- Synthesis, characterization and olefin polymerization behaviors of phenylene-bridged bis-β-carbonylenamine binuclear titanium complexes
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Binuclear and multinuclear complexes have attracted much attention due to their unique catalytic performances for olefin polymerization compared with their mononuclear counterparts. In this work, a series of phenyl-bridged bis-β-carbonylenamine [O-/
- Luo, Derong,Zeng, Yi,Chen, Xiong,Xia, Ping,Xie, Guangyong,You, Qingliang,Zhang, Li,Li, Tingcheng,Li, Xiangdan,Zhang, Aiqing
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- Diazonium exchange and migration of pivaloyl group upon azo coupling of β-enaminones
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4,4-Dimethyl-1-methylamino-1-phenyl-2-(substituted phenyldiazenyl)pent-1- en-3-ones (prepared upon azo coupling of 4,4-dimethyl-1-methylamino-1- phenylpent-1-en-3-one 6a with the corresponding benzenediazonium tetrafluoroborates) react with another molecule of substituted benzenediazonium tetrafluoroborate (in dichloromethane in the presence of anhydrous sodium acetate) to form substituted 4,4-bis(substituted phenyldiazenyl) derivatives 8. The second azo coupling is reversible. Derivatives 8 undergo either reverse cleavage of a diazonium ion or [1,3] sigmatropic rearrangement forming substituted formazane 9. In the case of the sequential use of two different diazonium tetrafluoroborates, the less electrophilic group splits off more easily. The structures of the products 9 were studied by means of X-ray, 1H, 13C, 19F and 15N NMR and MALDI HRMS analyses. The formazans 9 exhibit a reduced mobility of the phenyl group adjacent to the pivaloyl group, giving rise to anisochronism of proton and carbon atoms, to eventually form conformers. The reduced mobility was observed by means of NMR spectroscopy. A temperature dependence of the spectral behaviour was also studied. 4,4-Dimethyl-1-methylamino-1-phenyl-2-(substituted phenyldiazenyl)pent-1-en-3-ones react with benzenediazonium tetrafluoroborates through ipso attack, the products of which can undergo either migration of the pivaloyl group to form acylated formazans or reverse reaction to give the products of single azo coupling. With different diazonium salts an exchange of phenyldiazenyl groups is observed. Copyright
- Simunek, Petr,Bertolasi, Valerio,Machacek, Vladimir
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- I2-Promoted [3+2] Cyclization of 1,3-Diketones with Potassium Thiocyanate: a Route to Thiazol-2(3H)-One Derivatives
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An I2-promoted strategy has been developed for the synthesis of thiazol-2(3H)-one derivatives from 1,3-diketones with potassium thiocyanate. This [3+2] cyclization reaction involves C?S and C?N bond formation and exhibits good functional group tolerance. A series of thiazol-2(3H)-one derivatives are obtained in moderate to good yields. (Figure presented.).
- An, Zhenyu,Liu, Yafeng,Yan, Rulong,Zhao, Pengbo
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supporting information
p. 3240 - 3244
(2021/06/16)
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- Iridium(III)-Catalyzed C-H Functionalization of Triarylphosphine Oxides with Diazo Dicarbonyl Compounds: Synthesis of α-Aryl 1,3-Dicarbonyl Derivatives
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A novel (pentamethylcyclopenta-1,3-dienyl)iridium(III)-catalyzed direct C-H functionalization of triarylphosphine oxides with diazo dicarbonyl compounds through carbene insertion has been developed. This strategy provides a simple and efficient route to t
- Lou, Qin-Xin,Li, Jing-Yu,Yang, Shang-Dong
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supporting information
(2021/04/15)
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- Method for synthesizing 1, 3-dicarbonyl compound based on terminal alkyne and acyl halide by one-pot process
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The invention belongs to the technical field of catalytic synthesis, and discloses a method for synthesizing a 1, 3-dicarbonyl compound by a one-pot process, and the method comprises the following steps: by using simple palladium and copper salts as catalysts, reacting terminal alkyne with acyl halide at 0-80 DEG C for 0.5-12 hours under the action of trifluoromethanesulfonic acid to obtain the 1,3-dicarbonyl compound, wherein the molar ratio of the terminal alkyne to the acyl halide to the palladium salt to the copper salt to the trifluoromethanesulfonic acid is 1 to (1 to 2) to (0.00001 to0.10) to (0.00001 to 0.10) to (0.00004 to 0.40); the catalysts used in the method are common the commercialized palladium salt and copper salt, reagents used in the reaction are commercialized reagents, in addition, the raw materials are cheap and easy to obtain, functional group tolerance is good, reaction conditions are mild, operation is easy and convenient, and atom economy is high.
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Paragraph 0069-0074; 0114-0116
(2020/07/21)
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- Non-Diazo C?H Insertion Approach to Cyclobutanones through Oxidative Gold Catalysis
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Cyclobutanones are synthetically versatile compounds that often require extensive effort to access. Herein, we report a facile synthesis of cyclobutanones based on the C(sp3)?H insertion chemistry of oxidatively generated gold carbenes. Various cyclobutanones were obtained in synthetically useful yields from substrates with minimal structural prefunctionalization. This discovery reveals new synthetic utilities of gold-catalyzed oxidative transformations of alkynones.
- Zheng, Zhitong,Wang, Youliang,Ma, Xu,Li, Yuxue,Zhang, Liming
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supporting information
p. 17398 - 17402
(2020/08/14)
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- Synthesis of 1,3-Diketones and β-Keto Thioesters via Soft Enolization
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Ketones and thioesters undergo soft enolization and acylation using crude acid chlorides on treatment with MgBr2·OEt2 and i-Pr2NEt to give 1,3-diketones and β-keto thioesters, respectively. The use of crude acid chlorides adds efficiency and cost reduction by avoiding the need to purify and/or purchase them. The process is conducted in a direct fashion that does not require prior enolate formation, further enhancing its efficiency and making it very easy to carry out. The method is suitable for large scale applications. ?
- Aderibigbe, Sabrina O.,Coltart, Don M.
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p. 9770 - 9777
(2019/08/27)
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- Method of preparing 1,3-diketone compound by acetyenic ketone
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The invention relates to a preparation method of preparing a 1,3-diketone compound by acetyenic ketone. The preparation method comprises the following steps: S1, putting alpha-alkynyl ketone compound,water, gold salt and silver salt in a reaction solvent to obtain a precursor mixture, wherein the molar ratio of the alpha-alkynyl ketone compound, water, gold salt and silver salt is 1: (1-50): (0.001-0.10): (0.002-0.15); and S2, putting the precursor mixture obtained in the S1 to react at a reaction temperature of 0-50 DEG C to obtain the 1,3-diketone compound, wherein the reaction time is 5 min to 48 h. The method is simple in reaction condition, free of acid or alkaline additives and high in yield, and can be applied to modern production on a large scale.
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Paragraph 0132-0138
(2019/06/12)
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- Unsymmetrical bidentate ligands as a basis for construction of ambidentate ligands for functional materials: Properties of 4,4-dimethyl-1-phenylpentane-1,3-dionate
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To establish a background to the possible use of its ambidentate derivatives as stimulus-responsive ligands in functional complexes, the basic coordination chemistry of the anion derived from 4,4-dimethyl-1-phenylpentane-1,3-dione (benzoylpivaloylmethane,
- Ko?odziejski, Micha?,Walczak, Anna,Hnatejko, Zbigniew,Harrowfield, Jack,Stefankiewicz, Artur R.
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p. 270 - 277
(2017/09/20)
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- Oxidative Coupling of Enamines and Disulfides via Tetrabutylammonium Iodide/tert-Butyl Hydroperoxide-Mediated Intermolecular Oxidative C(sp2) S Bond Formation Under Transition Metal-Free Conditions
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The reaction of enamine compounds with disulfides in the presence of tert-butyl hydroperoxide and a catalytic amount of tetrabutylammonium iodide conveniently afforded a variety of α-thioenamine compounds through the intermolecular oxidative C(sp2) S coupling. Incorporating both of the sulfide moieties in the disulfides into the final products under oxidative conditions, this novel approach exhibits the feature of atom efficiency. A radical mechanistic pathway for the reaction process has been proposed. (Figure presented.) .
- Sun, Jiyun,Zhang-Negrerie, Daisy,Du, Yunfei
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supporting information
p. 2035 - 2040
(2016/07/16)
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- Trimethylchlorosilane-Mediated Mild α-Chlorination of 1,3-Dicarbonyl Compounds Promoted by Phenyliodonium Diacetate
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Trimethylchlorosilane was used as chlorine source for the α-chlorination of 1,3-dicarbonyl compounds with phenyliodonium diacetate as oxidant at room temperature. The reaction allows the selective synthesis of α-monochlorinated products from different kinds of 1,3-dicarbonyl compounds in good yield. The potential possibility of this conversion for bromination has also been investigated.
- Chong, Siying,Su, Yingpeng,Wu, Lili,Zhang, Weigang,Ma, Junyan,Chen, Xiaowei,Huang, Danfeng,Wang, Ke-Hu,Hu, Yulai
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supporting information
p. 1359 - 1370
(2016/05/02)
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- Variations in the blaise reaction: Conceptually new synthesis of 3-amino enones and 1,3-diketones
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Organic compounds with 3-amino enone or 1,3-diketone functional groups are extremely important, as they can be converted into a plethora of heterocyclic or carbocyclic compounds, or can be used as ligands in metal complexes. We have achieved a new, easy, straightforward and convenient synthesis of 3-amino enones and 1,3-diketones starting from aryl/heteroaryl/alkyl nitriles and 1-aryl/alkyl 2-bromoethanones. The reaction is a variation of the classical Blaise reaction, and it works with zinc and trimethylsilyl chloride as an activator. By running the hydrolysis of the reaction intermediate with HCl (3 N aq.) at 0-30 °C or at 100 °C, it is possible to form either 3-amino enones or 1,3-diketones, respectively. The newly developed method was used for the synthesis of avobenzone, an ingredient of sun-screen lotions. Furthermore, an easy synthesis of (Z)-3-amino-1-[4-(tertbutyl) phenyl]-3-(4-methoxyphenyl)prop-2-en-1-one, with UV/Vis absorption characteristics similar to those of avobenzone, was also achieved.
- Rao, H. Surya Prakash,Muthanna, Nandurka
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supporting information
p. 1525 - 1532
(2015/03/04)
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- Direct synthesis of 1,3-dicarbonyl compounds via radical coupling of aldehydes with ketones under metal-free conditions
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An efficient approach for the synthesis of 1,3-diketones from aldehydes and ketones has been developed using Bu4NI (TBAI) as the catalyst. In the presence of DTBP-TBHP/p-TsOH, aldehydes undergo radical coupling with ketones to provide the desired products in moderate to high yields at 120 °C. Although various substituents on the aromatic ring of aldehydes are well tolerable under the standard reaction conditions, the protocol is limited by the scope of ketones. The method exhibits advantages in terms of the easy access of the starting materials, operational simplicity, functional group tolerance, and the absence of metal catalyst.
- Shen, Xuqian,Borah, Arun Jyoti,Cao, Xihan,Pan, Weixiang,Yan, Guobing,Wu, Xiangmei
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supporting information
p. 6484 - 6487
(2015/11/16)
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- Transition-metal-free formal decarboxylative coupling of ?±-oxocarboxylates with ?±-bromoketones under neutral conditions: A simple access to 1,3-diketones
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A transition-metal-free formal decarboxylative coupling reaction between ?±-oxocarboxylates and ?±-bromoketones to synthesize 1,3-diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal-based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism and the ?±-bromoketone unprecedentedly serves as a nucleophile under neutral conditions. The rate-determining step is an unusual hydrogen-bond-assisted enolate formation by thermolysis.
- He, Zhen,Qi, Xiaotian,Li, Shiqing,Zhao, Yinsong,Gao, Ge,Lan, Yu,Wu, Yiwei,Lan, Jingbo,You, Jingsong
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p. 855 - 859
(2015/02/05)
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- Direct oxidative coupling of enamines and electron-deficient amines: TBAI/TBHP-mediated synthesis of substituted diaminoalkenes under metal-free conditions
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A metal-free cross-coupling of enamines and electron-de fi cient amines through oxidative C(sp2)-N bond formation has been realized by using TBAI as catalyst and TBHP as oxidant. This novel strategy allows for an efficient organocatalytic synthesis of the synthetically useful diaminoalkene derivatives and is highlighted by appealing features such as readily available of the starting materials, wide substrate scope and transition-metal-free characteristics. (Chemical Equation Presented).
- Yuan, Yucheng,Hou, Wenjuan,Zhang-Negrerie, Daisy,Zhao, Kang,Du, Yunfei
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supporting information
p. 5410 - 5413
(2015/01/09)
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- Highly enantioselective epoxidation catalyzed by cinchona thioureas: Synthesis of functionalized terminal epoxides bearing a quaternary stereogenic center
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A brilliant debut! Cinchona thioureas have been reported for the first time as catalysts in the area of asymmetric oxidations. They efficiently promote an unprecedented highly enantioselective epoxidation of deactivated 1,1-disubstituted alkenes to terminal epoxides containing a quaternary stereogenic center (see scheme). Copyright
- Russo, Alessio,Galdi, Gerardina,Croce, Gianluca,Lattanzi, Alessandra
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supporting information; scheme or table
p. 6152 - 6157
(2012/06/30)
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- 1,4-Addition of Bis(iodozincio)methane to α,β-Unsaturated ketones: Chemical and theoretical/computational studies
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1,4-Addition of bis(iodozincio)methane to simple α,β-unsaturated ketones does not proceed well; the reaction is slightly endothermic according to DFT calculations. In the presence of chlorotrimethylsilane, the reaction proceeded efficiently to afford a silyl enol ether of β-zinciomethyl ketone. The CZn bond of the silyl enol ether could be used in a cross-coupling reaction to form another C-C bond in a one-pot reaction. In contrast, 1,4-addition of the dizinc reagent to enones carrying an acyloxy group proceeded very efficiently without any additive. In this case, the product was a 1,3-diketone, which was generated in a novel tandem reaction. A theoretical/computational study indicates that the whole reaction pathway is exothermic, and that two zinc atoms of bis(iodozincio)methane accelerate each step cooperatively as effective Lewis acids.
- Sada, Mutsumi,Furayama, Taniyuki,Komagawa, Shinsuke,Uchiyama, Masanobu,Matsubara, Seijiro
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experimental part
p. 10474 - 10481
(2010/10/21)
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- MgBr2·OEt2-promoted coupling of ketones and activated acyl donors via soft enolization: A practical synthesis of 1,3-diketones
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Ketones undergo soft enolization and acylation on treatment with MgBr 2OEt2, i-Pr2NEt, and various acylating agents to give 1,3-diketones. The process is particularly efficient for N-acylbenzotriazoles and O-pentafluorophenyl esters, and, in these cases, is conducted using untreated, reagent grade CH2C12 open to the air, thus providing an exceptionally simple approach to the synthesis of this important class of compounds. Thieme Stuttgart.
- Lim, Daniel,Zhou, Guoqiang,Livanos, Alexandra E.,Fang, Fang,Coltart, Don M.
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scheme or table
p. 2148 - 2152
(2009/04/03)
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- Direct carbon - Carbon bond formation via soft enolization: A facile and efficient synthesis of 1,3-diketones
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Ketones undergo soft enolate formation and acylation on treatment with MgBr2·OEt2, i-Pr2NEt, and various acylating agents to give 1,3-diketones. The process is particularly efficient for N-acylbenzotriazoles and O-Pfp esters, and, in these cases, is conducted with untreated, reagent-grade CH2Cl2 open to the air, thus providing an exceptionally simple approach to the synthesis of this important class of compounds.
- Lim, Daniel,Fang, Fang,Zhou, Guoqiang,Coltart, Don M.
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p. 4139 - 4142
(2008/02/12)
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- Synthesis of sterically hindered 1,3-diketones
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An efficient and practical method for the synthesis of sterically hindered aliphatic/aromatic 1,3-diketones via coupling of ketones with esters using potassium tert-butoxide is described. The protocol requires milder operating conditions, and the products are obained in good to excellent yields. Copyright Taylor & Francis Group, LLC.
- Nandurkar, Nitin S.,Bhanushali, Mayur J.,Patil, Dinkar S.,Bhanage, Bhalchandra M.
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p. 4111 - 4115
(2008/03/13)
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- Enantioselective borohydride reduction catalyzed by optically active cobalt complexes
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The highly enantioselective borohydride reduction of aromatic ketones or imines to the corresponding alcohols was developed in the presence of a catalytic amount of an optically active cobalt(II) complex catalyst. This enantioselective reduction is carried out using a precisely premodified borohydride with alcohols such as tetrahydrofurfuryl alcohol, ethanol and methanol. High optical yields are obtained by choosing the appropriate alcohol as modifiers and a suitable β-ketoiminato ligand of the catalyst. The enantioselective borohydride reduction has been successfully applied to the preparation of optically active 1,3-diols, the stereoselective reduction of diacylferrocenes, and dynamic and/or kinetic resolution of 1,3-dicarbonyl compounds.
- Yamada, Tohru,Nagata, Takushi,Sugi, Kiyoaki D.,Yorozu, Kiyotaka,Ikeno, Taketo,Ohtsuka, Yuhki,Miyazaki, Daichi,Mukaiyama, Teruaki
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p. 4485 - 4509
(2007/10/03)
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- Synthesis of 1,3-diketones by reaction of α-haloketones with acyl cynides promoted by samarium diiodide
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α-Haloketones reacted with acyl cyanides to form 1,3-diketones in the presence of samarium diiodide. The reaction was assumed to proceed via a mechanism involving samarium enolates in situ from α-haloketones.
- Baek, Heung Soo,Yoo, Byung Woo,Keum, Sam Rok,Yoon, Cheol Min,Kim, Sung Hoon,Kim, Joong Hyup
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- A novel synthesis of 1,3-diketones by reaction of an α-bromoketone with acyl chlorides promoted by gallium triiodide
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Promoted by gallium triiodide, an α-bromoketone, bromomethyl phenyl ketone, is treated with acyl chlorides to synthesize 1,3-diketones in good yields under mild and neutral conditions.
- Chen, Rener,Wu, Huayue,Zhang, Yongmin
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p. 666 - 667
(2007/10/03)
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- A new route for the synthesis of 1,3-diketones
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A simple route for the synthesis of 1,3-diketones by the reaction of acetylenic ketones with amines followed by hydrolysis of the resulting aminovinylketones is siggested. - Key words: acetylenic ketones; 1,3-diketones; aminovinylketones; synthesis.
- Zanina, A. S.,Shergina, S. I.,Sokolov, I. E.,Myasnikova, R. N.
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p. 689 - 694
(2007/10/02)
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- Chiral Organosilicon Compounds in Asymmetric Synthesis of Chiral 1,3-Diols
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Chiral 1,3-diols can be prepared in high enantiomeric purity (>99percent ee) from the reactions of the chiral silylcarbanion 2 with epoxides followed by oxidative cleavage of the carbon-silicon bond with hydrogen peroxide.The absolute configurations of so
- Chan, T. H.,Nwe, K. T.
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p. 6107 - 6111
(2007/10/02)
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- Clemmensen Reduction. X. The Synthesis and Acidolysis of Some Aryl Alkyl Substituted Cyclopropane-1,2-diols
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The synthesis of a number of 1-alkyl-2-arylcyclopropane-1,2-diols is reported.Reductive treatment of suitably substituted 1,3-diketones gave a cyclopropanediyl diacetate from which the diol was obtained.Reaction of these diols with acid gave α-hydroxy ketones, in which an alkyl group, rather than an aryl group, was adjacent to the carbonyl function.Clemmensen reduction of the 1,3-diketones gave products of rearrangement, generally similar to those obtained by acidolysis of the cyclopropane-1,2-diols.The relationship of these results to thermochemical studies on the stability of carboxonium ions is discussed.
- Davis, Brian R.,Hinds, Mark G.,Ting, Philip P. C.
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p. 865 - 875
(2007/10/02)
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- CONDENSATION OF NITRILES WITH METHYL KETONES AS A METHOD FOR THE SYNTHESIS OF β-AMINOVINYL KETONES
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The condensation of nitriles containing aromatic substituents and of trichloroacetonitrile with methyl ketones in the presence of (phenylethylamino)magnesium bromide leads to β-aminovinyl ketones.Acid hydrolysis of the β-aminovinyl ketones gave high yields of the corresponding β-diketones.
- Sosnovskikh, V. Ya.,Ovsyannikov, I. S.
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p. 1801 - 1805
(2007/10/02)
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- Synthesis of 1,3-Dicarbonyl Compounds by the Oxidation of 3-Hydroxycarbonyl Compounds with Corey-Kim Reagent
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A new method for the preparation of various 1,3-dicarbonyl compounds is described.Oxidation of 3-hydroxycarbonyl compounds without substituent at C-2 position by the Corey-Kim reagent (N-chlorosuccinimide-dimethyl sulfide) afforded the stable dimethylsulfonium methylides, which on reductive desulfurization by zinc-acetic acid furnished the 1,3-dicarbonyl derivatives.On the other hand, the same treatment of 2-mono-, or 2,2-disubstituted 3-hydroxy-carbonyl compounds gave directly the corresponding 1,3-dicarbonyl analogous, respectively.
- Katayama, Sadamu,Fukuda, Kinue,Watanabe, Toshio,Yamauchi, Masashige
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p. 178 - 183
(2007/10/02)
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- The Crystallographic Characterization of an Unusual Chemical Reversal of Photoisomerization
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Imines formed from pinacolone and primary amines could be acylated by acid chlorides or anhydrides to products hydrolysable to 1,3-diones.Benzoyl chloride with pinacolone benzylimine gave 3-(N-benzoyl-N-benzylamino)-4,4-dimethyl-1-phenylpent-2-en-1-one, both geometrical isomers of which were prepared.The yellow Z isomer was converted into the colourless E isomer on exposure to daylight and this change was reversed by brief treatment of the E isomer with aqueous ethanolic alkali.The Z and E isomers have been characterized crystallographically.The E isomer is monoclinic, C2/c, a 10.241(4), b 17.199(6), c 25.495(9) Angstroem, β 100.45(3) deg, Z = 8; R was 0.052 for 1947 'observed reflections.The Z-isomer is orthorhombic, P212121, a 18.24(1), b 15.60(1), c 7.871(4) Angstroem, Z = 4; R was 0.61 for 902 'observed' reflections.
- Cornforth, John,Patrick, Vincent A.,White, Allan H.
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p. 1453 - 1460
(2007/10/02)
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- Use of β-Ketocarboxylic Acids for Syntheses of 6-Substituted 4-Hydroxy-2-pyrones and Acyclic β-Diketones
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β-Ketocarboxylic acids including β-ketoglutaric acid half-esters were cyclized by treating them with 1,1'-carbonyl-diimidazole to give 6-substituted 3-acyl-4-hydroxy-2-pyrones in good yields. 5-Aryl-3,5-dioxo-1-pentanoic acid and monomethyl malonate gave 6-aryl-4-hydroxy-2-pyrone and dimethyl β-ketoglutarate, respectively, on similar treatment.Anibin, one of the Aniba alkaloids, was synthesized from 5-(3-pyridyl)-4-hydroxy-2-pyrone.In addition, it was confirmed that reaction of magnesium β-ketocarboxylate with acylimidazolide gave the corresponding acyclic β-diketone in excellent yield.Keywords - β-ketocarboxilic acid; biogenetic-type synthesis; 4-hydroxy-2-pyrone; β-polyketide; β-ketoglutaric acid; dehydroacetic acid; anibin; Aniba alkaloid; 3-acyl-4-hydroxy-2-pyrone; β-diketone.
- Ohta, Shunsaku,Tsujimura, Atsuhiko,Okamoto, Masao
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p. 2762 - 2768
(2007/10/02)
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