- Catalyst-Free and Transition-Metal-Free Approach to 1,2-Diketones via Aerobic Alkyne Oxidation
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A catalyst-free and transition-metal-free method for the synthesis of 1,2-diketones from aerobic alkyne oxidation was reported. The oxidation of various internal alkynes, especially more challenging aryl-alkyl acetylenes, proceeded smoothly with inexpensive, easily handled, and commercially available potassium persulfate and an ambient air balloon, achieving the corresponding 1,2-diketones with up to 85% yields. Meanwhile, mechanistic studies indicated a radical process, and the two oxygen atoms in the 1,2-diketons were most likely from persulfate salts and molecular oxygen, respectively, rather than water.
- Shen, Duyi,Wang, Hongyan,Zheng, Yanan,Zhu, Xinjing,Gong, Peiwei,Wang, Bin,You, Jinmao,Zhao, Yulei,Chao, Mianran
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p. 5354 - 5361
(2021/05/05)
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- Palladium-Catalyzed Synthesis of 1,2-Diketones from Aryl Halides and Organoaluminum Reagents Using tert-Butyl Isocyanide as the CO Source
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In this work, an interesting and practical procedure for the synthesis of 1,2-diketones from aryl halides and organoaluminum reagents has been developed. Employing tert-butyl isocyanide as the CO source and palladium as the catalyst, the desired 1,2-diketones were isolated in good to excellent yields with good functional group tolerance. Concerning the reaction partners, besides aryl halides, both alkyl- A nd arylaluminum reagents were all suitable substrates here.
- Chen, Bo,Wu, Xiao-Feng
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supporting information
p. 636 - 641
(2020/01/31)
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- Synthetic method of 1,2-diketone compound
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The invention discloses a synthetic method of a 1,2-diketone compound. The method comprises the following steps: under room temperature, an alkyne compound is taken as a raw material, a Ru/C is takenas a catalyst, an oxidizing agent and sulfuric acid are added, acetonitrile and water with a volume ratio being 1-5:1 are taken as solvents, the materials are completely reacted at the temperature of20-30 DEG C, and a reaction solution is subjected to separating and purifying to obtain the 1,2-diketone compound. The method has the advantages that operation is simple, reaction time is short, yield(achieving to 100%) is high, substrate universality is wide, water and acetonitrile are taken as the primary solvents (the solvent acetonitrile is easily recovered and used), and a heterogeneous phase catalyst Ru/C is easily recovered. The synthetic method of the 1,2-diketone compound accords with green chemistry characteristic, and is very suitable for industrialization.
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Paragraph 0051-0054
(2018/06/14)
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- Synthesis of a new class of cationic Pd(II) complexes with 1,2,3-triazol-5-ylidene ligand and their catalytic application in the conversion of internal alkynes to 1,2-diketones
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A new class of cationic Pd(II) complexes of the type [Pd(Tz)(Cl)(bipy)]+Cl? and [Pd (Tz)(Cl)(phen)]+Cl? (Tz = 1,4-diaryl-3-methyl-1,2,3-triazol-5-ylidene, bipy = 2,2′-bipyridine and phen = 1,10-phenanthroline) with various wing tip groups were synthesized from the corresponding 1,2,3-triazolium iodide via the corresponding chloro bridged dinuclear complexes [(Tz)(Cl)Pd(μ-Cl)2Pd(Cl)(Tz)]. The synthesized cationic complexes were screened for their catalytic activity of hydration of alkynes and found to be excellent towards the selective conversion of internal alkynes to the corresponding 1,2-diketones in good yields. A plausible mechanism was proposed for this conversion.
- Shaik, Jeelani Basha,Ramkumar, Venkatachalam,Sankararaman, Sethuraman
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supporting information
p. 1 - 8
(2018/02/19)
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- A Desulfonylative Approach in Oxidative Gold Catalysis: Regiospecific Access to Donor-Substituted Acyl Gold Carbenes
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Donor-substituted acyl gold carbenes are challenging to access selectively by gold-promoted intermolecular oxidation of internal alkynes as the opposite regioisomers frequently predominate. By using alkynyl sulfones or sulfonates as substrates, the oxidative gold catalysis in the presence of substituted pyridine N-oxides offers regiospecific access to acyl/aryl, acyl/alkenyl, and acyl/alkoxy gold carbenes by in situ expulsion of sulfur dioxide. The intermediacies of these reactive species are established by their reactivities, including undergoing further oxidation by the same oxidant, cyclopropanation of styrenes, engaging in a [3+2] cycloaddition with α-methylstyrene, and conversion into dienones. Accept it: A desulfonylative approach was developed to regiospecifically access these underexplored acyl gold carbenes from either alkynyl aryl/alkenyl sulfones or alkynyl sulfonate substrates. The reactivities of these donor- and acceptor-substituted carbenes are examined.
- Chen, Hongyi,Zhang, Liming
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p. 11775 - 11779
(2015/10/05)
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- Nitroaldol (Henry) reaction of 2-oxoaldehydes with nitroalkanes as a strategic step for a useful, one-pot synthesis of 1,2-diketones
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The nitroaldol (Henry) reaction of 2-oxoaldehydes with a variety of nitroalkanes, under basic heterogeneous conditions and microwave irradiation, affords 1,2-diketones in a one-pot way. The key step of the process involves the nitrous acid elimination fro
- Palmieri, Alessandro,Gabrielli, Serena,Sampaolesi, Susanna,Ballini, Roberto
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p. 36652 - 36655
(2015/05/05)
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- A highly efficient catalyst for selective oxidative scission of olefins to aldehydes: Abnormal-NHC-Ru(II) complex in oxidation chemistry
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The utility and selectivity of the catalyst [Ru(COD)(L1)Br2] (1) bearing a fused π-conjugated imidazo[1,2-a][1,8]naphthyridine-based abnormal N-heterocyclic carbene ligand L1 is demonstrated toward selective oxidation of C=C bonds to aldehydes and C=C bonds to α-diketones in an EtOAc/CH3CN/H2O solvent mixture at room temperature using a wide range of substrates, including highly functionalized sugar- and amino acid-derived compounds.
- Daw, Prosenjit,Petakamsetty, Ramu,Sarbajna, Abir,Laha, Siladitya,Ramapanicker, Ramesh,Bera, Jitendra K.
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supporting information
p. 13987 - 13990
(2015/01/08)
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- Carbon–carbon bond formation via benzoyl umpolung attained by photoinduced electron-transfer with benzimidazolines
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A photoreaction between benzoyl compounds, such as benzoylformate derivatives, and 2-(p-anisyl)-1,3-dimethylbenzimidazoline in the presence of allyl bromide was found to give various allylated alcohols. In the reaction of benzoylformates, α-hydroxy ester enolates, for which the negative charge occurs on the carbonyl carbon of benzoyl (umpolung reactivity), are proposed to be generated as intermediates by electron-transfer from benzimidazolines to the photoexcited benzoylformates; these species react with allyl bromide to produce α-allyl-α-hydroxy esters.
- Igarashi, Tomohito,Tayama, Eiji,Iwamoto, Hajime,Hasegawa, Eietsu
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supporting information
p. 6874 - 6877
(2019/04/10)
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- Palladium-catalyzed carbonation-diketonization of terminal aromatic alkenes via carbon-nitrogen bond cleavage for the synthesis of 1,2-diketones
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A palladium-catalyzed carbonation-diketonization reaction of terminal alkenes via carbon-nitrogen bond cleavage under an atmosphere of oxygen has been developed. A series of 1,2-diketones were readily prepared from the reaction of aromatic terminal alkenes with nitroalkanes.
- Wang, Azhong,Jiang, Huanfeng,Li, Xianwei
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supporting information; experimental part
p. 6958 - 6961
(2011/10/02)
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- Gold-catalyzed oxidation of arylallenes: Synthesis of quinoxalines and benzimidazoles
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A gold-catalyzed oxidation of arylallenes to form α-diketones and aldehydes in good yields is presented. Further directed synthesis of quinoxalines and benzimidazoles, via the condensation of the resulting α-diketones and aldehydes with benzene-1,2-diamine, was achieved in high yields.
- Cui, Dong-Mei,Zhuang, Dan-Wen,Chen, Ying,Zhang, Chen
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experimental part
p. 860 - 865
(2011/08/05)
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- Ruthenium-catalyzed alkyne oxidation with part-per-million catalyst loadings
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Using a catalytic system of the (cymene)ruthenium dichloride dimer, [Ru(cymene)Cl2]2, (0.001 mol%) and iodine (10 mol%), a variety of alkynes bearing different functional groups were oxidized with tert-butyl hydroperoxide (TBHP; 70% solution in water) under mild conditions to give 1,2diketones in good to excellent yields. Two noteworthy features of the method are the extremely high catalyst productivity (TON up to 420,000) and scale-up to 1 mol. Preliminary mechanism investigations showed that iodonium ion and water were involved in the transformation.
- Ren, Wei,Liu, Jinfeng,Chen, Long,Wan, Xiaobing
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supporting information; experimental part
p. 1424 - 1428
(2010/08/19)
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- Synthesis of 1,2-diketones by the transition metal-catalyst-free reaction of α-oxo acid chlorides or oxalyl chloride with organostannanes
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(Chemical Equation Presented) The reaction of an α-oxo acid chloride with an organostannane proceeds transition metal-catalyst-free to afford a 1,2-diketone in an excellent yield. In addition, a sequence comprising pretreatment of oxalyl chloride with an
- Kashiwabara, Taigo,Tanaka, Masato
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supporting information; experimental part
p. 3958 - 3961
(2009/09/26)
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- One-Pot Synthesis of Unsymmetrical Ketones by the Reaction of Decacarbonyldimanganese with Two Kinds of Alkyllithiums
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Decacarbonyldimanganese (Mn2(CO)10) is utilized as a phosgene equivalent for the one-pot preparation of unsymmetrical ketones. By a successive treatment of Mn2(CO)10 with two kinds of alkyllithiums, unsymmetrical ketones are obtained in high selectivity. Unsymmetrical α-diketones are generated when the above reaction is carried out in the presence of trimethyl phosphite and is quenched with N-bromosuccinimide.
- Yamamoto, Hiroshi M.,Sakurai, Hidehiro,Narasaka, Koichi
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p. 157 - 161
(2007/10/03)
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- Synthesis of Symmetrically and Unsymmetrically Substituted α-Diones from Organometallic Reagents and 1,4-Dialkylpiperazine-2,3-diones
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The reaction of an equimolar mixture of N,N'-dialkylethylenediamines and diethyl oxalate in diethyl ether or 2-propanol leads to 1,4-dialkylpiperazine-2,3-diones.As cyclic and nearly planar tetraalkyl oxamides, these compounds are able to react with 2 equiv of organolithium or Grignard compounds to form, after hydrolysis, symmetrically substituted α-diones in excellent yields.The sequential addition of 1 equiv each ot two different organolithium compounds affords unsymmetrically substituted α-diones when the more soluble longer chain dialkyl derivatives of piperazine-2,3-dione are employed.The dialkylethylenediamines can conveniently be recovered and recycled to the 1,4-dialkylpiperazine -2,3-diones in good yields.
- Mueller-Westerhoff, Ulrich T.,Zhou, Ming
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p. 4988 - 4992
(2007/10/02)
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- A simple synthesis of symmetrical α-diones from organometallic reagents and 1,4-dimethyl-piperazine-2,3-dione
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Short reflux of an equimolar mixture of N-N′-dimethyl ethylenediamine and diethyl oxalate in ipropanol or diethyl ether leads to 1,4-dimethyl-piperazine-2,3-dione, which is able to react with two equivalent of organolithium or Grignard compounds to form symmetrically substituted α-diones in excellent yields.
- Mueller-Westerhoff, Ulrich T.,Zhou, Ming
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p. 571 - 574
(2007/10/02)
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- Synthesis of α-Diketones by Direct, Low-temperature, in Situ Nucleophilic Acylation of Esters by Acyllithium Reagents
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Addition of n-, sec-, or tert-butyllithium to a CO-saturated solution of an ester, R'CO2R'' in a solvent system of 4:4:1 (by volume) THF/Et2O/pentane at -110 deg C (or at -135 deg C in 3:1 (by volume) Me2O/THF), followed by hydrolysis with saturated aqueous NH4Cl, results in the formation of α-diketones, BuC(O)C(O)R', yellow liquids, in good yield.Similar reactions with diethyl succinate gave in one instance both t-BuC(O)C(O)CH2CH2CO2Et and t-BuC(O)C(O)CH2CH2C(O)C(O)Bu-t.The monoacylation product of dimethyl oxalate, t-BuC(O)C(O)CO2Me, readily formed a crystalline hydrate, t-BuC(O)C(OH)2CO2Me.
- Seyferth, Dietmar,Weinstein, Robert M.,Hui, Richard C.,Wang, Wei-Liang,Archer, Colin M.
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p. 5768 - 5773
(2007/10/02)
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- A Novel Oxidation of Internal Alkynes with Hydrogen Peroxide Catalyzed by Peroxotungsten Compounds
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Internal alkynes underwent a novel oxidation with aqueous hydrogen peroxide catalyzed by peroxotungsten compounds under two-phase conditions using chloroform as the solvent, giving α,β-epoxy ketones and α,β-unsaturated ketones as principal products.The epoxidation of α,β-unsaturated ketones by this catalyst-oxidant system appeared to involve the electrophilic attack of the peroxo species to the double bond.
- Ishii, Yasutaka,Sakata, Yasuyuki
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p. 5545 - 5547
(2007/10/02)
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- A Simple and Improved Procedure for the Conversion of Alkynes to 1,2-Diketones by Indirect Electrooxidation With Ruthenium Tetroxide as a Mediator
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Indirect electrooxidation of alkynes 1 using ruthenium tetroxide as a mediator, leading to 1,2-diones 2 in 72-87percent, is described.The electrolysis is carried out in the presence of a catalytic amount of ruthenium dioxide dihydrate in a two phase system of saturated aqueous sodium chloride and carbon tetrachloride.The overoxidation of 1,2-diones to the corresponding carboxylic acid, an unavoidable drawback generally encountered in the metal oxidation of acetylenes, is suppressed greatly by maintaining the pH of the aqueous phase at 4 and conducting the reaction at 0-5 deg C.The synthetic utility of this electrochemical oxidation is exemplified by the preparation of 2i (82percent), a key intermediate for the synthesis of furaneol 4, from the commercially available 1i.
- Torii, Sigeru,Inokuchi, Tsutomu,Hirata, Youzou
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p. 377 - 379
(2007/10/02)
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- UMWANDLUNG VON α-AMINOSAEUREN IN α-DIKETONE UEBER OXAZOLINZWISCHENSTUFEN
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A four step sequence for the conversion of α-amino acids into α-diketones under mild conditions is desribed.
- Leyendecker, Joachim,Niewoehner, Ulrich,Steglich, Wolfgang
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p. 2375 - 2378
(2007/10/02)
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- High-Yield Acyl Anion Trapping Reactions: Syntheses of α-Hydroxy Ketones and 1,2-Diketones
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The in situ generation of n-C4H9C(O)Li by the reaction of n-C4H9Li with CO at -110 deg C in the presence of ketones gives good (50-90percent) yields of α-hydroxy ketones.When the n-C4H9C(O)Li reaction is carried out in the presence of esters, good (65-80percent) yields of α-diketones are obtained, thus demonstrating that RC(O)Li can be reagents of practical utility.Similar reactions were observed with sec-C4H9Li and tert-C4H9Li.
- Seyferth, Dietmar,Weinstein, Robert M.,Wang, Wei-Liang
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p. 1144 - 1146
(2007/10/02)
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