- Palladium-catalysed addition of potassium phenyltrifluoroborate to dinitriles: Synthesis of diketone compounds
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Pd(OAc)2/1,10-phenanthroline-catalysed addition of potassium phenyltrifluoroborate to aliphatic dinitriles in 2-MeTHF has been developed, achieving diphenyl diones in moderate to excellent yields. The scope of the developed approach was successfully explored toward the addition of potassium phenyltrifluoroborate to aromatic dinitriles. Additionally, a plausible pathway for the formation of the diones has been proposed.
- Wang, Xingyong,Wang, Qingzong,Chen, Jiuxi,Liu, Miaochang,Ding, Jinchang,Wu, Huayue
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- Kinetics of the substitution of β-Diketones in β-diketonato(1,5-cyclooctadiene)rhodium(I) complexes by benzoyl-1,1,1-trifluoroacetone
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The kinetics and mechanism of the reactions between and trifluorobenzoylacetone (TFBA) to give have been studied in a petroleum-ether medium at various temperatures with UV spectroscopy.The rate law is -d/dt=(ks+ky) and the reaction is shown to proceed via an associative mechanism.The value of ks and ky were determined for various β-diketone complexes with β-diketone=acac, BA, DBM, TFAA and HFAA.The reactivities of the complexes fall as the β-diketone is varied in the sequence BA>acac>DBM>TFAA>HFAA, indicating that electronegative substituents in the β-diketone increase the trans-effect and therefore the strength of the Rh-O bonds.Since the ring opening is the rate-determining step in the reaction.It can be concluded that the complex containing the β-diketone with the largest trans-effect, which gives rise to the strongest Rh-O bonds, will undergo the slowest substitution.The effect of the substituents of the β-diketone (CF3, phenyl and CH3) on the trans-effect is discussed.
- Potgieter, J. H.
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- An alternative route to 1,3-diketones promoted by samarium diiodide
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Sml2 promoted condensation of α-haloketones with carboxylic acid chlorides or anhydrides leads to 1,3-diketones.
- Ying, Taokai,Bao, Weiliang,Zhang, Yongmin,Xu, Weinming
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- Copper-catalyzed domino synthesis of 2-imino-1H-imidazol-5(2H)-ones and Quinoxalines involving C-C bond cleavage with a 1,3-dicarbonyl unit as a leaving group
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Although 2-imino-1H-imidazol-5(2H)-ones have important biological activities in metabolism, their synthesis has rarely been investigated. Quinoxalines as privileged scaffolds in medicinal chemistry have been extensively investigated, but the development of novel and efficient synthetic methods remains very attractive. Herein, we have developed two copper-catalyzed domino reactions for the synthesis of 2-imino-1H-imidazol-5(2H) -ones and quinoxalines involving C-C bond-cleavage with a 1,3-dicarbonyl unit as a leaving group. The domino sequence for the synthesis of 2-imino-1H-imidazol- 5(2H)-ones includes aza-Michael addition, intramolecular cyclization, C-C bond-cleavage, 1,2-rearrangement, and aerobic dehydrogenation reaction, whereas the domino sequence for the synthesis of quinoxalines includes aza-Michael addition, intramolecular cyclization, elimination reaction, and C-C bond-cleavage reaction. The two domino reactions have significant advantages including high efficiency, mild reaction conditions, and high tolerance of various functional groups.
- Yang, Yan,Ni, Fan,Shu, Wen-Ming,Wu, An-Xin
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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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- STRUCTURE OF THE PRODUCTS OF THE REACTION OF 5,6-DIAMINO-1,3-DIMETHYLURACIL WITH 1,3-DIARYL-2,3-DIHALOPROPANONES
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The reaction of 5,6-diamino-1,3-dimethyluracil with α,β-dihalopropanones gives only β-(5-imino-6-amino-1,3-uracil)chalcones.An x-ray diffraction structural analysis was carried out for one of these products.
- Kolos, N. N.,Shishkin, O. V.,Orlov, V. D.,Struchkov, Yu. T.
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- Synthesis and application of 2,6-dicarboxy pyridinium fluorochromate as a new solid-phase oxidant
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2,6-Dicarboxypyridinium fluorochromate (2,6-DCPFC) was prepared and used for oxidation of alcohols, phenols, and hydroquinones under solvent-free conditions. This new compound is more efficient and has certain advantages over similar oxidizing agents in terms of the amount of oxidant, lack of solvent, short reaction times, and high yields. Copyright Taylor & Francis, Inc.
- Tajbakhsh,Hosseinzadeh,Sadatshahabi
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- β-Diketone synthesis by reaction of α-haloketones with acid chlorides or acid anhydrides promoted by samarium triiodide
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Promoted by SmI3, α-haloketones were reacted with acid chlorides or acid anhydrides and β-diketones were synthesized via intermediate samarium enolates.
- Ying, TaoKai,Bao, Weiliang,Zhang, Yongmin
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- Enamines as Surrogates of Alkene Carbanions for the Reductive Alkenylation of Secondary Amides: An Approach to Allylamines
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A new strategy to construct allylamines through reductive alkenylation of secondary amides with enamines is reported. The method features the use of trifluoromethanesulfonic anhydride as an activation reagent of amides, and enamines as unconventional alkenylation reagents. In this manner, enamines serve as surrogates of alkene carbanions instead of the classical enolates equivalents. A possible mechanism involving a Hoffmann-like elimination of the amine-borane complex intermediate is proposed.
- Wang, Ai-E,Yu, Cun-Cun,Chen, Ting-Ting,Liu, Yong-Peng,Huang, Pei-Qiang
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- Acylsilanes and C-Stannylimines as Anion Equivalents
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Acylsilanes and C-stannylimines react with organic halides in the presence of KF-18-crown-6 ether to give ketones and ketimines, respectively.
- Degl'Innocenti, Alessandro,Pike, Stephen,Walton, David R. M.,Seconi, Giancarlo,Ricci, Alfredo,Fiorenza, Mariella
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- Chemo- and regioselective preparation and reaction of a kinetic zinc enolate formed from a thiol ester and bis(iodozincio)methane
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(Chemical Equation Presented) Reactive functionalized enolates that are otherwise difficult to obtain can be prepared in a simple procedure by the treatment of a thiol ester with bis(iodozincio)methane in the presence of a palladium catalyst (see scheme). The terminal zinc enolates thus formed are kinetically controlled and react with a variety of electrophiles, such as aldehydes, ketones, and acyl cyanides. FG = functional group.
- Ikeda, Zenichi,Hirayama, Takaharu,Matsubara, Seijiro
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- Preparation of 1,3-diketones by the reaction of bis(iodozincio)methene with acyl cyanides or palladium-catalyzed reaction with acyl chlorides
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Bis(iodozincio)methane, prepared from lead-catalyzed reaction of zinc with diiodomethane, afforded 1,3-diketones either by the reaction with acyl cyanides or by palladium catalyzed reaction with acyl chlorides. Reaction with adipoyl dichloride gave cyclic enol ester by intramolecular reaction.
- Matsubara, Seijiro,Kawamoto, Kazunari,Utimoto, Kiitiro
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- Direct Access to 1,1-Dicarbonyl Sulfoxonium Ylides from Aryl Halides or Triflates: Palladium-Catalyzed Carbonylation
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The synthesis of 1,1-dicarbonyl sulfoxonium ylides by palladium-catalyzed carbonylation of aryl halides or triflates with α-carbonyl sulfoxonium ylides has been developed for the first time. This method provides a general approach to synthetically useful 1,1-dicarbonyl sulfoxonium ylides in high efficiency. The protocol displays a wide substrate scope, showing that the resulting 1,1-dicarbonyl sulfoxonium ylides have been converted into the corresponding 1,3-dicarbonyl compounds.
- Yuan, Yang,Wu, Xiao-Feng
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- Lanthanoid complexes supported by retro-Claisen condensation products of β-triketonates
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β-Triketonates have been recently used as chelating ligands for lanthanoid ions, presenting unique structures varying from polynuclear assemblies to polymers. In an effort to overcome low solubility of the complexes of tribenzoylmethane, four β-triketones with higher lipophilicity were synthesised. Complexation reactions were performed for each of these molecules using different alkaline bases in alcoholic media. X-ray diffraction studies suggested that the ligands were undergoing decomposition under the reaction conditions. This is proposed to be caused by in situ retro-Claisen condensation reactions, consistent with two examples that have been reported previously. The lability of the lanthanoid cations in the presence of a varying set of potential ligands gave rise to structures where one, two, or three of the molecules involved in the retro-Claisen condensation reaction were linked to the lanthanoid centres. These results, along with measurements of ligand decomposition in the presence of base alone, suggest the solvent used will modulate the impact of the retro-Claisen condensation in these complexes.
- Abad Galán, Laura,Sobolev, Alexandre N.,Zysman-Colman, Eli,Ogden, Mark I.,Massi, Massimiliano
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- The regioselective preparation of 1,3-diketones within a micro reactor
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We demonstrate a simple method for the regioselective preparation of 1,3-diketones within a micro reactor from silyl enol ethers where the products are free from both competing O-acylation and diacylation products.
- Wiles, Charlotte,Watts, Paul,Haswell, Stephen J.,Pombo-Villar, Esteban
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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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- The regioselective preparation of 1,3-diketones
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The regioselectivity of the acylation of Li enolates and silyl enol ethers is reported using acyl halides and acyl cyanides. We illustrate a simple method for the preparation of 1,3-diketones via the silyl enol ether in excellent yields, free from competing O-acylation and diacylation products.
- Wiles, Charlotte,Watts, Paul,Haswell, Stephen J.,Pombo-Villar, Esteban
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- Br?nsted acid-catalyzed enantioselective addition of 1,3-diones to in situ generated N-acyl ketimines
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A Br?nsted acid-catalyzed asymmetric Mannich-type addition of 1,3-diones to cyclic N-acyl ketimines is reported for the synthesis of enantioenriched isoindolinones. Various dicarbonyl-substituted isoindolinones bearing a quaternary carbon stereocenter were synthesized with excellent yields (up to 98%) and moderate to high enantioselectivities (up to 95% ee), and most of them possess a fluorine atom at the reactive center. Furthermore, the synthetic utility of the protocol has been demonstrated by the debenzoylation of the product.
- Ray, Sumit K.,Sadhu, Milon M.,Singh, Vinod K.,Unhale, Rajshekhar A.
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supporting information
p. 410 - 414
(2022/01/20)
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- PPh3-catalyzed β-selective addition of α-fluoro β-dicarbonyl compounds to allenoates
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A highly selective phosphine-catalyzed β-addition of α-fluoro β-dicarbonyl compounds to allenoates has been developed. Both α-fluoro β-diketones and α-fluoro β-keto esters prove to be competent fluorocarbon nucleophiles, giving a series of the β-addition products bearing a fluorinated quaternary carbon center in good to excellent yields and with excellent regioselectivities. A plausible reaction pathway is presented.
- Liu, Yong-Liang,Wang, Xiao-Ping,Wei, Jie,Li, Ya
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supporting information
(2021/12/02)
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- Discovery of pyrazole N-aryl sulfonate: A novel and highly potent cyclooxygenase-2 (COX-2) selective inhibitors
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Based on a new pyrazole sulfonate synthetic method, a novel class of molecules with a basic structure of pyrazole N-aryl sulfonate have been designed and synthesized. The interest in conducting intensive research stems from quite evident anti-inflammatory effects exhibited by the compounds in preliminary animal experiments. A series of compounds were synthesized by different substitutions of the R1, R2, and R3 groups. Within the series, 4-iodophenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate and phenyl 5-methyl-3-(4-(trifluoromethyl) phenyl)-1H-pyrazole-1-sulfonate exhibited excellent anti-inflammatory activity (% inhibition of auricular edemas = 27.0 and 35.9, respectively); the in vivo analgesic activity of phenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate and 2-chlorophenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate was confirmed to be effective (inhibition ratio of writhing = 50.7% and 48.5% separately), and compounds phenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate, 4-iodophenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate and 2-chlorophenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate were identified as selective COX-2 inhibitors (SI = 455, 10,497 and >189 severally). In Acute Oral Toxicity assays conducted in vivo, the lethal dose 50 (LD50) of 4-iodophenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate and 2-chlorophenyl 5-methyl-3-(p-tolyl)-1H-pyrazole-1-sulfonate to mice was >2000 mg/kg BW.
- Guo, Quanping,Wang, Mengran,Wang, Rui,Xu, Zhaoqing,Yao, Haiyan
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- Synthesis of Highly Substituted Biaryls by the Construction of a Benzene Ring via in Situ Formed Acetals
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Herein, we present an interesting method for the construction of a benzene ring using propargylic alcohols and 1,3-dicarbonyls, which involves three new C-C bond formations via cascade alkylation, formylation, annulation, and aromatization to make substituted biaryls. This one-pot Br?nsted acid-promoted protocol utilizes the unique reactivity of the acetal formed under the reaction conditions. Alkynyl methyl ketones could be employed instead of 1,3-dicarbonyls as they are converted to 1,3-dicarbonyls by hydration under the reaction conditions.
- Balamurugan, Rengarajan,Manojveer, Seetharaman,Tarigopula, Chandrahas
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p. 11871 - 11883
(2021/09/13)
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- Organocatalytic Asymmetric Cascade Michael-acyl Transfer Reaction between 2-Fluoro-1,3-diketones and Unsaturated Thiazolones: Access to Fluorinated 4-Acyloxy Thiazoles
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Quinine derived bifunctional urea catalyzed cascade Michael-acyl transfer reaction of 5-alkenyl thiazolones and monofluorinated β-diketones has been developed. The fluorine containing 4-acyloxy thiazoles were synthesized in high yields and good diastereo-and excellent enantioselectivities. Synthetic transformations, including synthesis of 4-hydroxy thiazoles, have been demonstrated.
- Biswas, Rayhan G.,Ray, Sumit K.,Unhale, Rajshekhar A.,Singh, Vinod K.
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supporting information
p. 6504 - 6509
(2021/08/30)
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- Rhodium-Catalyzed Aerobic Decomposition of 1,3-Diaryl-2-diazo-1,3-diketones: Mechanistic Investigation and Application to the Synthesis of Benzils
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The conversion of 1,3-diaryl-2-diazo-1,3-diketones to 1,2-daryl-1,2-diketones (benzils) is reported based on a rhodium(II)-catalyzed aerobic decomposition process. The reaction occurs at ambient temperatures and can be catalyzed by a few dirhodium carboxylates (5 mol %) under a balloon pressure of oxygen. Moreover, an oxygen atom from the O2 reagent is shown to be incorporated into the product, and this is accompanied by the extrusion of a carbonyl unit from the starting materials. Mechanistically, it is proposed that the decomposition may proceed via the interaction of a ketene intermediate resulting from a Wolff rearrangement of the carbenoid, with a rhodium peroxide or peroxy radical species generated upon the activation of molecular oxygen. The proposed mechanism has been supported by the results from a set of controlled experiments. By using this newly developed strategy, a large array of benzil derivatives as well as 9,10-phenanthrenequinone were synthesized from the corresponding diazo substrates in varying yields. On the other hand, the method did not allow the generation of benzocyclobutene-1,2-dione from 2-diazo-1,3-indandione because of the difficulty of inducing the initial rearrangement.
- Zhu, Jia-Liang,Tsai, Yi-Ting
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p. 813 - 828
(2020/12/22)
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- Tris-(2-pyridylmethyl)amine-ligated Cu(II) 1,3-diketonate complexes: Anaerobic retro-Claisen and dehalogenation reactivity of 2-chloro-1,3-diketonate derivatives
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We report synthetic, structural and reactivity investigations of tris-(2-pyridylmethyl)amine (TPA)-ligated Cu(ii) 1,3-diketonate complexes. These complexes exhibit anaerobic retro-Claisen type C-C bond cleavage reactivity which exceeds that found in analo
- Elsberg, Josiah G. D.,Anderson, Stephen N.,Tierney, David L.,Reinheimer, Eric W.,Berreau, Lisa M.
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p. 1712 - 1720
(2021/02/22)
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- Electrochemical Oxidative Cyclization: Synthesis of Polysubstituted Pyrrole from Enamines
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A conceptually novel method for the preparation of pyrrole is described by electrochemical-oxidation-induced intermolecular annulation via enamines. In a simple undivided cell, based on a sodium acetate-facilitated, polysubstituted pyrrole derivations has been facilely synthesized under external oxidant-free condition. This electrosynthetic approach providing an environmentally benign protocol for C?C bond cross-coupling and oxidative annulation, which features unparalleled broad scope of substrates and practicality.
- Chen, Zhiwei,Shi, Guang,Tang, Wei,Sun, Jie,Wang, Wenxing
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supporting information
p. 951 - 955
(2021/02/03)
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- NOVEL ORGANIC COMPOUND AND MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES COMPRISING THE SAME AND ORGANIC ELECTROLUMINESCENT DEVICES COMPRISING THE SAME
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The present invention provides a novel organic compound represented by chemical formula 1, a material for an organic electroluminescent device including the organic compound, and an organic electroluminescent device. The present invention can improve color purity and device life.
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Paragraph 0152; 0193-0196
(2020/12/16)
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- Non-metal catalytic method for preparing 1,3-diketone compounds based on acetyenic ketone
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The invention discloses a non-metal catalytic method for preparing 1,3-diketone compounds based on acetyenic ketone. The preparation method is a stepwise method or a one-pot method. The stepwise method comprises the following steps: mixing an acetyenic ketone compound I, a nitrogen-containing aromatic compound II and a No.1 base for a reaction, performing separation and purification to obtain an intermediate product, mixing the intermediate product and a No.2 base for a reaction, and performing separation and purification to obtain the product; and the one-pot method comprises the following steps: firstly mixing an acetyenic ketone compound I and a nitrogen-containing aromatic compound II, adding a No.1 base, performing a reaction for a period of time, adding a No.2 base, continuing a reaction for a period of time, and finally performing separation and purification to obtain the product. The method provided by the invention has mild reaction conditions, simple operation and a higher yield, wherein the yield is generally 80% or more, and the method has greater practical application value in drug synthesis.
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- Regio-and stereoselective C(sp2)-H acylation of enamides with aldehydes: Via transition-metal-free photoredox catalysis
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A straightforward and efficient C(sp2)-H acylation of enamides with aldehydes via transition-metal-free photoredox catalysis is demonstrated. The transformation proceeded smoothly without resorting to expensive and potentially toxic iridium or ruthenium polypyridyl-based photocatalysts under mild conditions, furnishing a diverse range of synthetically crucial, geometrically defined β-acylated enamides in a stereoselective and regioselective manner. This journal is
- Li, Wei-Ming,Loh, Teck-Peng,Tao, Ji-Yu,Wu, Jia-Xu,Wu, Xian-Dan,Zhang, Xiao-Chen,Zhao, Kai,Zhu, Tong-Hao
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p. 5497 - 5503
(2020/09/17)
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- Direct synthesis of 2,3,5-trisubstituted pyrroles: via copper-mediated one-pot multicomponent reaction
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We have developed a copper-mediated one-pot synthesis of 2,3,5-trisubstituted pyrroles from 1,3-dicarbonyl compounds and acrylates using ammonium acetate as a nitrogen source. The reaction achieves C-C and C-N bond formation and provides an efficient approach to access highly functionalized pyrroles without further raw material preparation. This method is operationally simple, compatible with a wide range of functional groups, and provides the target products in moderate to good yields. This journal is
- He, Jian-Ping,Huang, Guo-Sheng,Luo, Nan,Zhan, Zhen-Zhen,Zhang, Ming-Ming
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supporting information
p. 9831 - 9835
(2021/01/05)
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- Metal-Free Synthesis of Indolopyrans and 2,3-Dihydrofurans Based on Tandem Oxidative Cycloaddition
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The synthesis of versatile scaffold indolopyrans based on C-C radical-radical cross-coupling under metal-free conditions is described. The reaction involving single electron transfer between coupling partners followed by cage collapse allows highly selective cross-coupling while employing only equimolar amounts of coupling partners. Moreover, the mechanistic manifold was expanded for the functionalization of enamines to give the stereoselective synthesis of 2,3-dihydrofurans. This iodine-mediated oxidative coupling features mild conditions and fast reaction kinetics.
- Choi, Subin,Oh, Hyeonji,Sim, Jeongwoo,Yu, Eunsoo,Shin, Seunghoon,Park, Cheol-Min
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supporting information
p. 5528 - 5534
(2020/07/24)
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- Nucleophilic versus Electrophilic Activation of Hydrogen Peroxide over Zr-Based Metal-Organic Frameworks
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Zr-based metal-organic frameworks (Zr-MOF) UiO-66 and UiO-67 catalyze thioether oxidation in nonprotic solvents with unprecedentedly high selectivity toward corresponding sulfones (96-99% at ca. 50% sulfide conversion with only 1 equiv of H2O2). The reaction mechanism has been investigated using test substrates, kinetic, adsorption, isotopic (18O) labeling, and spectroscopic tools. The following facts point out a nucleophilic character of the peroxo species responsible for the superior formation of sulfones: (1) nucleophilic parameter XNu = 0.92 in the oxidation of thianthrene 5-oxide and its decrease upon addition of acid; (2) sulfone to sulfoxide ratio of 24 in the competitive oxidation of methyl phenyl sulfoxide and p-Br-methyl phenyl sulfide; (3) significantly lower initial rates of methyl phenyl sulfide oxidation relative to methyl phenyl sulfoxide (kS/kSO = 0.05); and (4) positive slope ρ = +0.42 of the Hammett plot for competitive oxidation of p-substituted aryl methyl sulfoxides. Nucleophilic activation of H2O2 on Zr-MOF is also manifested by their capability of catalyzing epoxidation of electron-deficient C═C bonds in α,β-unsaturated ketones accompanied by oxidation of acetonitrile solvent. Kinetic modeling on methyl phenyl sulfoxide oxidation coupled with adsorption studies supports a mechanism that involves the interaction of H2O2 with Zr sites with the formation of a nucleophilic oxidizing species and release of water followed by oxygen atom transfer from the nucleophilic oxidant to sulfoxide that competes with water for Zr sites. The nucleophilic peroxo species coexists with an electrophilic one, ZrOOH, capable of oxygen atom transfer to nucleophilic sulfides. The predominance of nucleophilic activation of H2O2 over electrophilic one is, most likely, ensured by the presence of weak basic sites in Zr-MOFs identified by FTIR spectroscopy of adsorbed CDCl3 and quantified by adsorption of isobutyric acid.
- Chesalov, Yuriy A.,Evtushok, Vasiliy Yu.,Glazneva, Tatyana S.,Ivanchikova, Irina D.,Kholdeeva, Oxana A.,Larionov, Kirill P.,Skobelev, Igor Y.,Zalomaeva, Olga V.
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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
(2020/07/21)
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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 0188-0193
(2019/06/12)
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- 1,2-Diazacyclopentane-3,5-diyl Diradicals: Electronic Structure and Reactivity
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Localized singlet diradicals are key intermediates in bond homolysis. A thorough study of the reactive species is needed to clarify the mechanisms of the homolytic bond cleavage and formation processes. In general, the singlet diradicals are quite short-lived because of the fast radical-radical coupling reactions. The short-lived characteristic has retarded the thorough study on bond homolysis. In this study, a new series of long-lived singlet diradicals, viz., 1,2-diazacyclopentane-3,5-diyl, were identified, and their electronic structures and novel reactivities were thoroughly studied using laser-flash photolysis (LFP), product analysis, and computational studies. A direct observation of the thermal equilibration (fast process) between the singlet diradicals and the corresponding ring-closing compounds was undertaken on the submicrosecond time scale. The solvent and substituent effects on the equilibration constant and rate constants for the ring-closing reaction and ring-opening reaction clarify the novel nitrogen-atom effect on the localized singlet 1,3-diyl diradicals. Two types of alkoxy-migrated compounds, 9 and 10, were isolated with high yields as the final products. Crossover, spin-trapping, and LFP experiments for the formation of alkoxy-group migration products (i.e., 9 versus 10) revealed the unique temperature effect on the product ratio of the two types of alkoxy-migration products. The temperature-insensitive intersystem crossing process (slow process, millisecond time scale) was found to be a key step in the formation of 9, which is an entropy-controlled pathway. An intramolecular migration process was identified for the formation of 10 that was accelerated by a polar solvent in an enthalpy-controlled process. This unique heteroatom effect has opened up a new series of localized singlet diradicals that are crucial intermediates in bond homolysis.
- Yoshidomi, Shohei,Abe, Manabu
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supporting information
p. 3920 - 3933
(2019/03/07)
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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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- Electrochemical oxidative cyclization of olefinic carbonyls with diselenides
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The tandem cyclization of olefinic carbonyls with easily accessible diselenides facilitated by electrochemical oxidation has been successfully developed, which provides an environmentally friendly method for the construction of C-Se and C-O bonds simultaneously. A series of seleno dihydrofurans and seleno oxazolines, bearing fragile heterocycles, subtle C-I bonds and supernumerary vinyl groups, were forged using this elegant chelation strategy. Neither metal catalysts nor external chemical oxidants are required to promote this transformation.
- Guan, Zhipeng,Wang, Yunkun,Wang, Huamin,Huang, Yange,Wang, Siyuan,Tang, Hongding,Zhang, Heng,Lei, Aiwen
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supporting information
p. 4976 - 4980
(2019/09/30)
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- Enolization rates control mono-: Versus di-fluorination of 1,3-dicarbonyl derivatives
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Fluorine-containing 1,3-dicarbonyl derivatives are essential building blocks for drug discovery and manufacture. To understand the factors that determine selectivity between mono- and di-fluorination of 1,3-dicarbonyl systems, we have performed kinetic studies of keto-enol tautomerism and fluorination processes. Photoketonization of 1,3-diaryl-1,3-dicarbonyl derivatives and their 2-fluoro analogues is coupled with relaxation kinetics to determine enolization rates. Reaction additives such as water accelerate enolization processes, especially of 2-fluoro-1,3-dicarbonyl systems. Kinetic studies of enol fluorination with Selectfluor and NFSI reveal the quantitative effects of 2-fluorination upon enol nucleophilicity towards reagents of markedly different electrophilicity. Our findings have important implications for the synthesis of α,α-difluoroketonic compounds, providing valuable quantitative information to aid in the design of fluorination and difluorination reactions.
- Rozatian, Neshat,Beeby, Andrew,Ashworth, Ian W.,Sandford, Graham,Hodgson, David R.W.
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p. 10318 - 10330
(2019/11/20)
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- ONE-STEP, FAST, 18F-19F ISOTOPIC EXCHANGE RADIOLABELING OF DIFLUORO-DIOXABORININS AND USE OF SUCH COMPOUNDS IN TREATMENT
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A compound according to Formula (I) or a pharmaceutically acceptable salt and/or solvate thereof, wherein X1 and X2 are each independently 18F or 19F; R1 and R2 are each independently alkyl, amine, perfluoroalkyl, alkenyl, alkynyl, aryl, or aralkenyl; and R3 is H, halo, alkyl, alkyl ester, alkenyl, alkynyl, aryl, or aralkenyl; or wherein: R1 and R3 or R2 and R3 join to form a 6-membered cycloalkyl or heterocyclyl; or R1 and R3, R2 and R3, or R1, R2, and R3 join to form a substituted or unsubstituted polycyclic ring, wherein the polycyclic ring comprises fused cycloalkyl, heterocycloalkyl, aryl, or heteroaryl rings.
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-
Paragraph 0019; 0204-0205
(2019/12/15)
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- Mild Cu-Catalyzed Oxidation of Benzylic Boronic Esters to Ketones
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The oxidation of benzylic boronic esters directly to the ketone is reported. This mild Cu-catalyzed method uses an ambient atmosphere of air as the terminal oxidant and is notably chemoselective. Oxidation of the C-B bond occurs selectively, even in the presence of unprotected alcohols. Initial investigation suggests the reaction proceeds through an alkylboron to Cu transmetalation, peroxide formation, and rearrangement to give the carbonyl.
- Grayson, James D.,Partridge, Benjamin M.
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p. 4296 - 4301
(2019/05/14)
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- PhIO/Et3N ? 3HF-Mediated Formation of Fluorinated 2H-Azirines via Domino Fluorination/Azirination Reaction of Enamines
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A variety of enamine carboxylic esters and enaminones were converted to the biologically interesting fluorinated 2H-azirines through reactions with PhIF2 generated in situ by PhIO and Et3N ? 3HF in 1,2-dichroloethane, which features the hypervalent iodine reagents-mediated introduction of fluorine atom and formation of the 2H-azirine skeleton under metal-free conditions. The domino reaction is postulated to proceed via a PhIF2-mediated oxidative fluorination and a subsequent azirination of the fluorinated enamine intermediates. (Figure presented.).
- Zhang, Yong,Zhao, Xiaoyuan,Zhuang, Chen,Wang, Senlin,Zhang-Negrerie, Daisy,Du, Yunfei
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supporting information
p. 2107 - 2112
(2018/04/19)
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- Reinventing the de Mayo reaction: Synthesis of 1,5-diketones or 1,5-ketoesters via visible light [2+2] cycloaddition of β-diketones or β-ketoesters with styrenes
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A visible light mediated De Mayo reaction between 1,3-diketones and styrenes following a [2+2] cycloaddition pathway via a photosensitization mechanism gives access to 1,5-diketones. The reaction has been applied to substituted styrenes and aryl- and alkyl-substituted ketones. Moreover, the method converts β-ketoesters, β-amido esters, and β-cyano ketones. Seven membered rings, a frequent structural motif of natural products, are also accessible using this methodology.
- Martinez-Haya, Rebeca,Marzo, Leyre,K?nig, Burkhard
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supporting information
p. 11602 - 11605
(2018/10/31)
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- Synthesis of enaminones via copper-catalyzed decarboxylative coupling reaction under redox-neutral conditions
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A novel copper-catalyzed C(sp3)-H oxidative functionalization of aromatic oxime acetates with α-oxocarboxylic acids was reported. This process involved N-O/C-C bond cleavages and C-C bond formations to furnish substituted enaminones under redox-neutral conditions. The oxime acetates served as both reactants and internal oxidants. Furthermore, this transformation also features good functional group tolerance and needs no ligands or additional bases.
- Zhu, Zhongzhi,Tang, Xiaodong,Li, Jianxiao,Li, Xianwei,Wu, Wanqing,Deng, Guohua,Jiang, Huanfeng
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p. 3228 - 3231
(2017/03/20)
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- Method for directly oxidizing benzyl-position C-H bond into ketone
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The invention discloses a method for directly oxidizing a benzyl-position C-H bond into ketone, wherein aryl ethyl compounds are catalyzed and oxidized by nitrite ester; a synergistic catalytic system of free radical initiator and nitrite ester is adopted, and a catalytic system of non-metallic catalyst and oxygen is adopted, the oxidization of the C-H bond of a free radical-activated aryl side chain is simple in operation; after completing the reaction, petroleum ether/ethyl acetate at a volume ratio of (50-1):1 is used as an eluent; column chromatography separation is performed to obtain a target product. The catalytic system in the invention uses oxygen as an oxygen source and has high atomic economy; the invention is a non-metallic catalytic system and provides a novel method for avoid metal residues in synthetic drugs; for diethyl aromatic hydrocarbon, the method provided by the invention can be adopted to selectively oxidize diethyl aromatic hydrocarbon into monoketone and diketone; the method of the invention can be adopted to efficiently synthesize tranquillizer lenperone, so that a novel method for synthesizing lenperone is provided.
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-
Paragraph 0108; 0109; 0112; 0113
(2017/08/29)
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- Organopromoted Selectivity-Switchable Synthesis of Polyketones
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In this work, an organopromoted metal-free pharmaceutical-oriented selectivity-switchable benzylic oxidation was developed, affording mono-, di-, and trioxygenation products, respectively, using oxygen as the oxidant under mild conditions. This process facilitates dioxygenation of 2,6-benzylic positions of heterocycles, which could be inhibited by heterocycle chelation to the metal cocatalysts. Enantiopure chiral ketones could also be prepared. The noninvolvement of transition metals and toxins avoids metal or hazardous residues, consequently ensuring a final-stage gram-scale synthesis of Lenperone.
- Liu, Jie,Hu, Kang-Fei,Qu, Jian-Ping,Kang, Yan-Biao
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supporting information
p. 5593 - 5596
(2017/10/25)
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- Room-Temperature Coupling/Decarboxylation Reaction of α-Oxocarboxylates with α-Bromoketones: Solvent-Controlled Regioselectivity for 1,2- and 1,3-Diketones
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A transition-metal-free and room-temperature coupling/decarboxylation reaction between α-oxocarboxylates and α-bromoketones is reported herein. It represents the first mild and regioselective synthesis of either 1,2- or 1,3-diketones from the same starting materials. Notably, the regioselectivity is simply controlled by solvents. The preliminary experimental data and DFT calculations suggest sequential Darzens-type coupling, alkaline hydrolysis, KOH-promoted oxirane opening and decarboxylation in one pot. This method is efficient for the synthesis of α,β-epoxy-γ-butyrolactone and curcuminoids.
- He, Zhen,Qi, Xiaotian,She, Zhijie,Zhao, Yinsong,Li, Shiqing,Tang, Junbin,Gao, Ge,Lan, Yu,You, Jingsong
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supporting information
p. 1403 - 1411
(2017/02/10)
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- A 1,3-diones substitution alkone method of synthesizing α-
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The invention discloses a method for synthesizing alpha-substituted ketone by using a 1,3-diketone compound, and belongs to the field of preparation of fine chemical engineering. The 1,3-diketone compound with an electron-withdrawing substituent group at 2-position is used as a substrate, an accelerant is added, and alpha-substituted ketone is synthesized by utilizing mixed solvent of tetrahydrofuran and water. An efficient and single method for synthesizing the alpha-substituted ketone, which is mild in condition, low in cost and suitable for large-scale production is provided.
- -
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Paragraph 0061; 0062; 0063; 0064; 0065; 0066
(2016/10/10)
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- KI/TBHP-mediated oxidative cross-coupling of enamines and carboxylic acids under metal-free conditions: A facile access to functionalized 2H-azirines
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KI/TBHP-mediated oxidative cross coupling of enamines with carboxylic acids has been realized for the synthesis of functionalized 2H-azirines through the azirination of enamine intermediates. The metal-free strategy has several notable features, including the formation of C-O and C-N bonds in a one-pot procedure, broad functional group tolerance, good reaction yields, short reaction time, and high atom economy. It is the first example for direct formation of functionalized 2H-azirines via KI/TBHP-mediated intermolecular cross-coupling of enamines and carboxylic acids.
- Duan, Xiyan,Kong, Xianglei,Zhao, Xiaoyong,Yang, Kun,Zhou, Huiyun,Zhou, DongJu,Zhang, Yanping,Liu, Jianwei,Ma, Junying,Liu, Ning,Wang, Zhicheng
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supporting information
p. 1446 - 1450
(2016/03/12)
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- Efficient epoxide isomerization within a self-assembled hexameric organic capsule
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The isomerization of epoxides to the corresponding carbonyl compounds is efficiently catalyzed by the supramolecular organic nano-capsule formed by the self-assembly of six resorcin[4]arene units. The capsule provides a combination of weak Br?nsted acidity and a suitable nano-environment that favors the metal-free isomerization reaction.
- Caneva, Thomas,Sperni, Laura,Strukul, Giorgio,Scarso, Alessandro
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p. 83505 - 83509
(2016/11/01)
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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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- 2,2-Difluoro-1,3-diketones as gem-Difluoroenolate Precusors for Asymmetric Aldol Addition with N-Benzylisatins
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2,2-Difluoro-1,3-diketones are introduced as gem-difluoroenolate precursors for the first example of an organocatalytic asymmetric aldol addition with N-benzylisatins to form 3-difluoroalkyl-3-hydroxyoxindoles. (Figure presented.).
- Qian, Jinlong,Yi, Wenbin,Huang, Xin,Jasinski, Jerry P.,Zhang, Wei
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p. 2811 - 2816
(2016/09/13)
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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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- Organic base-catalysed solvent-tuned chemoselective carbotrifluoromethylation and oxytrifluoromethylation of unactivated alkenes
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An unprecedented and efficient organic base-catalysed highly chemoselective carbo- and oxytrifluoromethylation of unactivated alkenes with Togni's reagent was developed. The switchable chemoselectivity was tuned by simply changing the organic base catalyst and solvent. Mechanistic studies indicated that a radical cyclization pathway for carbotrifluoromethylation in DMSO and a carbocation pathway for oxytrifluoromethylation in DCE were probably involved.
- Yang, Ning-Yuan,Li, Zhong-Liang,Ye, Liu,Tan, Bin,Liu, Xin-Yuan
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supporting information
p. 9052 - 9055
(2016/07/21)
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- Aerobic oxidation of aromatics catalyzed by CoSPc and NHPI
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An efficient method to convert aromatics into the corresponding oxides, catalyzed by a combined catalytic system consisting of CoSPc and NHPI, has been developed. The products have been diversified with the number of hydrogen atoms on the benzyl positions. When only one hydrogen atom is present on the benzyl position, a C-C bond dissociation occurs, if there are two or three hydrogen atoms present on the benzyl positions, carbonyl or carboxyl products are generated. Whether the oxidation takes place or not mainly depends on the BDEs of benzyl C-H bonds, steric hindrances only influence the oxidation speeds, and an oxidation process is proposed at the end of discussion.
- Zhou, Yulu,Lin, Shasha,Bian, Yinghui,Xia, Daohong,Xiang, Yuzhi
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p. 624 - 628
(2017/01/18)
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- The base-promoted synthesis of multisubstituted benzo[b][1,4]oxazepines
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A novel protocol to synthesize multisubstituted benzo[b][1,4]oxazepines from N-(2-haloaryl)enaminones has been developed. In this procedure, only 2 equiv. of Cs2CO3 was required. A variety of polysubstituted benzo[b][1,4]oxazepine derivatives were provided in up to 95% yield for 27 examples.
- Shen, Jinhai,Xue, Lulu,Lin, Xing,Cheng, Guolin,Cui, Xiuling
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p. 3292 - 3295
(2016/02/27)
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- An Efficient Synthesis of Polysubstituted Pyridines via C sp 3 -H Oxidation and C-S Cleavage of Dimethyl Sulfoxide
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An expedient cleavage of the C-S bond of dimethyl sulfoxide (DMSO) has been developed for the preparation of substituted pyridines from ketones. In this transformation, the co-product formic acid was formed from ammonium formate, which acted as an important catalyst for the reaction. Notably, this transformation exhibited a broad substrate scope towards a wide variety of different ketones to give the corresponding substituted pyridines in high yields. Mechanistic studies suggested that dimethyl sulfoxide delivered a methylene fragment, which was subsequently captured in situ to give a pyridine.
- Wu, Xia,Zhang, Jingjing,Liu, Shan,Gao, Qinghe,Wu, Anxin
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p. 218 - 225
(2016/02/16)
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- 1,5-Diketones Synthesis via Three-Component Cascade Reaction
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A mild and efficient cascade synthesis of 1,5-diketones from readily available N,N-dicyclohexylmethylamine, 1,3-dicarbonyl compounds, and trifluoromethyl β-diketones has been developed. This cascade reaction occurs via an oxidation/Mannich reaction/Cope elimination/Michael addition/retro-Claisen reaction sequence, and provides multiple C-C bond formations in one pot. In addition, exquisite chemoselectivity is achieved in the reaction between 1,3-dicarbonyl compounds and trifluoromethyl β-diketones.
- Xing, Li-Juan,Lu, Tao,Fu, Wei-Li,Lou, Mei-Mei,Chen, Bo,Wang, Zhi-Shen,Jin, Yang,Li, Dan,Wang, Bin
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supporting information
p. 3076 - 3080
(2015/11/03)
-
- 2-Hydroxylation of 1,3-Diketones with Atmospheric Oxygen
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An efficient method for the 2-hydroxylation of 1,3-diketones by using atmospheric oxygen as an oxidant under transition-metal-free condition is described. The protocol has the advantages of using an inexpensive and stable oxidant, producing high yields, and requiring ecofriendly conditions.
- Li, Zheng,Li, Tianpeng,Li, Jiasheng,He, Lili,Jia, Xianggui,Yang, Jingya
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supporting information
p. 2863 - 2865
(2015/12/18)
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- Chemo- and regioselective preparation of zinc enolate from thiol esters by palladium catalyzed cross-coupling reaction
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The palladium catalyzed cross-coupling reaction of thiol esters with bis(iodozincio)methane or 1,1-bis(iodozincio)ethane gave Reformatsky-type enolates. They can react with some electrophiles to give the corresponding adducts and were also trapped by silylation reagents to afford silyl enol ethers. As the method applicable to the thiol ester carrying ketone moiety, it afforded zinc enolates carrying ketone in the same molecule.
- Haraguchi, Ryosuke,Ikeda, Zenichi,Ooguri, Akihiro,Matsubara, Seijiro
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p. 8830 - 8837
(2015/10/20)
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- Palladium anchored on amine-functionalized K10 as an efficient, heterogeneous and reusable catalyst for carbonylative Sonogashira reaction
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The present work describes the immobilization of palladium chloride (II) on the amine functionalized K10 support and its application toward the carbonylative Sonogashira reactions. The various catalyst characterization techniques revealed the successful grafting of APTES moiety on the K10 clay surface through covalent bonding and Pd with the NH2 groups of APTES@K10 through co-ordinate bonding. The immobilized catalyst was successively applied for copper and phosphine free carbonylative Sonogashira reaction of aryl and hetero aryl iodides with terminal alkynes. To our delight, the electron withdrawing aryl halides can be efficiently utilized as an electrophiles giving higher selectivity toward carbonylated products. Moreover, dibenzoylmethane which is a potential synthetic intermediate in organic transformation has been also synthesized using this protocol. Recovery of catalyst by simple filtration and its reuse up to four consecutive cycles ensure the robustness of present catalytic protocol.
- Chavan, Sujit P.,Varadwaj, G.Bishwa Bidita,Parida, Kulamani,Bhanage, Bhalchandra M.
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p. 237 - 245
(2015/10/12)
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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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- Preparation of iodonium ylides: Probing the fluorination of 1,3-dicarbonyl compounds with a fluoroiodane
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The isolation of iodonium ylide 8, from the reaction of fluoroiodane 1 with ethyl 3-oxo-3-phenylpropanoate 5 in the presence of potassium fluoride, provides strong evidence that 1,3-dicarbonyl compounds undergo an addition reaction with fluoroiodane 1 to form an iodonium intermediate which can be deprotonated to generate an iodonium ylide. In the presence of TREAT-HF, however, the iodonium intermediate reacts to form the 2-fluoro-1,3-dicarbonyl product and we propose that fluoroiodane 1 simulates electrophilic fluorination via an addition/substitution mechanism. Further evidence to support this mechanism was obtained by successfully reacting the isolated iodonium ylide 8 with TREAT-HF, hydrochloric acid, acetic acid and p-toluenesulfonic acid to form the 2-fluoro-, 2-chloro-, 2-acetyl- and 2-tosyl-1,3-ketoesters respectively. This journal is
- Geary, Gemma C.,Hope, Eric G.,Singh, Kuldip,Stuart, Alison M.
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p. 16501 - 16506
(2015/03/04)
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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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- Cooperative catalysis by polymetallic copper-zinc complexes in the efficient oxidation of alcohols under solvent free condition
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The oxidation of alcohols to corresponding aldehydes and ketones has been achieved using polymetallic complexes as catalyst with hydrogen peroxide as the terminal oxidant under a solvent free condition. These polymetallic complexes linked to a single ligand system exhibited remarkable cooperative effect in the oxidation process. This ecologically friendly procedure releases water as the only by-product.
- Borthakur, Rosmita,Asthana, Mrityunjaya,Kumar, Arvind,Lal, Ram A.
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p. 198 - 201
(2014/07/07)
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- METHOD FOR SYNTHESIZING BETA-DICARBONYL COMPOUNDS
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A method for synthesizing beta-dicarbonyl compounds, particularly beta-diketones, from at least two carbonyl compounds, such as esters and ketones, in the presence of a strong base or a mixture of strong bases by Claisen condensation with a titer of greater than 95%. The method includes providing a synthesis reactor on which a separation column, provided with a condenser and with at least one microwave generator, is mounted; feeding a first carbonyl compound and the strong base into the synthesis reactor; heating the reactor and starting up the condenser; starting up the microwave generator(s); when the mixture is brought to a boil at total flux, feeding the second carbonyl compound into the reactor; and after a waiting time, stopping the reactor and acidifying and washing the reaction mixture.)
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Paragraph 0121; 0122; 0123; 0124
(2014/04/03)
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