- Generation of Dimethyl Sulfoxide Coordinated Thermally Stable Halogen Cation Pools for C?H Halogenation
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A method to generate halogen cation pools from the reaction of 1,2-dihaloethanes (hal=Br, I) and dimethyl sulfoxide (DMSO) for C?H halogenation of arenes and heteroarenes was reported. The initial reaction of DMSO and 1,2-dihaloethane generates the sulfur
- Dalai, Pallaba Ganjan,Palit, Kuntal,Panda, Niranjan
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supporting information
p. 1031 - 1038
(2022/02/02)
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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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- Catalyst-Free and Transition-Metal-Free Approach to 1,2-Diketones via Aerobic Alkyne Oxidation
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A catalyst-free and transition-metal-free method for the synthesis of 1,2-diketones from aerobic alkyne oxidation was reported. The oxidation of various internal alkynes, especially more challenging aryl-alkyl acetylenes, proceeded smoothly with inexpensive, easily handled, and commercially available potassium persulfate and an ambient air balloon, achieving the corresponding 1,2-diketones with up to 85% yields. Meanwhile, mechanistic studies indicated a radical process, and the two oxygen atoms in the 1,2-diketons were most likely from persulfate salts and molecular oxygen, respectively, rather than water.
- Shen, Duyi,Wang, Hongyan,Zheng, Yanan,Zhu, Xinjing,Gong, Peiwei,Wang, Bin,You, Jinmao,Zhao, Yulei,Chao, Mianran
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p. 5354 - 5361
(2021/05/05)
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- 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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- Method for synthesizing benzil derivatives
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The invention discloses a method for synthesizing benzil derivatives. The method comprises the steps that a diphenyl acetylene compound, halogenated ammonium salt or iodine chloride and a sulfur source serve as reactants, the reactants react in a solvent for a period of time, purification is conducted, and then the benzil derivatives are obtained. According to the method, a metal catalyst and toxic iodine are not used, the applied reactants are low in price, poisonless and tasteless, the operation method is simple, the yield is high, aftertreatment is easy, and the method is suitable for industrial production.
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Paragraph 0064; 0065; 0066; 0067
(2019/01/23)
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- Coordination Booster-Catalyst Assembly: Remote Osmium Outperforming Ruthenium in Boosting Catalytic Activity
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Presented herein is a set of bimetallic and trimetallic “coordination booster-catalyst” assemblies in which the coordination complexes [RuII(terpy)2] and [OsII(terpy)2] acted as boosters for enhancement of the catalytic activity of [RuII(NHC)(para-cymene)]-based catalytic site. The boosters accelerated the oxidative loss of para-cymene from the catalytic site to generate the active catalyst during the oxidation of alkenes and alkynes into corresponding aldehydes, ketones and diketones. It was found that the boosting efficiency of the [OsII(terpy)2] units was considerably higher than its congener [RuII(terpy)2] unit in these assemblies. Mechanistic studies were conducted to understand this unique improvement.
- Mandal, Tanmoy,Singh, Vivek,Choudhury, Joyanta
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supporting information
p. 4774 - 4779
(2019/11/11)
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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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- 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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- NH4I/EtOCS2K promoted synthesis of substituted benzils from diphenylacetylene derivatives
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A facile protocol is described for the synthesis of benzil derivatives from readily accessible diarylacetylene derivatives using the NH4I/EtOCS2K system. This novel protocol results in excellent chemoselectivity and provided good to excellent yields. A control experiment indicated that the reaction proceeds via NH4I promoted EtOCS2K dimerization to give the corresponding dixanthogen and subsequent dixanthogen assisted oxidation.
- Jiang, Shaohua,Li, Yibiao,Luo, Xianglin,Huang, Guoling,Shao, Yan,Li, Dongli,Li, Bin
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supporting information
p. 3249 - 3252
(2018/07/21)
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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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- 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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- 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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- 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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- 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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- 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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- Wacker- type oxidation of alkynes into 1, 2-diketones using molecular oxygen
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An intriguing new Wacker- type oxidation of alkynes catalyzed by PdBr 2 and CuBr2 is described, which opens an efficient access to 1, 2-diketones using molecular oxygen. Under the optimized conditions, a variety of alkynes, including diarylalkynes, arylalkylalkynes, and dialkylalkynes, were compatible substrates in this transformation. The mechanism of this reaction was preliminarily investigated by control experiments.
- Ren, Wei,Xia, Yuanzhi,Ji, Shun-Jun,Zhang, Yong,Wan, Xiaobing,Zhao, Jing
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supporting information; experimental part
p. 1841 - 1844
(2009/09/05)
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- DMSO-PdI2 as a powerful oxidizing couple of alkynes into benzils: one-pot synthesis of nitrogen-containing five- or six-membered heterocycles
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PdI2 in DMSO promoted the oxidation of functionalized diarylalkynes into benzil derivatives in excellent yields. This new oxidation reaction was achieved with short reaction times and low loading of palladium catalyst. This efficient catalytic
- Mousset, Céline,Provot, Olivier,Hamze, Abdallah,Bignon, Jér?me,Brion, Jean-Daniel,Alami, Mouad
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p. 4287 - 4294
(2008/09/19)
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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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