2048-07-9Relevant academic research and scientific papers
Reduction of benzoyl tributylphosphonium chlorides by samarium diiodide as a novel access to 4-benzoylbenzaldehydes
Maeda,Huang,Hino,Yamauchi,Ohmori
, p. 2307 - 2308 (2000)
Addition of samarium diiodide to a well-stirred THF solution of benzoyl tributylphosphonium chlorides generated in situ from benzoyl chlorides and tributylphosphine at -40 °C gave 4-benzoylbenzaldehydes as predominant products from benzoyl chlorides without para-substituents, while benzoyl chloride bearing p-methyl or chloro groups was exclusively converted into the corresponding α-diketone.
Dendrimer-like core cross-linked micelle stabilized ultra-small gold nanoclusters as a robust catalyst for aerobic oxidation of α-hydroxy ketones in water
Yu, Yangyang,Lin, Chenlu,Li, Bing,Zhao, Pengxiang,Zhang, Shiyong
, p. 3647 - 3655 (2016)
As one of the most general and promising stabilizers, dendrimers have been widely used to prepare ultra-small gold nanoclusters. However, the complex synthesis of dendrimers hinders the further application of protected nanoclusters. Here we report a facile strategy to prepare an alternative material via core cross-linking of self-assembled micelles. The resulting dendrimer-like core cross-linked micelles (DCCMs) retain the main characteristics of dendrimers and avoid complex chemical synthesis. As expected, the DCCMs could easily encapsulate gold nanoparticles within their cores. The ultra-small clusters of Au5 were prepared without the participation of external reductants. Importantly, the DCCM stabilized noble gold clusters furnish excellent catalytic activity and perfect reusability for aerobic oxidation of α-hydroxy ketones in water. Only in open air the oxidation could be repeated up to 48 times with negligible turn-over frequency change. The total turnover number (TON) of the reaction reached unexpectedly >48 000, the highest TON for metal catalysed oxidation of hydroxy ketones so far. The further mechanism study hints that the carboxylic group of substrates might be involved in the catalytic process. The simple catalyst preparation, the environmentally benign reaction conditions, and the excellent catalytic performance and durability make the novel DCCM protected gold nanocluster a green catalyst.
Synthesis of α-Ketoimidoyl Fluorides via Geminal Fluorine-Promoted Azide Rearrangement
Kim, Ha Eun,Choi, Jun-Ho,Chung, Won-Jin
, p. 8810 - 8815 (2021/11/20)
Despite the promising synthetic potential, the utilization of imidoyl fluorides has been hampered by the lack of broadly applicable preparative methods. Herein, bench-stable α-ketoimidoyl fluorides were synthesized from geminal chlorofluorides through tandem azidation/rearrangement under mild conditions. The efficiency was consistently high, regardless of the steric and electronic environments. The synthetic utility of the α-ketoimidoyl fluoride was also demonstrated. Furthermore, the remarkable accelerating effect of the geminal fluorine substituent was identified and rationalized by density functional theory calculation.
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.
Conversion of alkynes into 1,2-diketones using HFIP as sacrificial hydrogen donor and DMSO as dihydroxylating agent
Gujjarappa, Raghuram,Vodnala, Nagaraju,Putta,Ganga Reddy, Velma,Malakar, Chandi C.
supporting information, (2020/01/21)
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.
Substituent Effect in the Synthesis of α,α-Dibromoketones, 1,2-Dibromalkenes, and 1,2-Diketones from the Reaction of Alkynes and Dibromoisocyanuric Acid
Cho, Eunjeong,Jayaraman, Aravindan,Lee, Junseong,Ko, Kyoung Chul,Lee, Sunwoo
, p. 1846 - 1858 (2019/03/07)
Internal alkynes reacted with dibromoisocyanuric acid/H2O to afford α,α-dibromoketone and 1,2-diketone derivatives. Diarylalkynes with activating groups provided 1,2-diketone derivatives as the major products, whereas diarylalkynes with a non-activating group or alkylarylalkynes gave α,α-dibromoketone derivatives as the major products. In addition, diarylalkynes with deactivating groups provided 1,2-dibromoalkenes. The reaction was conducted at room temperature and showed good yields in most cases. Reaction pathways have been proposed on the basis of experimental observations and density functional theory (DFT) calculations. (Figure presented.).
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
Shaik, Jeelani Basha,Ramkumar, Venkatachalam,Sankararaman, Sethuraman
supporting information, p. 1 - 8 (2018/02/19)
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.
NaBrO3/bmim[HSO4]: a versatile system for the selective oxidation of 1,2-diols, α-hydroxyketones, and alcohols
Khurana, Jitender M.,Lumb, Anshika,Chaudhary, Ankita
, p. 381 - 386 (2017/02/10)
Abstract: Sodium bromate with bmim[HSO4] has been found to be an excellent oxidizing agent in aqueous medium. NaBrO3:bmim[HSO4] oxidized 1,2-diols, α-hydroxyketones, and alcohols to the corresponding carbonyl compounds in excellent yields. This method offers advantages such as low cost reagents, aqueous reaction conditions, moderate temperatures and short reaction times and hence environmentally benign reaction. Moreover, the ionic liquid bmim[HSO4] could be recycled for at least three times without loss of significant activity. Graphical abstract: [Figure not available: see fulltext.]
Copper-catalyzed TEMPO oxidative cleavage of 1,3-diketones and β-keto esters for the synthesis of 1,2-diketones and α-keto esters
Zhou, Peng-Jun,Li, Cheng-Kun,Zhou, Shao-Fang,Shoberu, Adedamola,Zou, Jian-Ping
, p. 2629 - 2637 (2017/04/03)
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.
Preparation method of 1,2-diketone derivative
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Paragraph 0029, (2016/10/08)
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.
