- Access to α,α-dihaloacetophenones through anodic C[dbnd]C bond cleavage in enaminones
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We have developed a method to synthesize α,α-dihaloketones under electrochemical conditions. In this reaction, the Cl- or Br- is oxidized to Cl2 or Br2 at the anode, which undergoes two-step addition reactions with the N,N-dimethyl enaminone, and finally breaks C[dbnd]C of the N,N-dimethyl enaminone to generate α,α-dihaloketones. The electrosynthesis reaction can be conveniently carried out in an undivided electrolytic cell at room temperature. In addition, various functional groups are compatible with this green protocol which can be applied simultaneously to the gram scale without significantly lower yield.
- Zhang, Zhenlei,Yang, Jiusi,Wu, Kairui,Yu, Renjie,Bu, Jiping,Huang, Zijun,Li, Shaoke,Ma, Xiantao
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supporting information
(2021/12/20)
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- Electrochemical Oxidative Oxydihalogenation of Alkynes for the Synthesis of α,α-Dihaloketones
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An electrochemical oxydihalogenation of alkynes has been developed for the first time. Using this sustainable protocol, a variety of α,α-dihaloketones can be prepared with readily available CHCl3, CH2Cl2, ClCH2CH2Cl, and CH2Br2 as the halogen source under electrochemical conditions at room temperature.
- Meng, Xiangtai,Zhang, Yu,Luo, Jinyue,Wang, Fei,Cao, Xiaoji,Huang, Shenlin
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supporting information
p. 1169 - 1174
(2020/02/04)
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- Electrochemical synthesis of α,α-dihaloacetophenones from terminal alkyne derivatives
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By virtue of electrochemistry, a series of α,α-dihaloacetophenones were easily obtained with good to excellent yields. This electrochemical procedure was taken in a divided cell with constant current in aqueous media. The reaction can be carried out smoothly at room temperature under metal and oxidant free condition, which provides an eco-friendly synthesis for the α,α-dihaloacetophenone derivatives.
- Li, Zhibin,Sun, Qi,Qian, Peng,Hu, Kangfei,Zha, Zhenggen,Wang, Zhiyong
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supporting information
p. 1855 - 1858
(2020/03/10)
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- Iodine-DMSO-promoted divergent reactivities of arylacetylenes
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An unprecedented set of efficient, economical, atom-economic and exceedingly selective I2-DMSO-promoted methods is described for the generation of different structures. The reaction represents the first of its kind, involving the use of different iodine concentrations, temperatures, acids and salt to adjust the selectivity for the synthesis of different alkenes, α-functionalized ketones and α-ketomethylthioesters.
- Rather, Suhail A.,Kumar, Atul,Ahmed, Qazi Naveed
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supporting information
p. 4511 - 4514
(2019/04/26)
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- Dichloroacetophenones targeting at pyruvate dehydrogenase kinase 1 with improved selectivity and antiproliferative activity: Synthesis and structure-activity relationships
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Dichloroacetophenone is a pyruvate dehydrogenase kinase 1 (PDK1) inhibitor with suboptimal kinase selectivity. Herein, we report the synthesis and biological evaluation of a series of novel dichloroacetophenones. Structure-activity relationship analyses (SARs) enabled us to identify three potent compounds, namely 54, 55, and 64, which inhibited PDK1 function, activated pyruvate dehydrogenase complex, and reduced the proliferation of NCI-H1975 cells. Mitochondrial bioenergetics assay suggested that 54, 55, and 64 enhanced the oxidative phosphorylation in cancer cells, which might contribute to the observed anti-proliferation effects. Collectively, these results suggested that 54, 55, and 64 could be promising compounds for the development of potent PDK1 inhibitors.
- Zhang, Shao-Lin,Yang, Zheng,Hu, Xiaohui,Tam, Kin Yip
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supporting information
p. 3441 - 3445
(2018/09/29)
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- Micelle-Enabled Photoassisted Selective Oxyhalogenation of Alkynes in Water under Mild Conditions
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Using micelles of FI-750-M, visible light, photocatalysts, and inexpensive halogenating reagents, such as N-bromosuccinimide and N-chlorosuccinimde, selective oxyhalogenations of alkynes were achieved in water under very mild conditions. No halogenation at the aromatic rings was detected, and control experiments revealed the radical pathway. The easily conducted protocol exhibited high reproducibility, was readily adjusted to gram scale, and allowed for recycling of reaction medium and catalyst.
- Finck, Lucie,Brals, Jeremy,Pavuluri, Bhavana,Gallou, Fabrice,Handa, Sachin
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p. 7366 - 7372
(2018/07/29)
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- Method for removal of methanamide by dichlorination
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A method for removal of methanamide by dichlorination is disclosed, according to the method, a finished product is obtained by removal of methanamide by dichlorination by one-step-reaction of various beta-carbonyl amide derivatives as raw materials, 2,2,6,6-Tetramethylpiperidinooxy (TEMPO) and an alkali as additives and N-chlorosuccinimide as a reagent in a reaction solvent, and then concentration and purification. According to the method, synthesis of an alpha-dichloroacetophenone derivative can be realized for the first time by a method of removal of methanamide by fracturation of carbon-carbon single bond. The method is novel and unique, has certain universality, is mild in reaction conditions, low in requirement of production equipment, and simple in technology, has the advantages of high efficiency, simple operation, high safety, economy and environmentally-friendliness; high-quality diverse alpha-dichloroacetophenone derivative products can be prepared by the method, and the products prepared by the method are important drug synthesis intermediates and material intermediates, can be widely used in the synthesis of heterocycles, unsaturated acids, acetylene alcohols and other compounds and cyclopropanation, and have wide market prospects.
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Paragraph 0020-0049; 0080-0084
(2017/10/12)
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- One-pot dichlorinative deamidation of primary β-ketoamides
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An approach to the dichlorinative deamidation of primary β-ketoamides through ketonic cleavage is described, and a series of α,α-dichloroketones were furnished mostly in the presence of TEMPO. Based on control experiments, a mechanism involving tandem dichlorination and deamidation is proposed to interpret the observed reactivity.
- Zheng, Congke,Zhang, Xiaohui,Ijaz Hussain, Muhammad,Huang, Mingming,Liu, Qing,Xiong, Yan,Zhu, Xiangming
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p. 574 - 577
(2017/01/16)
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- Pathways in the Degradation of Geminal Diazides
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The degradation of geminal diazides is described. We show that diazido acetates are converted into tetrazoles through the treatment with bases. The reaction of dichloro ketones with azide anions provides acyl azides, through in situ formation of diazido ketones. We present experimental and theoretical evidence that both fragmentations may involve the generation of acyl cyanide intermediates. The controlled degradation of terminal alkynes into amides (by loss of one carbon) or ureas (by loss of two carbons) is also shown.
- Holzschneider, Kristina,H?ring, Andreas P.,Haack, Alexander,Corey, Daniel J.,Benter, Thorsten,Kirsch, Stefan F.
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p. 8242 - 8250
(2017/08/14)
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- Ultrasound-assisted tandem reaction of alkynes and trihaloisocyanuric acids by thiourea as catalyst in water
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With water as the sole solvent, a green and efficient method has been developed for the synthesis of various α,α-dihaloketones via ultrasound assisted p-tolylthiourea catalyzed tandem reaction of alkynes with trihaloisocyanuric acids. This synthetic route
- Zhang, Xingyu,Wu, Yundong,Zhang, Ya,Liu, Huilan,Xie, Ziyu,Fu, Shengmin,Liu, Fang
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p. 4513 - 4518
(2017/07/10)
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- N-Chloro-N-methoxybenzenesulfonamide: A Chlorinating Reagent
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A structurally simple and reactive chlorinating reagent, N-chloro-N-methoxybenzenesulfonamide, was conveniently and economically prepared in high yield. 1,3-Diketones, β-keto esters, benzoyl trifluoroacetones, phenols, anisoles, heteroarenes, and aromatic amines were successfully chlorinated, and the products were obtained in good to high yields.
- Pu, Xiaoqiu,Li, Qingwei,Lu, Zehai,Yang, Xianjin
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supporting information
p. 5937 - 5940
(2016/12/26)
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- K 2S 2O 8-mediated difunctionalization of C≡C bonds in water: A simple and efficient approach to α, α -dihaloacetophenones from phenylacetylenes and NaX
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A novel K2S2O8-mediated oxy-1,1-dihalogenation of alkynes with NaX in the presence of water has been developed, affording α,α-dihaloacetophenones in moderate to good yields. The advantages of this reaction are mild reaction conditions, operational simplicity, and use of pure water as reaction medium. A plausible reaction mechanism is proposed on the basis of mechanistic studies.
- Wang, Jing-Yu,Jiang, Qing,Guo, Can-Cheng
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supporting information
p. 3130 - 3138
(2015/10/12)
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- A simple, mild, and efficient method for the preparation of α,α-dichloroketones with DCDMH catalyzed by ammonium chloride
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New process that can selectively prepare α,α-dichloro ketones from various ketones with 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) using ammonium chloride as a catalyst is reported. The effects of ammonium salts, solvents, DCDMH, and reaction temperature were investigated. Under the optimal condition, most of α,α-dichlorinated products were selectively obtained in 86-98% yield.
- Zheng, Zubiao,Han, Bingbing,Cheng, Peng,Niu, Jiangxiu,Wang, Aidong
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p. 9814 - 9818
(2015/01/09)
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- α-Halogenation of carbonyl compounds: Halotrimethylsilane-nitrate salt couple as an efficient halogenating reagent system
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A mixture of chloro/bromotrimethylsilane and nitrate salt is found to be an effective reagent system for the α-chlorination/bromination of carbonyl compounds. The reaction occurs under mild conditions yielding the products in moderate to good yields.
- Prakash, G.K. Sxurya,Ismail, Rehana,Garcia, Jessica,Panja, Chiradeep,Rasul, Golam,Mathew, Thomas,Olah, George A.
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experimental part
p. 1217 - 1221
(2011/03/22)
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- Cu(OTf)2-catalyzed α-halogenation of ketones with 1,3-dichloro-5,5'-dimethylhydantoin and N-bromosuccinimide
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Copper(II) triflate catalyses efficiently the α-halogentaion of aryl or alkyl ketones with l.3-diehloro-5.5'-dimethylhydantoin and N-bromosuccinimde to give the corresponding α,α-dichloroketones and α-bromoketones in high yield with excellent product selectivity.
- Jagdale, Arun R.,Chouthaiwale, Pandurang V.,Sudalai, Arumugam
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experimental part
p. 1424 - 1430
(2010/02/28)
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- Selective preparation of α,α-dichloroketones with copper(II) chloride
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Aryl and enolizable alkyl ketones react with copper(II) chloride in dimethylformamide to produce the corresponding α,α-dichloroketone in high yields. Remarkable qualities of the process are high selectivity towards these substrates, undetected polychlorinated by-products, easy work-up, commercially available reagents and HCl as the only waste stream.
- Nobrega, Jose Arimateia,Goncalves, Simone Maria C.,Peppe, Clovis
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p. 3711 - 3717
(2007/10/03)
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- Reactions of 1-aryl-2,2-dihalogenoethanone oximes with tetrasulfur tetranitride (S4N4): A general method for the synthesis of 3-aryl-4-halogeno-1,2,5-thiadiazoles
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1-Aryl-2,2-dichloro-7, 1-aryl-2,2-dibromo-8, 1-aryl-2-bromo-2-fluoro-9 and 1-aryl-2-chloro-2-fluoroethanone oximes 10 have been prepared by allowing the corresponding ketones to react with hydroxylamine hydrochloride in EtOH at room temperature. Stereoche
- Yoon, Sung Cheol,Cho, Jaeeock,Kim, Kyongtae
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p. 109 - 116
(2007/10/03)
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