl methy ketone
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The invention belongs to the field of preparation of chemical intermediates, and particularly relates to a preparation method of 1-adamantyl methy ketone. The preparation method comprises the following steps of step 1, enabling adamantane and liquid bromine to react, so as to obtain 1-bromoadamantane; step 2, using concentrated sulfuric acid as a catalyst, adding the 1-bromoadamantane and n-hexane, and dripping formic acid, so as to obtain 1-adamantanecarboxylic acid; step 3, enabling the 1-adamantanecarboxylic acid and thionyl chloride to react, heating and refluxing, extracting by benzene, and directly applying the extracting liquid for the reaction in next step; step 4, dripping a mixed solution of benzene, diethyl malonate and anhydrous ethyl alcohol into a mixed solution of magnesiumpowder, iodine, anhydrous ethyl alcohol and benzene, dripping a benzene solution of 1-adamantanecarbonyl chloride, extracting by benzene, drying and distilling, so as to obtain 2- adamantanecarbonyl diethyl malonate; step 5, adding glacial acetic acid, water and concentrated sulfuric acid into the residue. The preparation method has the advantage that the yield rate is high.
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Paragraph 0011; 0013; 0014; 0016
(2019/06/08)
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- Biomimetic Oxidative Deamination Catalysis via ortho-Naphthoquinone-Catalyzed Aerobic Oxidation Strategy
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An ortho-naphthoquinone-catalyzed oxidative deamination reaction has been developed where the molecular oxygen and water serve as the sole oxidant and nucleophile. The current aerobic deamination reaction proceeds via the ketimine formation between ortho-naphthoquinones and amines followed by the prototropic rearrangement and hydrolysis by water, representing a biomimetic oxidative deamination of amine species in the human body by the liver and kidneys. The compatibility of ortho-naphthoquinone organocatalysts with molecular oxygen and water opens up a new biomimetic catalyst system that can function as versatile deaminases for a variety of amine-containing molecules such as amino acids and DNA nuclear bases.
- Golime, Gangadhararao,Bogonda, Ganganna,Kim, Hun Young,Oh, Kyungsoo
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p. 4986 - 4990
(2018/05/14)
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- A method for synthesizing diamond ethylamine
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The invention discloses a synthetic method for rimantadine. The synthetic method is characterized by comprising the following steps: firstly, obtaining 1-bromoadamantane by reacting adamantine with liquid bromine; then, acidifying to obtain adamantanecarboxylic acid after reacting 1-bromoadamantane with magnesium and anhydrous ether; obtaining adamantine carbonyl chloride by performing reflux reaction on tehadamantanecarboxylic acid with thionyl chloride; obtaining adamantane methyl ketone by reacting the adamantine carbonyl chloride with (CH3)2CdCu; and finally, obtaining the rimantadine by hydriding and reacting adamantane methyl ketone with hydrochloric acid and ammonia water in the presence of sodium borohydride. The synthetic method disclosed by the invention is gentle in condition, simple in follow-up processing, high in yield, cheap in raw material and low in synthesis cost.
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Paragraph 0047; 0048
(2017/03/22)
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- Chemoselective Ketone Synthesis by the Addition of Organometallics to N-Acylazetidines
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A general and highly chemoselective method for the synthesis of ketones by the addition of organometallics to N-acylazetidines via stable tetrahedral intermediates is reported for the first time. The transformation is characterized by its wide substrate scope and exquisite selectivity for the ketone products even when a large excess of nucleophilic reagents is used. Even of broader interest is the use of N-acylazetidines as bench-stable, readily available amide acylating reagents, in which the reactivity is controlled by amide pyramidalization and strain of the four-membered ring to afford synthetically valuable building blocks.
- Liu, Chengwei,Achtenhagen, Marcel,Szostak, Michal
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p. 2375 - 2378
(2016/06/09)
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- Reactions of methyl esters of adamantane acids with acetonitrile
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Methyl adamantane-1-carboxylate and methyl (1-adamantyl)acetate react with acetonitrile in the presence of sodium hydride to give 3-(1-adamantyl)-3-oxopropanenitrile and 4-(1-adamantyl)-3-oxobutanenitrile, respectively. Reaction involving methyl (1-adamantyl)-acetate produces also 2-(1-adamantyl)-N-(E-1-cyanoprop-1-ene-2-yl)acetamide; the structure of this side product was established by X-ray diffraction analysis.
- Shiryaev,Belen′kaya,Shiryaev,Rybakov,Klimochkin, Yu. N.
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p. 2966 - 2969
(2016/09/28)
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- Synthesis and initial evaluation of quinoline-based inhibitors of the SH2-containing inositol 5′-phosphatase (SHIP)
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Recently, inhibition of the SH2-containing inositol 5′-phosphatase 1 (SHIP1) has become an attractive strategy for facilitating engraftment of MHC-I mismatched bone marrow grafts, increasing the number of adult stem cells in vivo, and inducing mobilization of hematopoietic stem cells. Utilizing high-throughput screening, two quinoline small molecules (NSC13480 and NSC305787) that inhibit SHIP1 enzymatic activity were discovered. New syntheses of these inhibitors have been developed which verified the relative stereochemistry of these structures. Utilizing this synthetic route, some analogs of these quinolines have been prepared and tested for their ability to inhibit SHIP. These structure activity studies determined that an amine tethered to the quinoline core is required for SHIP inhibition. SHIP inhibition may explain the antitumor effects of similar quinoline amino alcohols and provides an impetus for further synthetic studies in this class of compounds.
- Russo, Christopher M.,Adhikari, Arijit A.,Wallach, Daniel R.,Fernandes, Sandra,Balch, Amanda N.,Kerr, William G.,Chisholm, John D.
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supporting information
p. 5344 - 5348
(2015/11/09)
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- A clean and selective radical homocoupling employing carboxylic acids with titania photoredox catalysis
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A titania photoredox catalysis protocol was developed for the homocoupling of C-centered radicals derived from carboxylic acids. Intermolecular reactions were generally efficient and selective, furnishing the desired dimers in good yields under mild neutral conditions. Selective cross-coupling with two acids proved unsuccessful. An intra-molecular adaptation enabled macrocycles to be prepared, albeit in modest yields. (Chemical Equation Presented).
- Manley, David W.,Walton, John C.
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supporting information
p. 5394 - 5397
(2015/02/19)
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- A convenient method for the synthesis of (S)-N-boc-3- hydroxyadamantylglycine: A key intermediate of saxagliptin
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(S)-N-Boc-3-Hydroxyadamantylglycine is a key intermediate of saxagliptin. It was synthesized from 1- adamantanecarboxylic acid to afford 1-acetyladamantane (2), which was converted into 2-(1-adamantyl)-2-oxoacetic acid (3) through oxidation, and then into 1-adamantyl-2-hydroxyimino acetic acid (4) followed by treatment of hydroxylamine hydrochloride, then 4 was reducted and Boc-protected to give N-Boc-adamantylglycine (5), which was oxidized with KMnO4 and treated with a chiral base. Utilizing this route, (S)-N-Boc-3- Hydroxyadamantylglycine was prepared. This work is to elaborate a convenient route to synthesize (S)-N-Boc-3-Hydroxyadamantylglycine and provide a new idea for the synthesis of saxagliptin.
- Wang, Anmin,Deng, Yu,Pan, Xinmei,Chen, Yingjie,Tao, Zhu,Liang, Dinghua,Hu, Xiangnan
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p. 627 - 631
(2014/07/21)
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- A novel method for the synthesis of 2-(3-hydroxy-1-adamantyl)-2-oxoacetic acid
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A simple and efficient synthetic route to 2-(3-hydroxy-1-adamantyl)-2- oxoacetic acid is described by a direct oxidation reaction of adamantan-1-yl-ethan-1-one which could be prepared by a Grignard reaction. In this approach, the oxidation reaction introduced the hydroxyl and carboxyl group by a one-pot reaction.
- Pan, Xianhua,Lu, Qingling,Li, Xiaojun,Zhang, Jianshui,Yu, Wansheng,Liu, Feng
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p. 722 - 723
(2014/01/23)
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- QUINOLINE-OXAZOLINE COMPOUNDS AND THEIR USE IN OXIDATION SYNTHESIS
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A quinoline-oxazoline compound having the formula: where one of X1 and X2 is N and the other is C and one of R1, R2 and R3 is Z wherein Z is an oxazoline radical having the formula such that when X1 is N R2 is Z and R1 is absent, and when X2 is N either R1 or R3 is Z and R2 is absent. R1 and R3 through R12 are independently H or a pendant moiety which does not interfere with coordination of either N in the quinoline compound with a coordination center. These compounds can be complexed with a suitable coordination center such as catalytically active palladium and can be highly useful in catalytically oxidizing alkenes with high regioselectivity.
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Page/Page column 10
(2011/04/14)
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- Conformationally constrained adamantaneoxazolines of pharmacological interest
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New conformationally constrained adamantane 2-oxazoline building blocks 1-4 were synthesized and their antimicrotubule and antitrypanosomal potency was investigated. Although most of the new compounds affect tubulin polymerization, this does not make a major contribution to trypanocidal activity.
- Papanastasiou, Ioannis,Foscolos, George B.,Tsotinis, Andrew,Olah, Judit,Ovadi, Judit,Radhika Prathalingam,Kelly, John M.
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experimental part
p. 2043 - 2061
(2009/04/06)
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- A short-cut from 1-acetyl adamantane to 2-(1-adamantyl)pyrroles
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The oxime of 1-acetyl adamantane 2 is added to acetylene (KOH/DMSO, 70 °C, initial acetylene pressure 13 atm, 30 min) to afford the corresponding O-vinyl oxime 5 in 80% yield. The latter upon heating (DMSO, 120 °C, 1 h) gives 2-(1-adamantyl)pyrrole 3, 1-acetyl adamantane 1, and adamantane (6:3:1 mass ratio), the yield of the pyrrole 3 being 83% (based on 1-acetyl adamantane 1 consumed). Under harsher conditions (NaOH/DMSO, 130 °C, atmospheric pressure of acetylene, 4 h) oxime 2 reacts with acetylene to furnish pyrrole 3, 1-acetyl adamantane 1, 1-vinyl adamantane 9, and adamantane (6:7:3:1 mass ratio), with the isolated yield of pyrrole 3 reaching 34%. Under pressure (NaOH/DMSO, 120 °C, initial acetylene pressure 14 atm, 1 h) the same reaction leads to 2-(1-adamantyl)-1-vinylpyrrole 4 and ketone 1 in 48% (based on consumed ketone 1) and 24% yields, respectively. The pyrrole 4 is easily deprotected to the corresponding 1H-pyrrole 3 in 77% yield by treatment (aqueous MeCN) with Hg(OAc)2 and NaBH4.
- Trofimov, Boris A.,Schmidt, Elena Yu.,Zorina, Nadezhda V.,Senotrusova, Elena Yu.,Protsuk, Nadezhda I.,Ushakov, Igor A.,Mikhaleva, Al'bina I.,Méallet-Renault, Rachel,Clavier, Gilles
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p. 4362 - 4365
(2008/09/21)
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- Novel anti-Markovnikov regioselectivity in the Wacker reaction of styrenes
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The Wacker reaction is one of the longest known palladium-catalysed organic transformations, and in the vast majority of cases proceeds with Markovnikov regioselectivity. Palladium(II)-mediated oxidation of styrenes was examined and in the absence of reoxidants was found to proceed in an anti-Markovnikov sense, giving aldehydes. Studies on the mechanism of this unusual transformation were carried out, and indicate the possible involvement of a η4-palladium-styrene complex. With a heteropolyacid as the terminal oxidant, oxidation of styrene to give the anti-Markovnikov aldehyde as the major product was found to be catalytic.
- Wright, Joseph A.,Gaunt, Matthew J.,Spencer, Jonathan B.
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p. 949 - 955
(2007/10/03)
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- SPHINGOSINE KINASE INHIBITORS
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The invention relates to substituted adamantane compounds, pharmaceutical compositions thereof, processes for their preparation, and methods for inhibiting sphingosine kinase and for treating or preventing hyperproliferative disease, inflammatory disease, or angiogenic disease.
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Page/Page column 44
(2008/06/13)
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- Preparation of 1-adamantyl ketones: Structure, mechanism of formation and biological activity of potential by-products
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Reactions between adamantane-1-carbonyl chloride and several Grignard reagents as well as interactions with solvents have been examined. Some new and unexpected adamantane derivatives were isolated, fully characterized and their biological activity determined. In particular, an unexpected isochromanone 16 was formed in an SEAr process, in which a stable hydrocarbon was the leaving group.
- Vicha, Robert,Necas, Marek,Potacek, Milan
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p. 709 - 722
(2008/02/01)
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- Six- and eightfold palladium-catalyzed gross-coupling reactions of hexa- and octabromoarenes
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Palladium-catalyzed sixfold coupling of hexabromobenzene (20) with a variety of alkenylboronates and alkenylstannanes provided hexaalkenylbenzenes 1 in up to 73% and 16 to 41% yields, respectively. In some cases pentaalkenylbenzenes 21 were isolated as the main products (up to 75%). Some functionally substituted hexaalkenylbenzene derivatives containing oxygen or sulfur atoms in each of their six arms have also been prepared (16 to 24% yield). The sixfold coupling of the less sterically encumbered 2, 3, 6, 7, 10, 11-hexabromotriphenylene (24) gave the desired hexakis(3,3-dimethyl-1-butenyl) triphenylene (25) in 93% yield. The first successful cross-coupling reaction of octabromonaphthalene (26) gave octakis-(3,3-dimethyl-1-butenyl)naphthalene (27) in 21% yield. Crystal structure analyses disclose that, depending on the nature of the substituents, the six arms are positioned either all on the same side of the central benzene ring as in 1a and 1i, making them nicely cup-shaped molecules, or alternatingly above and below the central plane las in 1h and 23. In 27, the four arms at C-1, 4, 6, 7 are down, while the others are up, or vice versa. Upon catalytic hydrogenation, 1a yielded 89% of hexakis(tert-butylethyl)benzene (23). Some efficient accesses to alkynes with sterically demanding substituents are also described. Elimination of phosphoric acid from the enol phosphate derived from the corresponding methyl ketones gave 1-ethynyladamantane (3b, 62% yield), 1-ethynyl-1-methylcyclohexane (3c, 85%) and 3,3-dimethylpentyne (3e, 65%). 1-(Trimethylsilyl)ethynylcyclopropane (7) was used to prepare 1-ethynyl-1-methylcyclopropane (3d) (two steps, 64% overall yield). The functionally substituted alkynes 3 f-h were synthesized in multistep sequences starting from the propargyl chloride 11, which was prepared in high yields from the dimethylpropargyl alcohol 10 (94%). The alkenylstannanes 19 were prepared by hydrostannation of the corresponding alkynes in moderate to high yields (42-97%), and the alkenylboronates 2 and 4 by hydroboration with catecholborane (27-96% yield) or pinacolborane (26-69% yield).
- Stulgies, Balder,Prinz, Peter,Magull, Joerg,Rauch, Karsten,Meindl, Kathrin,Ruehl, Stephan,De Meijere, Armin
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p. 308 - 320
(2007/10/03)
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- Asymmetric transesterification of secondary alcohols catalyzed by feruloyl esterase from Humicola insolens
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A new asymmetric transesterification of secondary alcohols catalyzed by feruloyl esterase from Humicola insolens has been found. Although alcohols are not the natural substrates for this enzyme, a high R enantioselectivity was observed. Stereochemical studies showed that variations in substrate structure lead to strong variations in enantioselectivity. The highest enantioselectivities are obtained when the β-carbon of the secondary alcohol is tertiary or quaternary.
- Hatzakis, Nikos S.,Smonou, Ioulia
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p. 325 - 337
(2007/10/03)
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- Influence of catalytic system composition on formation of adamantane containing ketones
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The preparation of non-symmetrical ketones by the reaction of acyl chlorides and the corresponding Grignard reagents in the presence of catalytic amounts of metal halides is described. The composition of catalyst has a great influence on the yield of the required ketone as well as on side product formation. For each catalytic system, the yield of ketone and the number of side products changes with the time of addition of the Grignard reagent. We examined the influence of both factors in our model reaction of adamantane-1-carbonyl chloride with ethylmagnesium bromide and discussed the possible mechanisms from this point of view. We have found ZnCl2, MnCl2, AlCl 3 and CuCl to be active catalytic components and developed very efficient, cheap and fast methods for the preparation of alkyl adamantyl ketones. The procedure was also tested for the synthesis of other alkyl aryl ketones. Graphical Abstract.
- Vícha, Robert,Potá?ek, Milan
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- 5-METHYLENE-1,3-DIOXOLAN-4-ONE DERIVATIVES, PROCESS FOR THEIR PRODUCTION, POLYMERS OF THE DERIVATIVES, RESIST COMPOSITIONS, AND PATTERN FORMATION PROCESS
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The 5-methylene-1,3-dioxolan-4-one derivative of the present invention is represented by the formula (1) indicated below, and it is a novel monomer from which a homopolymer and a copolymer excellent in light transparency and heat stability are obtained. Moreover, the polymer obtained by (co)polymerizing a monomer composition comprising the derivative represented by the formula (1) indicated below is excellent in the resist performance such as sensitivity, resolution and dry etching resistance, and solubility in an organic solvent, also having little line edge roughness, and thus it is preferably used as a resin for a resist composition. wherein R1 represents a bridged cyclic hydrocarbon group containing 4 to 16 carbon atoms, or a linear or branched alkyl group containing 1 to 6 carbon atoms which has a bridged cyclic hydrocarbon group containing 4 to 16 carbon atoms as a substituent; R2 represents a hydrogen atom, or a linear or branched alkyl group containing 1 to 6 carbon atoms; or R1 and R2 represent a bridged cyclic hydrocarbon group containing 4 to 16 carbon atoms together with the carbon atom to which they are bound, ???provided that the alkyl group and the bridged cyclic hydrocarbon group may have at least one substituent selected from a group consisting of a linear or branched alkyl group containing 1 to 6 carbon atoms which may be optionally substituted, a hydroxy group, a carboxy group, an acyl group containing 2 to 6 carbon atoms, an alkoxy group containing 1 to 6 carbon atoms, and a carboxy group esterified with an alcohol containing 1 to 6 carbon atoms.
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- Chlorination of Adamantane and Its Derivatives by Carbon Tetrachloride in the Presence of Manganese-, Vanadium-, and Molybdenum-containing Catalysts
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The feasibility of catalytic chlorination of adamantane and its derivatives by carbon tetrachloride in the presence of manganese-, vanadium-, and molybdenum-containing catalysts activated by nitrile ligands or alcohols was established. The optimum molar ratios of catalyst components and reactants and the optimum reaction conditions for selective syntheses of mono-, di-, and trichlorosubstituted adamantane derivatives with high yields were found.
- Khusnutdinov,Shchadneva,Baiguzina,Lavrent'eva,Burangulova,Dzhemilev
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p. 126 - 133
(2007/10/03)
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- Titanium dioxide photocatalysis of adamantane
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TiO2 photocatalysis of adamantane in oxygen equilibrated MeCN yields 1- and 2-adamantanol and adamantanone with limited degradation and preference for functionalization at the 1 position, particularly in the presence of silver salts. Oxidation in CH2Cl2 is less selective. The oxidation of cyclohexane and cyclododecane is slower. In N2-flushed solutions with Ag+ as a sacrificial acceptor, products from the trapping of both 1-adamantyl radical (adamantyl methyl ketone) and cation (N-adamantylacetamide) are obtained. Furthermore, alkylation of an electrophilic alkene (isopropylydenmalononitrile) has been obtained, though in a low yield.
- Cermenati, Laura,Dondi, Daniele,Fagnoni, Maurizio,Albini, Angelo
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p. 6409 - 6414
(2007/10/03)
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- Methods of acylating adamantane, tricyclo[5.2.1.02,6], and decalin compounds
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An acylating agent of the invention includes (A) a 1,2-dicarbonyl compound or its hydroxy reductant, (B) oxygen, and (C) at least one compound selected from (c1) a metallic compound and (C2) N-hydroxyphthalimide or another imide compound. As the 1,2-dicarbonyl compound or its hydroxy reductant (A), biacetyl, 2,3-butanediolor the like canbeused. As the metallic compound (c1), cobalt acetate, or another cobalt compound, for example, can be employed. By reacting an adamantane derivative or another compound having a methine carbon atom with the acylating agent, an acyl group can be introduced to the methine carbon atom with efficiency.
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- Catalyst comprising nitrogen-containing heterocyclic compound, and process for producing organic compound using the catalyst
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A catalyst is for use in a reaction using an oxygen-atom-containing reactant and includes a nitrogen-containing heterocyclic compound of the following formula (1): wherein each of R1and R2is, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group, and R1and R2may be combined to form a double bond or to form an aromatic or non-aromatic ring with the adjacent two carbon atoms, where one or two of heterocyclic ring containing three nitrogen atoms indicated in the formula may be further formed on the R1or R2, or on the double bond or aromatic or non-aromatic ring formed by R1and R2; X is an oxygen atom or a hydroxyl group; and Y is a single bond, a methylene group, or a carbonyl group. This catalyst can introduce an oxygen-atom-containing group into an organic substrate under mild conditions.
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- Adamantanemethanol derivatives and production processes thereof
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An adamantanemethanol derivative of the invention is represented by the following formula (1), wherein Rais a hydrogen atom or a hydrocarbon group; Rbis a hydrocarbon group having a carbon atom, to which carbon atom at least one hydrogen atom is bonded, at a bonding site with the adjacent carbon atom; Rc, Rdand Reare each a hydrogen atom, a hydroxyl group which may be protected by a protective group or the like; provided that a hydroxyl group protected by a protective group or the like is bonded to at least one carbon atom constituting the adamantane skeleton when Rais a hydrogen atom or a methyl group and Rbis a methyl group; and at least one substituent, in addition to the HO—C(Ra)(Rb)— group indicated in the formula (1), is bonded to the adamantane ring when one of Raand Rbis a methyl group and the other is an ethyl group.
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Referential example 1
(2008/06/13)
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- Evidence that the availability of an allylic hydrogen governs the regioselectivity of the Wacker oxidation
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The allylic hydrogen is found to have a dramatic effect on the regioselectivity of the Wacker oxidation, leading to the postulation that an agostic hydrogen or enyl (σ + π) complex helps to stabilise the key intermediate.
- Gaunt,Yu,Spencer
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p. 1844 - 1845
(2007/10/03)
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- PROCESS FOR THE PREPARATION OF ORGANIC COMPOUNDS WITH IMIDE CATALYSTS
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(A) A compound capable of forming a stable radical and selected from (A1) oxygen-atom-containing compounds each having a carbon-hydrogen bond at the adjacent position to an oxygen atom, (A2) carbonyl-group-containing compounds, and (A3) compounds each having a hydrocarbon group with a methine carbon atom is allowed to react with (B) a radical scavenging compound selected from, for example, (B1) unsaturated compounds, and (B2) compounds each having a hydrocarbon group with a methine carbon atom, in the presence of molecular oxygen by catalysis of, for example, an imide compound shown by the following formula (1): wherein each of R1 and R2 is a hydrogen atom or the like, where R1 and R2 may be combined to form a double bond, or an aromatic or non-aromatic ring; X is an oxygen atom or a hydroxyl group, to yield a product of an addition or substitution reaction of the compound (A) and the compound (B) or its oxidized product. The process can efficiently produce a variety of organic compounds by an addition or substitution reaction using molecular oxygen under mild conditions.
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- Catalytic radical acetylation of adamantanes with biacetyl by a cobalt salt under atmospheric dioxygen
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Exposure of a mixture of adamantane and biacetyl under O2 in the presence of Co(OAc)2 (0.1 mol%) in AcOH led to 1-acetyladamantane (47%) and 1,3-diacetyladamantane (20%) as major products along with small amounts of adamantan-1-ol (4%) and adamantan-2-one (3%).
- Kishi, Arata,Kato, Susumu,Sakaguchi, Satoshi,Ishii, Yasutaka
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p. 1421 - 1422
(2007/10/03)
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- A new route to 3-labeled or 3-substituted 4-homoadamantanones
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The pinacol rearrangement of 3,4-dihydroxyhomoadamantanes containing carbon-13, deuterium, and alkyl, or an aryl subsituent at the C-4 position provides a new route to the title compounds.
- Takeuchi,Yoshida,Nishida,Kohama,Kitagawa
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- Synthesis and formal [4 + 2] cycloaddition reactions of vinylimido complexes of titanocene
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Sources of the methylidene complex of titanocene, Cp2Ti=CH2, react with nitriles in the presence of donor ligands to afford vinylimido titanocene complexes. The vinylimido complexes react readily with ketones, nitriles, and imines, y
- Doxsee, Kenneth M.,Farahi, Judah B.,Hope, H?kon
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p. 8889 - 8898
(2007/10/02)
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- Synthesis and Reactivity of Vinylimido Complexes of Titanocene
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Tebbe's reagent (Cp2TiCH2*AlMe2Cl) or titanocene metallacyclobutanes react with nitriles in the presence of a Lewis base such as trimethylphosphine to afford vinylimido complexes of titanocene; these undergo follow-up reactions with unsaturated organic molecules to yield new heterocyclic compounds of titanocene.
- Doxsee, Kenneth M.,Farahi, Judah B.
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p. 1452 - 1454
(2007/10/02)
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- REACTION OF ORGANOMAGNESIUM COMPOUNDS OF THE ADAMANTANE SERIES WITH CARBONYL COMPOUNDS
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In the transformations of organomagnesium compounds of the adamantane series involving aldehydes, ketones, esters, and acid chlorides the nature of the reaction products and their yields are determined by the steric hindrances at the reaction centers of the organomagnesium and carbonyl compounds and by the ease of homolysis of the C-H bonds of the carbonyl reagent.The retardation of the faster addition of the Grignard reagent at the carbonyl group as a result of steric hindrances permits homolytic removal of a hydrogen atom from the carbonyl compounds by the adamantyl radical.
- Yurchenko, A. G.,Fedorenko, T. V.
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p. 875 - 880
(2007/10/02)
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