- Synthesis of 1,2-diketones by mercury-catalyzed alkyne oxidation
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The first mercury-catalyzed synthesis of 1,2-diketones by alkyne oxidation has been developed. This inexpensive method extends the potential of mercury catalysis and allows the rapid construction of various 1,2-diketones and α-carbonyl amides in good yields with high functional group tolerance.
- Mei, Xiaochuan,Hu, Weican,Gao, Kexin,Gao, Haotian,Wang, Chaoyang,Qian, Guoying,Rong, Zhouting
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supporting information
p. 2661 - 2667
(2021/07/09)
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- Lanthanide complexes based on an anthraquinone derivative ligand and applications as photocatalysts for visible-light driving photooxidation reactions
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Four isostructural lanthanide coordination complexes based on 3,7-diamino-9,10-anthraquinone-2,6-disulfonate (dianionic, L) have been synthesized by hydrothermal method, namely [Er(L)(H2O)6]?[Er(H2O)8]?2L?8H2O (Er-L), [Tm(L)(H2O)6]?[Tm(H2O)8]?2L?8.5H2O (Tm-L), [Yb(L)(H2O)6]?[Yb(H2O)8]?2L?9H2O (Yb-L), [Lu(L)(H2O)6]?[Lu(H2O)8]?2L?9H2O (Lu-L). Single-crystal X-ray analysis reveals the existence of both coordinated and free ligand L in the crystal structure. Versatile sulfonate groups on these distinct L ligands, together with very rich coordinated and lattice water molecules, form a lot of hydrogen-bonding motifs that contribute to the stabilization of the crystal packing. It is interesting that the ligands stack into columns through strong π-π interactions and the centroid-centroid distances are between 3.281 and 3.331 ?. These ligands are stacked in an alternate off-set mode to avoid the steric hindrance between the bulky sulfonate groups, generating a repeated structural unit involving six stacked ligands. These lanthanide complexes proved to be good heterogeneous photocatalyst for promoting the visible-light driving photooxidation reactions of diarylacetylenes and thioethers. The Er-L complex exhibited the best catalytic activity and showed good catalytic efficiency over a wide range of substrates for both reaction systems. The Er-L photocatalyst can be easily isolated by simple filtration as crystalline material upon completion of the photooxidation reaction without structure change, and can be recycled for at least five catalytic cycles with persistent catalytic efficiency without any need of activation or regeneration. This family of lanthanide complexes represent a category of promising heterogeneous photocatalysts in terms of green chemistry, with the potential of promoting organic transformations highly efficiently under the irradiation of visible light.
- Zhu, Ting-Ting,Tao, Yu-Tong,Sun, Yue,Wang, Xue,Zhang, Xiao-Wen,Chai, Jia-Lu,Han, Jie,Zhao, Xiao-Li,Chen, Xu-Dong
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- Visible-Light-Induced Photocatalytic Oxidative Decarboxylation of Cinnamic Acids to 1,2-Diketones
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A concerted metallophotoredox catalysis has been realized for the efficient decarboxylative functionalization of α,β-unsaturated carboxylic acids with aryl iodides in the presence of perylene bisimide dye to afford 1,2-diketones.
- Chand, Shiv,Pandey, Anand Kumar,Singh, Rahul,Singh, Krishna Nand
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p. 6486 - 6493
(2021/05/06)
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- One-pot cascade synthesis of α-diketones from aldehydes and ketones in water by using a bifunctional iron nanocomposite catalyst
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A new methodology for the synthesis of α-diketones was reportedviaa one-pot cascade process from aldehydes and ketones catalyzed by a bifunctional iron nanocomposite using H2O2as a green oxidant in water. The one-pot strategy showed excellent catalytic stability, comprehensive suitability of substrates and important practical utility for directly synthesizing biologically active and medicinally valuable N-heterocyclesviaan intermittent process.
- Song, Tao,Zhou, Xin,Wang, Xiaoxue,Xiao, Jianliang,Yang, Yong
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supporting information
p. 1955 - 1959
(2021/03/26)
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- High heat-resistant polyimide films containing quinoxaline moiety for flexible substrate applications
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The development of thermostable polyimides (PIs) is urgently required for application in traditional aerospace and newly designing flexible-display substrates. The root to obtain intrinsic heat-resistant PIs is to seek novel monomers. Based on the high bo
- Chen, Shuangshuang,Ding, Tong-Mei,Jiang, Wei,Liu, Tuan-Qing,Lu, Qinghua,Ma, Xiaoru,Zhang, Shu-Yu,Zheng, Feng
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- Nature of the Nucleophilic Oxygenation Reagent Is Key to Acid-Free Gold-Catalyzed Conversion of Terminal and Internal Alkynes to 1,2-Dicarbonyls
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2,3-Dichloropyridine N-oxide, a novel oxygen transfer reagent, allows the conductance of the gold(I)-catalyzed oxidation of alkynes to 1,2-dicarbonyls in the absence of any acid additives and under mild conditions to furnish the target species, including those derivatized by highly acid-sensitive groups. The developed strategy is effective for a wide range of alkyne substrates such as terminal- and internal alkynes, ynamides, alkynyl ethers/thioethers, and even unsubstituted acetylene (40 examples; yields up to 99%). The oxidation was successfully integrated into the trapping of reactive dicarbonyls by one-pot heterocyclization and into the synthesis of six-membered azaheterocycles. This synthetic acid-free route was also successfully applied for the total synthesis of a natural 1,2-diketone.
- Dubovtsev, Alexey Yu.,Shcherbakov, Nikolay V.,Dar'in, Dmitry V.,Kukushkin, Vadim Yu.
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p. 745 - 757
(2020/02/04)
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- Conversion of alkynes into 1,2-diketones using HFIP as sacrificial hydrogen donor and DMSO as dihydroxylating agent
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A metal-free and hypervalent iodine free conversion of internal alkynes into 1,2-diketo compounds has been described. The efficacy of the present protocol rely on the use of HFIP (1,1,1,3,3,3-Hexafluoro-2-propanol) as reducing agent of alkynes and DMSO as dihydroxylating agent of olefins to acquire the desired chemical transformations. The obtained 1,2-diketones were further transformed into useful derivatives.
- Gujjarappa, Raghuram,Vodnala, Nagaraju,Putta,Ganga Reddy, Velma,Malakar, Chandi C.
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supporting information
(2020/01/21)
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- Ruthenium/dendrimer complex immobilized on silica-functionalized magnetite nanoparticles catalyzed oxidation of stilbenes to benzil derivatives at room temperature
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A new ruthenium/dendrimer complex stabilized on the surface of silica-functionalized nano-magnetite was fabricated and well characterized. The nano-catalyst showed good activity in the synthesis of benzil derivatives via the oxidation of stilbenes with high turnover frequency (TOF) at room temperature. Moreover, the catalyst could also be reused up to fifteen times without any loss of its activity.
- Ghanaatzadeh, Niloofar,Hashemi, Hajar,Moghadam, Majid,Niknam, Khodabakhsh,Saberi, Dariush
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- A Bifunctional Iron Nanocomposite Catalyst for Efficient Oxidation of Alkenes to Ketones and 1,2-Diketones
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We herein report the fabrication of a bifunctional iron nanocomposite catalyst, in which two catalytically active sites of Fe-Nx and Fe phosphate, as oxidation and Lewis acid sites, were simultaneously integrated into a hierarchical N,P-dual doped porous carbon. As a bifunctional catalyst, it exhibited high efficiency for direct oxidative cleavage of alkenes into ketones or their oxidation into 1,2-diketones with a broad substrate scope and high functional group tolerance using TBHP as the oxidant in water under mild reaction conditions. Furthermore, it could be easily recovered for successive recycling without appreciable loss of activity. Mechanistic studies disclose that the direct oxidation of alkenes proceeds via the formation of an epoxide as intermediate followed by either acid-catalyzed Meinwald rearrangement to give ketones with one carbon shorter or nucleophilic ring-opening to generate 1,2-diketones in a cascade manner. This study not only opens up a fancy pathway in the rational design of Fe-N-C catalysts but also offers a simple and efficient method for accessing industrially important ketones and 1,2-diketones from alkenes in a cost-effective and environmentally benign fashion.
- Ma, Zhiming,Ren, Peng,Song, Tao,Xiao, Jianliang,Yang, Yong,Yuan, Youzhu
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p. 4617 - 4629
(2020/05/19)
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- (Ar-tpy)RuII(ACN)3: A Water-Soluble Catalyst for Aldehyde Amidation, Olefin Oxo-Scissoring, and Alkyne Oxygenation
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The synthetic chemists always look for developing new catalysts, sustainable catalysis, and their applications in various organic transformations. Herein, we report a new class of water-soluble complexes, (Ar-tpy)RuII(ACN)3, utilizing designed terpyridines possessing electron-donating and -withdrawing aromatic residues for tuning the catalytic activity of the Ru(II) complex. These complexes displayed excellent catalytic activity for several oxidative organic transformations including late-stage C-H functionalization of aldehydes with NH2OR to valuable primary amides in nonconventional aqueous media with excellent yield. Its diverse catalytic power was established for direct oxo-scissoring of a wide range of alkenes to furnish aldehydes and/or ketones in high yield using a low catalyst loading in the water. Its smart catalytic activity under mild conditions was validated for dioxygenation of alkynes to highly demanding labile synthons, 1,2-diketones, and/or acids. This general and sustainable catalysis was successfully employed on sugar-based substrates to obtain the chiral amides, aldehydes, and labile 1,2-diketones. The catalyst is recovered and reused with a moderate turnover. The proposed mechanistic pathway is supported by isolation of the intermediates and their characterization. This multifaceted sustainable catalysis is a unique tool, especially for late-stage functionalization, to furnish the targeted compounds through frequently used amidation and oxygenation processes in the academia and industry.
- Joarder, Dripta De,Gayen, Subrata,Sarkar, Rajarshi,Bhattacharya, Rajarshi,Roy, Sima,Maiti, Dilip K.
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p. 8468 - 8480
(2019/07/03)
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- Method for synthesis of nitroquinoxaline or derivative thereof and aminoquinoxaline or derivative thereof
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The invention relates to a method for synthesis of nitroquinoxaline or derivative thereof. The method includes: in the presence of a catalyst o-benzoyl sulfimide, reacting mononitro-substituted o-phenylenediamine or derivative thereof with mononitro-subst
- -
-
Paragraph 0067; 0068; 0069; 0075; 0076; 0077
(2020/01/12)
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- ICl/AgNO3 Co-catalyzed radical oxidation of diaryl- A nd alkylarylalkynes into 1,2-diketones
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A novel ICl/AgNO3 co-catalyzed radical oxidation of diaryl- A nd alkylarylalkynes into 1,2-diketones is reported. The reaction proceeded smoothly under mild conditions and generated 1,2-diketones in moderate to good yields with a good tolerance of functional groups. Furthermore, the obtained C4-(1,2-diketoaryl)isoxazoles could react smoothly with 1,2-diaminobenzene to form C4-(3-arylquinoxalin-2-yl)isoxazoles. At last, a new one-pot strategy for the synthesis of quinoxalines from 1,2-diphenylethynes and 1,2-diaminobenzene is also reported.
- Yang, Wen,Chen, Yu,Yao, Yongqi,Yang, Xin,Lin, Qifu,Yang, Dingqiao
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p. 11080 - 11090
(2019/09/09)
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- Rate Enhancement in CAN-Promoted Pd(PPh3)2Cl2-Catalyzed Oxidative Cyclization: Synthesis of 2-Ketofuran-4-carboxylate Esters
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Stoichiometric ceric ammonium nitrate (CAN) and a catalytic amount of Pd(PPh3)2Cl2 (5 mol %) can rapidly produce multisubstituted 2-ketofuran-4-carboxylate esters from 2-propargylic 1,3-ketoesters via oxidative O-cyclization reaction. Pd(PPh3)2Cl2 was found to be the crucial catalyst as its inclusion greatly enhanced the rate of the reaction and cleanly afforded the products within minutes. Over 30 substrates were successfully converted to the desired compounds in mostly moderate to good yields.
- Ruengsangtongkul, Sureeporn,Chaisan, Nattawadee,Thongsornkleeb, Charnsak,Tummatorn, Jumreang,Ruchirawat, Somsak
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supporting information
p. 2514 - 2517
(2019/04/30)
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- Electrochemical synthesis of 1,2-diketones from alkynes under transition-metal-catalyst-free conditions
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We report an electrochemical protocol for the direct oxidation of internal alkynes in air to provide 1,2-diketones. A variety of functional groups and heterocycle-containing substrates can be tolerated well under mild conditions.
- Zhou, Jie,Tao, Xiang-Zhang,Dai, Jian-Jun,Li, Chen-Guang,Xu, Jun,Xu, Hong-Mei,Xu, Hua-Jian
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supporting information
p. 9208 - 9211
(2019/08/07)
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- Gold-Catalyzed Oxidation of Internal Alkynes into Benzils and its Application for One-Pot Synthesis of Five-, Six-, and Seven-Membered Azaheterocycles
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Internal alkynes have been shown to undergo oxidation to substituted benzils (1,2-diarylethane-1,2-diones) by α-picoline N-oxide in the presence of Ph3PAuNТf2 (5 mol-%). In addition to the unsubstituted benzil, the method allows preparing, under markedly mild conditions (50 °C in chlorobenzene), various non-symmetrical products, including heteroaromatic versions thereof which are much more difficult to obtain otherwise. This gold(I)-catalyzed transformation was integrated into one-pot reaction sequence delivering a range of 5- to 7-membered ring systems (imidazoles, quinoxalines, 1,2,4-triazines, pyrazines, and 1,4-diazepines), thus linking these important heterocyclic motifs to the internal alkyne reagent space.
- Dubovtsev, Alexey Yu.,Dar'in, Dmitry V.,Krasavin, Mikhail,Kukushkin, Vadim Yu.
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p. 1856 - 1864
(2019/02/19)
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- Sequentially Pd/Cu-Catalyzed Alkynylation-Oxidation Synthesis of 1,2-Diketones and Consecutive One-Pot Generation of Quinoxalines
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We report a simple and efficient one-pot synthesis of 1,2-diketones by concatenation of two Pd/Cu-catalyzed processes: Pd0/CuI-catalyzed Sonogashira coupling of terminal alkynes with aryl (pseudo)halides furnishes internal alkynes, which are directly transformed by PdII/CuII-catalyzed Wacker-type oxidation with DMSO and oxygen as dual oxidants to furnish 1,2-diketones. With this efficient, catalyst economical process, various aryl iodides and triflates are efficiently transformed in high yields into symmetrically and unsymmetrically substituted 1,2-diketones with various functional groups. This process can be readily extended to a consecutive one-pot synthesis of quinoxalines in a diversity-oriented fashion.
- Niesobski, Patrik,Martínez, Ivette Santana,Kustosz, Sebastian,Müller, Thomas J. J.
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supporting information
p. 5214 - 5218
(2019/07/31)
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- Metal-Free Iodine-Catalyzed Oxidation of Ynamides and Diaryl Acetylenes into 1,2-Diketo Compounds
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Metal-free oxidation of ynamides is described, employing pyridine-N-oxides as oxidants under molecular iodine catalysis. In stark contrast to Br?nsted acid catalysis, iodophilic activation of ynamides diverts the reaction manifold into a dioxygenation pathway. This oxidation is very rapid at room temperature with only 2.5 mol % I2. Furthermore, this protocol could be extended to nonactivated alkynes, such as diarylacetylenes, to deliver various benzil derivatives.
- Kim, Seung Woo,Um, Tae-Woong,Shin, Seunghoon
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supporting information
p. 4703 - 4711
(2018/04/26)
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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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- Design and synthesis of functionalized coordination polymers as recyclable heterogeneous photocatalysts
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The functionalized ligand 9,10-anthraquinone-1,4-dicarboxylate acid (H2AQDC) was designed and synthesized in order to develop metal-organic coordination polymers as heterogeneous catalysts with a photosensitizing feature. Two major considerations of the ligand design are anthraquinone moieties for photosensitizing to harvest light and carboxylate groups for polymeric coordination toward less solubility. A series of transition metal complexes based on this ligand were synthesized subsequently, namely {Co(AQDC)(H2O)3·2H2O}n (Co-AQDC), {Ni(AQDC)(H2O)3·2H2O}n (Ni-AQDC), {[Cu(AQDC)(H2O)3][Cu(AQDC)(H2O)2(DMF)]·(H2O)4}n (Cu-AQDC), {Zn1.5(AQDC)(OH)(H2O)2·H2O}n (Zn-AQDC), {Ag2(AQDC)(CH3OH)}n (Ag-AQDC). Both the ligand and its transition metal complexes are able to catalyze the visible-light driven oxidation reactions of alkynes into 1,2-diketones in air under mild conditions, in which compound Ni-AQDC demonstrates the best activity. This catalyst can be easily isolated from the reaction mixture by filtration with a trace amount of loss in solution and is ready for recycled use after simple washing and drying without any need for regeneration. Remarkably, the catalyst shows no loss of activity after five catalytic cycles and X-ray powder diffraction proves no change in the structure after five runs. This designed metal-organic coordination polymer represents an environmentally friendly, economical and recyclable photocatalyst, constituting a good candidate for photocatalytic organic syntheses in terms of green chemistry.
- Ye, Cai-Ping,Xu, Gan,Wang, Zheng,Han, Jie,Xue, Lian,Cao, Fu-Yu,Zhang, Qi,Yang, Lin-Feng,Lin, Li-Zhou,Chen, Xu-Dong
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supporting information
p. 6470 - 6478
(2018/05/23)
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- Two-Step One-Pot Synthesis of Unsymmetrical (Hetero)Aryl 1,2-Diketones by Addition-Oxygenation of Potassium Aryltrifluoroborates to (Hetero)Arylacetonitriles
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An efficient one-pot two-step procedure for the synthesis of unsymmetrical (hetero)aryl 1,2-diketones has been developed. The reaction proceeds through a palladium-catalyzed nucleophilic addition of potassium aryltrifluoroborates to aliphatic nitriles followed by a copper-catalyzed aerobic benzylic C–H oxygenation using molecular oxygen as a green oxidant. This represents the first example of the direct synthesis of unsymmetrical diaryl 1,2-diketones from arylacetonitriles. This method utilizes inexpensive, stable, nontoxic, and readily available starting materials, is highly effective in the presence of both electron-rich and electron-poor nitriles and aryltrifluoroborates, and tolerates a wide variety of functional groups. The synthetic utility of this transformation was shown by increasing the scale of the reaction and by carrying out the one-pot protocol for the preparation of quinoxaline and benzimidazole derivatives. A plausible reaction mechanism has also been proposed.
- Kumar, Yogesh,Jaiswal, Yogesh,Kumar, Amit
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p. 494 - 505
(2018/02/09)
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- Reaction of arynes with trifluoroacetylated β-diketones: Novel formation of isocoumarins and phenanthrenes
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Polysubstituted isocoumarins were synthesized by the reaction of substituted 2-(trimethylsilyl)aryl triflates with trifluoromethylated β-diketones in the presence of CsF. The reaction proceeded through carbon-carbon bond insertion of aryne and intramolecular cyclization to form intermediates of alcohol anions, which extruded trifluoromethyl anion to afford isocoumarins. By using CuBr as a catalyst, 2 eq. of aryne reacted with β-diketones to afford phenanthrenes and 1,2-diarylethanones. Although reaction of 2-(trimethylsilyl)phenyl triflate with 1,1,1-trifluoro-4′-methylbenzoylacetone in the presence of CsF gave 3-(4′-methylphenyl)isocoumarin in 67% yield, addition of 0.2 eq. of CuCN resulted in the formation of 9-(4-methylbenzoyl)-10-trifluoromethylphenanthrene in 35% yield.
- Okuma, Kentaro,Tanabe, Yukiko,Fukami, Takuto,Ishibashi, Yuto
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- Copper-catalyzed TEMPO oxidative cleavage of 1,3-diketones and β-keto esters for the synthesis of 1,2-diketones and α-keto esters
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A copper-catalyzed efficient and practical method has been developed for the synthesis of 1,2-diketones and α-keto esters. TEMPO was used as a radical initiator and scavenger, oxidizing the cleavage of α-methylene of 1,3-diketones and β-keto esters to form 1,2-diketones and α-keto esters. This method provided a general way for the formation of 1,2-dicarbonyl compounds.
- Zhou, Peng-Jun,Li, Cheng-Kun,Zhou, Shao-Fang,Shoberu, Adedamola,Zou, Jian-Ping
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p. 2629 - 2637
(2017/04/03)
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- Synthesis of 1,2-Diketones via a Metal-Free, Visible-Light-Induced Aerobic Photooxidation of Alkynes
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1,2-Diketones were synthesized by the oxidation of corresponding alkynes using air as the oxidant under metal-free conditions upon irradiation of blue light. A cheap and readily available organic dye, eosin Y, was used as the photocatalyst. For various substituents on the aryl ring, the reaction proceeded smoothly to give the dicarbonylation products in moderate to good yields. Some oxidation-sensitive groups, such as formyl and the carbon-carbon double bond, were tolerated under the developed reaction conditions.
- Liu, Xu,Cong, Tiantian,Liu, Ping,Sun, Peipei
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p. 7256 - 7261
(2016/08/30)
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- Preparation method of 1,2-diketone derivative
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The invention discloses a preparation method of a 1,2-diketone derivative. The method comprises the step of enabling a raw material 1,3-diketone derivative to react with a cheap and easily obtained industrial product 2,2,6,6-tetramethyl-1-piperidinyloxy under the catalysis of copper so as to obtain the product 1,2-diketone derivative. According to the preparation method, the 1,3-diketone derivative is used as an initiator, and the raw material is easy to obtain and wide in variety; by utilizing the preparation method, the obtained product types are varied, can be directly used, and can be used for other further reactions; in addition, the reagent dosage in the reaction is less, the pollution is reduced, and the production cost is lowered; moreover the reaction conditions are mild, the reaction operation and the after-treatment process are simple, the reaction time is short, the yield is high, and the preparation method is suitable for industrial production.
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Paragraph 0022
(2016/10/08)
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- Diversity-Oriented Synthesis of a Library of Star-Shaped 2H-Imidazolines
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A library of star-shaped 2H-imidazolines has been synthesized via Debus-Radziszewski condensation from 1,2-diketones and ketone starting materials. Selective reduction of one imine group of the 2H-imidazole intermediate with LiAlH4 or catalytic flow hydrogenation furnished 2H-imidazolines, which could be conveniently diversified by reacting the amine N with electrophiles, resulting in a set of 21 amide-, carbamate-, urea-, and allylamine-containing products. In total, five points of diversification could be used, which allow the production of a set of functionally diverse compounds. The synthesis of acylated 2H-imidazolidines resulted in intrinsically labile compounds, which spontaneously degraded to acyclic derivatives, as shown for the reaction of 2H-imidazolidine with hexylisocyanate.
- Yu, Xuepu,Guttenberger, Nikolaus,Fuchs, Elisabeth,Peters, Martin,Weber, Hansj?rg,Breinbauer, Rolf
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supporting information
p. 682 - 690
(2015/11/17)
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- Copper-catalyzed base-accelerated direct oxidation of C-H bond to synthesize benzils, isatins, and quinoxalines with molecular oxygen as terminal oxidant
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We describe herein an efficient and general copper (II)-catalyzed base-accelerated oxidation of the C-H bond to synthesize benzils and isatins. With similar oxidation system an efficient one-pot procedure for the synthesis of quinoxaline derivatives was realized. The two protocols feature using molecular oxygen as terminal oxidant, low catalyst loading, wide substrate scope, and high functional-group tolerance.
- Yu, Jing-Wen,Mao, Shuai,Wang, Yong-Qiang
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p. 1575 - 1580
(2015/03/14)
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- Mild Mn(OAc)3-Mediated Aerobic Oxidative Decarboxylative Coupling of Arylboronic Acids and Arylpropiolic Acids: Direct Access to Diaryl 1,2-Diketones
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A simple and efficient method for the synthesis of diaryl 1,2-diketones has been developed. The reaction represents the first example of diaryl 1,2-diketones that are synthesized directly from arylboronic acids and arylpropiolic acids by a radical pathway in moderate to good yields. This reaction proceeds under mild reaction conditions and with good tolerance of a variety of functional groups. Preliminary mechanistic studies were conducted.
- Lv, Wen-Xin,Zeng, Yao-Fu,Zhang, Shang-Shi,Li, Qingjiang,Wang, Honggen
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supporting information
p. 2972 - 2975
(2015/06/30)
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- Oxidative cleavage of olefins by in situ-generated catalytic 3,4,5,6-tetramethyl-2-iodoxybenzoic acid/oxone
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Oxidative cleavage of a variety of olefins to the corresponding ketones/carboxylic acids is shown to occur in a facile manner with 3,4,5,6-tetramethyl-2-iodobenzoic acid (TetMe-IA)/oxone. The simple methodology involves mere stirring of the olefin and catalytic amount (10 mol %) of TetMe-IA and oxone in acetonitrile-water mixture (1:1, v/v) at rt. The reaction mechanism involves initial dihydroxylation of the olefin with oxone, oxidative cleavage by the in situ-generated 3,4,5,6-tetramethyl-2-iodoxybenzoic acid (TetMe-IBX), and oxidation of the aldehyde functionality to the corresponding acid with oxone. Differences in the reactivities of electron-rich and electron-poor double bonds have been exploited to demonstrate chemoselective oxidative cleavage in substrates containing two double bonds.
- Moorthy, Jarugu Narasimha,Parida, Keshaba Nanda
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p. 11431 - 11439
(2015/02/05)
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- Ruthenium-catalyzed synthesis of 1,2-diketones from alkynes
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The ruthenium-catalyzed synthesis of 1,2-diketones through the oxidation of alkynes by using sodium hypochlorite has been investigated. RuO4 was generated in situ from inexpensive RuCl3·xH2O, and NaOCl as the oxidant demonstrated high performance at room temperature in the solvent diethyl carbonate. A variety of diketones were prepared in good yields by using this environmentally friendly procedure.
- Miao, Yanan,Dupe, Antoine,Bruneau, Christian,Fischmeister, Cedric
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p. 5071 - 5077
(2014/08/18)
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- Copper-catalyzed direct synthesis of diaryl 1,2-diketones from Aryl iodides and propiolic acids
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Benzil derivatives such as diaryl 1,2-diketones are synthesized via the direct decarboxylative coupling reaction of aryl propiolic acids and their oxidation. The optimized conditions are that the reaction of aryl propiolic acids and aryl iodides is conducted at 140°C for 6 h in the presence of 10 mol % CuI/Cu(OTf)2 and Cs2CO3, after which HI (aq) is added and further reacted. The method shows good functional group tolerance toward ester, aldehyde, cyano, and nitro groups. In addition, symmetrical diaryl 1,2-diketones are obtained from aryl iodides and propiolic acid in the presence of palladium and copper catalysts.
- Min, Hongkeun,Palani, Thiruvengadam,Park, Kyungho,Hwang, Jinil,Lee, Sunwoo
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p. 6279 - 6285
(2014/07/21)
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- Copper-mediated aerobic oxidative cleavage of α,β-unsaturated ketones to 1,2-diketones
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The copper-mediated aerobic oxidative cleavage of α,β- unsaturated ketones to synthesize 1,2-diketones by using potassium acetate as a catalyst and sodium iodide as a promoter in acetic acid is described. The protocol has the advantages of using inexpensive and non-toxic raw materials, high yield and simple work-up procedure. the Partner Organisations 2014.
- Li, Zheng,Yin, Junjun,Wen, Gong,Li, Tianpeng,Shen, Xiaoli
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p. 32298 - 32302
(2014/08/18)
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- Ruthenium-catalyzed oxidation of alkynes to 1,2-diketones under room temperature and one-pot synthesis of quinoxalines
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A ruthenium-catalyzed alkyne oxidation to 1,2-diketones using Oxone under room temperature is reported. Both substrate scope and mechanism were discussed. Notably, combination of the alkyne oxidation and condensation cyclization in one pot offers a very efficient and convenient entry into quinoxaline derivatives.
- Xu, Yuan,Wan, Xiaobing
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supporting information
p. 642 - 645
(2013/02/23)
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- Pd/Cu-catalyzed oxidation of alkynes into 1,2-diketones using DMSO as the oxidant
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A facile and practical method for the palladium/copper-catalyzed transformation of internal alkynes into 1,2-diketones has been described, affording the desired products in moderate to excellent yields. The mechanistic studies were also preliminarily pursued using diphenyl sulfoxide as the oxidant, and the diphenyl sulfide was isolated as the reduced product.
- Gao, Ang,Yang, Fan,Li, Ji,Wu, Yangjie
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experimental part
p. 4950 - 4954
(2012/07/30)
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- One-pot synthesis of unsymmetrical benzils by oxidative coupling using selenium dioxide and p-toluenesulfonic acid monohydrate
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The oxidative coupling of the α-carbon atom of aromatic ketones with unactivated arenes in the presence of selenium dioxide and p-toluenesulfonic acid monohydrate is described. A number of unsymmetrical benzils have been prepared in good yields (38-75 % with high regioselectivity. The generality and functional tolerance of this new protocol is demonstrated. The mechanistic pathway for the oxidative coupling reaction is also described. The reaction displays superiority in terms of minimization of steps with the C-C bond formation promoted by SeO2 and pTsOH·H2O. This method is advantageous as the reactants used as the solvent can be recovered. Copyright
- Rohman, Md. Rumum,Kharkongor, Icydora,Rajbangshi, Mantu,Mecadon, Hormi,Laloo, Badaker M.,Sahu, Priti R.,Kharbangar, Iadeishisha,Myrboh, Bekington
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experimental part
p. 320 - 328
(2012/02/04)
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- Pyridine N-oxide mediated oxidation of diarylalkynes with palladium on carbon
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Pyridine N-oxide works as an effective oxidant of 1,2-diarylalkynes at 120 °C to form benzil derivatives under Pd/C-catalyzed solvent-free conditions, and Pd/C could be reused up to five times after simple filtration.
- Sawama, Yoshinari,Takubo, Masato,Mori, Shigeki,Monguchi, Yasunari,Sajiki, Hironao
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experimental part
p. 3361 - 3367
(2011/07/29)
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- Facile aerobic photo-oxidative synthesis of α-diketones from alkynes
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We report a useful method for facile aerobic photo-oxidative synthesis of α-diketones from alkynes with MgBr2·OEt2. This procedure provides a practical synthetic method of α-diketones using easily handled bromine sources, harmless visible light, and molecular oxygen as terminal oxidant.
- Nobuta, Tomoya,Tada, Norihiro,Hattori, Kasumi,Hirashima, Shin-Ichi,Miura, Tsuyoshi,Itoh, Akichika
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experimental part
p. 875 - 877
(2011/03/20)
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- Synthesis of unsymmetrical benzils using N-heterocyclic carbene catalysis
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In this paper, we propose a novel and efficient method for the preparation of various unsymmetrical benzils. We first demonstrate the nucleophilic aroylation of N-phenylbenzimidoyl chlorides with aromatic aldehydes using N-heterocyclic carbene as the catalyst to afford 1-aryl-2-phenyl-2-(phenylimino) ethanones. These iminoethanones were then converted to 1,2-diaryl-1,2-diketones by acid-promoted hydrolysis.
- Suzuki, Yumiko,Bakar, Abu,Tanoi, Takashi,Nomura, Naoko,Sato, Masayuki
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experimental part
p. 4710 - 4715
(2011/06/27)
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- Palladium on Carbon-Catalyzed synthesis of benzil derivatives from 1,2-Diarylalkynes with DMSO and molecular oxygen as dual oxidants
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A palladium on carbon (Pd/C)-catalyzed synthetic method for the preparation of benzil derivatives from 1,2-diarylalkynes has been established using dimethyl sulfoxide (DMSO) and molecular oxygen as dual oxidants. Regardless of the electrical nature of the functional groups on the aromatic rings, 1,2-diarylalkynes were oxidized to the corresponding benzil derivatives in high to excellent yields. Furthermore, the oxidation could efficiently be catalyzed by both the dry and wet types of Pd/C under atmospheric conditions.
- Mori, Shigeki,Takubo, Masato,Yanase, Takayoshi,Maegawa, Tomohiro,Monguchi, Yasunari,Sajiki, Hironao
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supporting information; experimental part
p. 1630 - 1634
(2010/08/22)
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- Direct synthesis of 1,2-diketones by catalytic aerobic oxidative decarboxylation of 1,3-diketones with iodine and base under irradiation of fluorescent light
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We report a catalytic direct synthesis of 1,2-diketone from 1,3-diketone through iodine/base-catalyzed aerobic photooxidation under visible-light irradiation of fluorescent lamp. Georg Thieme Verlag Stuttgart.
- Tada, Norihiro,Shomura, Motoki,Nakayama, Hiroki,Miura, Tsuyoshi,Itoh, Akichika
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experimental part
p. 1979 - 1983
(2010/10/03)
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- Mild oxidation of diarylacetylenes to 1,2-diketones using oxone in trifluoroacetic acid
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A variety of 1,2-diaryldiketones were synthesized in 15-90% yields by treatment of diarylacetylenes with Oxone as the oxidant in trifluoroacetic acid. Oxidation of 1-nitro-2-(phenylethynyl) benzene and 2,4¢-(ethyne-1,2-diyl) bis(nitrobenzene) furnished 1-benzoylbenzo[c]isoxazol-3(1H)-one and benzo[c]isoxazol-3-yl(4-nitrophenyl)methanone as the major products, respectively. Georg Thieme Verlag Stuttgart.
- Chu, Jean-Ho,Chen, Yen-Ju,Wu, Ming-Jung
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experimental part
p. 2155 - 2162
(2009/12/27)
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- A convenient and practical approach to α-diketones via reactions of internal aryl alkynes with N-iodosuccinimide/water
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A convenient and practical approach to α-diketones via reactions of alkynes with N-iodosuccinimides/water at 70°C has been developed. Georg Thieme Verlag Stuttgart.
- Niu, Mingyu,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
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experimental part
p. 2879 - 2882
(2009/04/06)
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- Synthesis, antileukemic and antiplatelet activities of 2,3-diaryl-6,7-dihydro-5H-1,4-diazepines
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The synthesis, antileukemic and antiplatelet activity evaluation of 2,3-diaryl-6,7-dihydro-5H-1,4-diazepines are described. In general, it was found that compound 17o showed moderate antileukemic activity against MOLT3 human leukemic cancer cell lines. An arachidonic acid induced platelet aggregation effect on washed rat platelets was studied. Compound 17i was found to be the most potent. The antiplatelet properties may be mediated by interference with the arachidonic acid pathway.
- Ramajayam,Giridhar, Rajani,Yadav,Balaraman,Djaballah, Hakim,Shum, David,Radu, Constantin
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p. 2004 - 2010
(2008/12/22)
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- Convenient synthetic route to a dehydrorotenoid via selective intramolecular aldol condensation of 1,2-diaryl diketone
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Synthesis of dehydrorotenoid (1) was successfully achieved via an intramolecular aldol reaction of the corresponding 1,2-diaryl diketone intermediate. The 1,2-diaryl diketone was prepared using a ruthenium-catalyzed oxidation of the corresponding substituted diaryl acetylene. Treatment of this 1,2-diketone with l-proline induced a selective intramolecular aldol condensation reaction, forming the desired benzopyranone over the alternative benzofuran. Deprotection, cyclization, and dehydration gave the target compound in good overall yield.
- Tummatorn, Jumreang,Khorphueng, Prapas,Petsom, Amorn,Muangsin, Nongnuch,Chaichit, Narongsak,Roengsumran, Sophon
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p. 11878 - 11885
(2008/03/13)
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- Microwave-assisted efficient synthesis of 1,2-diaryldiketones: a novel oxidation reaction of diarylalkynes with DMSO promoted by FeBr3
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This paper reports the oxidation of functionalized diarylalkynes with DMSO in the presence of the environmentally friendly FeBr3 catalyst. This non-toxic procedure is general and has been applied successfully under microwave irradiation leading rapidly to benzil derivatives in good yields.
- Giraud, Anne,Provot, Olivier,Peyrat, Jean-Fran?ois,Alami, Mouad,Brion, Jean-Daniel
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p. 7667 - 7673
(2007/10/03)
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- Synthesis of novel substituted diaryl-1,4-diazepines
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In this paper a convenient route to new 2,3-diaryl-substituted 1,4-diazepines is described through cyclization of ethanedione derivatives and 1,3-propanediamine. The ethanedione derivatives required were synthesized by microwave-assisted oxidation from ethanones.
- Ramajayam,Giridhar, Rajani,Yadav
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p. 901 - 906
(2008/02/12)
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- An efficient and time saving microwave-assisted selenium dioxide oxidation of 1,2-diarylethanones
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Selenium dioxide oxidation of 1,2-diarylethanones to corresponding diones by conventional method takes upto 8 hr. The same oxidation under microwave radiations using dimethylsulfoxide as solvent reduces the reaction time considerably (30 to 90 sec). The method reported is efficient and time saving.
- Shirude,Patel,Giridhar,Yadav
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p. 1080 - 1085
(2007/10/03)
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- A Novel Practical Reaction of Diarylalkynes With Sulfur Trioxide: Oxidation to 1,2-Diketones
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A new reaction of arylalkynes with the SO3-dioxane complex gives the corresponding aromatic 1,2-diketones in good yield.
- Rogatchov, Victor O.,Filimonov, Victor D.,Yusubov, Mehman S.
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p. 1001 - 1003
(2007/10/03)
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- New Convenient Oxidation of 1,2-Diarylethenes and 1,2-Diaryl-1,2-dibromoethanes to 1,2-Diarylethanediones by Sulfuric Acid-Based Reagents
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1,2-Diarylethenes are readily oxidized to corresponding 1,2-diarylethanediones by boiling in a mixture of sulfuric and acetic acids with addition of bromine, iodine, or hydrohalic acids and their salts. The first oxidation stage involves electrophilic addition of a halogen at the double bond. 1,2-Diaryl-1,2-dibromoethanes are oxidized to corresponding 1,2-diarylethanediones in the presence of the same compounds, as well as of sodium sulfite.
- Krasnokutskaya,Yusubov,Filimonov,Habicher
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p. 1001 - 1004
(2007/10/03)
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- New DMSO-Based Reagents in Oxidation of Double and Triple Bonds and Synthesis of 1,2-Diketones
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Preparative possibilities of oxidation of arylethenes and arylethynes using new reagents, iodine or palladium compounds in dimethylsulfoxide, in syntheses of 1,2-diketones are considered.The system PdCl2-Me2SO is shown to possess lower activity as compared to I2-Me2SO in oxidation of the double bonds, higher selectivity in oxidation of the triple bonds of diarylethynes and phenylpropyne, but more sensitive to steric effects of the substrate.
- Yusubov, M. S.,Chi, Ki Whan,Krasnokutskaya, E. A.,Vasil'eva, V. P.,Filimonov, V. D.
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p. 1503 - 1506
(2007/10/03)
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- CONVENIENT PREPARATION OF UNSYMMETRICALLY SUBSTITUTED BENZILS BY PERMANGANATE OXIDATION OF β-OXO PHOSPHORUS YLIDES
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Oxidative cleavage of a range of ylides 4 with R1 and/or R2 being aromatic groups, using KMnO4 in a two-phase system, affords unsymmetrical benzils and 1-arylpropane-1,2-diones 5 in moderate to good yield, and the ylide formation and oxidation can be combined in a convenient one-pot method.Key words: Phosphorus ylides, oxidation, 1,2-diketones, benzils, permanganate, oxoalkylidenetriphenylphosphoranes.
- Aitken, R. Alan,Cadogan, J. I. G.,Gosney, Ian
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p. 281 - 286
(2007/10/02)
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