36803-53-9Relevant academic research and scientific papers
Rhodium-Catalyzed Aerobic Decomposition of 1,3-Diaryl-2-diazo-1,3-diketones: Mechanistic Investigation and Application to the Synthesis of Benzils
Zhu, Jia-Liang,Tsai, Yi-Ting
, p. 813 - 828 (2020/12/22)
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.
Catalyst-Free and Transition-Metal-Free Approach to 1,2-Diketones via Aerobic Alkyne Oxidation
Shen, Duyi,Wang, Hongyan,Zheng, Yanan,Zhu, Xinjing,Gong, Peiwei,Wang, Bin,You, Jinmao,Zhao, Yulei,Chao, Mianran
, p. 5354 - 5361 (2021/05/05)
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.
Sequentially Pd/Cu-Catalyzed Alkynylation-Oxidation Synthesis of 1,2-Diketones and Consecutive One-Pot Generation of Quinoxalines
Niesobski, Patrik,Martínez, Ivette Santana,Kustosz, Sebastian,Müller, Thomas J. J.
supporting information, p. 5214 - 5218 (2019/07/31)
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.
Method for synthesizing benzil derivatives
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Paragraph 0054; 0055; 0056; 0057, (2019/01/23)
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.
Electrochemical synthesis of 1,2-diketones from alkynes under transition-metal-catalyst-free conditions
Zhou, Jie,Tao, Xiang-Zhang,Dai, Jian-Jun,Li, Chen-Guang,Xu, Jun,Xu, Hong-Mei,Xu, Hua-Jian
supporting information, p. 9208 - 9211 (2019/08/07)
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.
NH4I/EtOCS2K promoted synthesis of substituted benzils from diphenylacetylene derivatives
Jiang, Shaohua,Li, Yibiao,Luo, Xianglin,Huang, Guoling,Shao, Yan,Li, Dongli,Li, Bin
supporting information, p. 3249 - 3252 (2018/07/21)
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.
Two-Step One-Pot Synthesis of Unsymmetrical (Hetero)Aryl 1,2-Diketones by Addition-Oxygenation of Potassium Aryltrifluoroborates to (Hetero)Arylacetonitriles
Kumar, Yogesh,Jaiswal, Yogesh,Kumar, Amit
, p. 494 - 505 (2018/02/09)
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.
Mild Mn(OAc)3-Mediated Aerobic Oxidative Decarboxylative Coupling of Arylboronic Acids and Arylpropiolic Acids: Direct Access to Diaryl 1,2-Diketones
Lv, Wen-Xin,Zeng, Yao-Fu,Zhang, Shang-Shi,Li, Qingjiang,Wang, Honggen
supporting information, p. 2972 - 2975 (2015/06/30)
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.
Cobalt(II) catalyzed C(sp)-H bond functionalization of alkynes with phenyl hydrazines: Facile access to diaryl 1,2-diketones
Bharate, Jaideep B.,Abbat, Sheenu,Sharma, Rohit,Bharatam, Prasad V.,Vishwakarma, Ram A.,Bharate, Sandip B.
, p. 5235 - 5242 (2015/05/13)
A cobalt acetylacetonate catalyzed oxidative diketonation of alkynes via C(sp)-H bond functionalization has been described. The reaction involves a free-radical mechanism, wherein the phenyl radical formed from phenyl hydrazine couples with Co(ii) activated alkyne to produce 1,2-diketones. The reaction proceeds at room temperature in DMF with the use of Ag2O/air as the oxidizing system. The utility of the protocol for the synthesis of a series of imidazoles including a potent platelet aggregation inhibitor trifenagrel has been demonstrated.
Copper-catalyzed direct synthesis of diaryl 1,2-diketones from Aryl iodides and propiolic acids
Min, Hongkeun,Palani, Thiruvengadam,Park, Kyungho,Hwang, Jinil,Lee, Sunwoo
, p. 6279 - 6285 (2014/07/21)
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.
