- Decarboxylative Oxyacyloxylation of Propiolic Acids: Construction of Alkynyl-Containing α-Acyloxy Ketones
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Novel decarboxylative oxyacyloxylation of propiolic acids has been developed. This reaction provides an efficient access to alkynyl-containing α-acyloxy ketones from readily available starting materials and exhibits significant functional group tolerance. Furthermore, oxyacyloxylation of terminal alkynes and aliphatic propiolic acids was also developed. A possible reaction mechanism is proposed based on mechanistic studies.
- Chen, Xin,Xin, Yangchun,Zhao, Zhi-Wei,Hou, Yu-Jian,Wang, Xiang-Xiang,Xia, Wen-Jin,Li, Ya-Min
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p. 8216 - 8225
(2021/06/28)
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- Sulfur-mediated difunctionalization of internal and terminal alkynes for the synthesis of α-acetoxy ketones
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The sulfur-mediated difunctionalization of alkynes is reported to give α-acetoxy ketones in a one-pot operation under mild conditions with 19–92% yield. By using wet potassium acetate as both the aqueous base and nucleophilic reagent, both terminal alkynes and internal alkynes could be converted into the α-acetoxy ketone products.
- Li, Pingfan,Zhang, Zhong
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- Metal-Free Amidation Reactions of Terminal Alkynes with Benzenesulfonamide
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A novel and efficient approach has been developed to synthesize α-sulfonylamino ketones through the reaction between terminal alkynes and sulfonamides under ambient air using PIDA (diacetoxy iodobenzene). A library of α-sulfonylamino ketone derivatives having a variety of substituents has been synthesized. A plausible reaction pathway has been predicted. This reaction offers a broad substrate scope, metal-free synthesis, excellent regioselectivity, easily accessible reactants, and room temperature reaction conditions under ambient air and is operationally simple. A gram-scale synthesis demonstrates the potential applications of the present method. In addition, we have also synthesized α-acetoxy ketones in the case of absence of sulfonamide.
- Mahato, Sachinta,Santra, Sougata,Zyryanov, Grigory V.,Majee, Adinath
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- Natural products as sources of new fungicides (V): Design and synthesis of acetophenone derivatives against phytopathogenic fungi in vitro and in vivo
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A series of acetophenone derivatives (10a–10i, 11, 12a–12g, 13a–13g, 14a–14d and 15a–15l) were designed, synthesized and evaluated for antifungal activities in vitro and in vivo. The antifungal activities of 53 compounds were tested against several plant pathogens, and their structure–activity relationship was summarized. Compounds 10a–10f displayed better antifungal effects than two reference fungicides. Interestingly, the most potent compound 10d exhibited antifungal properties against Cytospora sp., Botrytis cinerea, Magnaporthe grisea, with IC50 values of 6.0–22.6 μg/mL, especially Cytospora sp. (IC50 = 6.0 μg/mL). In the in vivo antifungal assays, 10d displayed the significant protective efficacy of 55.3% to Botrytis cinerea and 73.1% to Cytospora sp. The findings indicated that 10d may act as a potential pesticide lead compound that merits further investigation.
- Dan, Wen-Jia,Tuong, Thi-Mai-Luong,Wang, Da-Cheng,Li, Ding,Zhang, An-Ling,Gao, Jin-Ming
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p. 2861 - 2864
(2018/07/25)
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- Oxidative α-Acetoxylation of a β-Oxime Ester with (Diacetoxyiodo)benzene Catalyzed by ScIII Salts: An Approach to the Docetaxel Side Chain
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Hypervalent iodine(III) compounds have emerged as reagents of choice for α-oxidation of various ketones under mild reaction conditions. We report herein a simple method for α-hydroxylation of a β-oxime ester, which involves an oxidative α-acetoxylation us
- Miyamoto, Kazunori,Hoque, Md. Mahbubul,Senoh, Yuhki,Ali, Mohammad Idrish,Nemoto, Hisao,Mandai, Tadakatsu
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supporting information
p. 2841 - 2845
(2018/06/21)
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- PhI(OAc)2-promoted umpolung acetoxylation of enamides for the synthesis of α-acetoxy ketones
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Umpolung is a fundamental concept in organic chemistry, which provides an alternative strategy for the synthesis of target compounds which were not easily accessible by conventional methods. Herein, a mild and efficient PhI(OAc)2-promoted umpolung acetoxylation reactions of enamides was developed for the synthesis of α-acetoxy ketones. The reaction tolerates a wide range of functional groups and affords α-acetoxy ketones in good to excellent yields. PhI(OAc)2 serves as a source of acetoxy in the reaction.
- Chen, Ming,Zhang, Wei,Ren, Zhi-Hui,Gao, Wen-Yun,Wang, Yao-Yu,Guan, Zheng-Hui
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p. 761 - 768
(2017/06/05)
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- Novel and efficient transformation of enamides into α-acyloxy ketones via an acyl intramolecular migration process
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Hydrogen peroxide and anhydride mediated transformation of enamides to afford substituted α-acyloxy ketones is described. This transition-metal-free cascade reaction has a broad substrate scope and high efficiency. The acyl intramolecular migration procedure successfully achieved this acyloxylation process under mild conditions and increased the atom efficiency.
- Zhou, Xiaoqiang,Ma, Haojie,Cao, Jinhui,Liu, Xingxing,Huang, Guosheng
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supporting information
p. 10070 - 10073
(2016/11/06)
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- Iron-Catalyzed Dioxygenation of Alkenes and Terminal Alkynes by using (Diacetoxyiodo)benzene as Oxidant
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An iron-catalyzed syn-diacetoxylation of alkenes and 1,2-oxyacetoxylation of terminal alkynes has been developed using (diacetoxyiodo)benzene as oxidant. A broad range of internal and terminal alkenes, including electron-rich as well as electron-deficient alkenes, gave the desired products in good to excellent yields with high diastereoselectivity (up to >99:1 dr). In addition the high catalytic activity of iron catalysis for the 1,2-oxyacetoxylation of terminal alkynes is also reported. The roles of catalyst, oxidant and other reaction parameters were evaluated for activation of the unsaturated bond.
- Srinivas,Rawat, Vikas S.,Sreedhar, Bojja
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supporting information
p. 3587 - 3596
(2016/01/25)
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- Straightforward and highly efficient synthesis of α-acetoxy ketones through gold-catalyzed intermolecular oxidation of terminal alkynes
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A variety of terminal alkynes were efficiently converted into the corresponding α-acetoxy ketones through gold-catalyzed intermolecular oxidation in the presence of 8-methylquinoline 1-oxide as the oxidant. The reaction probably proceeds through an α-oxo gold carbene intermolecular O-H insertion.
- Wu, Chao,Liang, Zhiwu,Yan, Dong,He, Weimin,Xiang, Jiannan
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p. 2605 - 2611
(2013/09/24)
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- Silver(I)-catalyzed reaction of terminal alkynes with (diacetoxyiodo) benzene: A convenient, efficient and clean preparation of α-acetoxy ketones
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Silver(I)-catalyzed reaction of terminal alkynes with (diacetoxyiodo) benzene in wet acetonitrile at room temperature afforded the corresponding α-acetoxy ketones in 55-93% yields. The salient features of this reaction are the effective utilization of PhI
- Deng, Guisheng,Luo, Jing
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p. 5937 - 5944
(2013/07/27)
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- Synthesis of α-hydroxyacetophenones
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A general method for the preparation of α-hydroxyacetophenones is presented. Functionalized arylmagnesium species are transmetalated to the corresponding arylzinc intermediates, which undergo Cu(I)-catalyzed reaction with acetoxyacetyl chloride. Acidic hy
- McLaughlin, Mark,Belyk, Kevin M.,Qian, Gang,Reamer, Robert A.,Chen, Cheng-Yi
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experimental part
p. 5144 - 5148
(2012/07/03)
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- Iron-catalyzed ketonization of 2-aryl-1,1-dibromoalkenes with KOAc: Synthesis of α-acetoxy aryl ketones via a Michael-like addition process
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A novel and convenient iron-catalyzed ketonization of 2-aryl-1,1- dibromoalkenes with KOAc has been achieved. A series of α-acetoxy aryl ketones were prepared with moderate yields via 2-carbon position functionalization of 2-aryl-1,1-dibromoalkenes.
- Zhao, Ming,Kuang, Chun Xiang,Cheng, Xue Zhi,Yang, Qing
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experimental part
p. 571 - 574
(2012/01/13)
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- A sustainable byproduct catalyzed domino strategy: Facile synthesis of α-formyloxy and acetoxy ketones via iodination/nucleophilic substitution/hydrolyzation/oxidation sequences
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The sustainable byproduct catalyzed domino strategy has been performed for the facile synthesis of α-formyloxy and acetoxy ketones via iodination/nucleophilic substitution/hydrolyzation/oxidation sequences from simple and readily available aromatic ketone
- Zhu, Yan-Ping,Gao, Qing-He,Lian, Mi,Yuan, Jing-Jing,Liu, Mei-Cai,Zhao, Qin,Yang, Yan,Wu, An-Xin
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supporting information; experimental part
p. 12700 - 12702
(2012/01/03)
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- Biocatalytic reduction of prochiral aromatic ketones to optically pure alcohols by a coupled enzyme system for cofactor regeneration
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A simple, highly efficient, and economical biphasic cell-free system was developed for biocatalytic reduction of prochiral aromatic ketones to furnish enantiopure alcohols. This system is characterized by using endogenous enzymes of the cell-free extract to form enzyme-coupled NADPH recycling system. Besides, it offered much higher productivity than whole cells and greatly simplified the preparation process of biocatalysts in comparison with isolated enzymes. Various prochiral aromatic ketones, especially α-substituted acetophenone derivatives, were reduced to chiral alcohols with excellent enantiomeric excess (ee) and moderate to good yield by this cell-free system.
- Yan, Zhen,Nie, Yao,Xu, Yan,Liu, Xiang,Xiao, Rong
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supporting information; experimental part
p. 999 - 1002
(2011/03/21)
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- Copper(II) and 2,2'-biimidazole-promoted novel reaction of 4,4,4-trifluoro-1-phenylbutane-1,3-diones with iodobenzene diacetate
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A new and efficient way was developed to carry out the reaction of 4,4,4-trifluoro-1-phenylbutane-1,3-dione with iodobenzene diacetate under the assistance of Cu(II) and 2,2'-biimidazole at a low temperature in excellent yield. 2-Acetoxyacetophenone was obtained unexpectedly.
- Zhou, Chunmei,Zeng, Runsheng,Zou, Jianping
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experimental part
p. 294 - 298
(2010/10/21)
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- The reaction of terminal alkynes with PhI(OAc)2: a convenient procedure for the preparation of α-acyloxy ketones
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Treatment of terminal alkynes with PhI(OAc)2 in different acids at 70 °C provided the corresponding α-acyloxy ketones in good to excellent yields. A plausible mechanism has been proposed based on the experimental results.
- Mo, Dong-Liang,Dai, Li-Xin,Hou, Xue-Long
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supporting information; experimental part
p. 5578 - 5581
(2011/02/22)
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- One-pot synthesis of α-formyloxy ketones from enolizable ketones
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One-pot synthesis of α-formyloxy tones as well as α-acetoxy ketones from enolizable ketones and [hydroxy(tosyloxy) iodo] benzene (HTIB)/polymer supported [hydroxy(tosyloxy) iodo] benzene (PSHTIB) in N,N-dimethylformamide (DMF)/N, N-dimethylacetamide (DMA)
- Kumar, Sunil,Kumar, Ashok,Gupta, Rakesh K.,Kumar, Devinder
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p. 338 - 345
(2008/04/01)
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- An efficient method for the α-acetoxylation of ketones
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α-Acetoxylation of ketones catalyzed by iodobenzene using 30% aqueous hydrogen peroxide and acetic anhydride as the oxidant is an effective and economical method for the preparation of a-acetoxy ketones. The reaction gave the products in good yields witho
- Sheng, Jinmei,Li, Xiaolong,Tang, Mingfang,Gao, Botao,Huang, Guosheng
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p. 1165 - 1168
(2008/02/03)
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- Synthesis and biological evaluation of quinoline salicylic acids as P-selectin antagonists
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Leukocyte recruitment of sites of inflammation and tissue injury involves leukocyte rolling along the endothelial wall, followed by firm adherence of the leukocyte, and finally transmigration of the leukocyte across cell junctions into the underlying tissue. The initial rolling step is mediated by the interaction of leukocyte glycoproteins containing active moieties such as sialyl Lewisx (sLex) with P-selectin expressed on endothelial cells. Consequently, inhibition of this interaction by means of a small molecule P-selectin antagonist is an attractive strategy for the treatment of inflammatory diseases such as arthritis. High-throughput screening of the Wyeth chemical library identified the quinoline salicylic acid class of compounds (1) as antagonists of P-selectin, with potency in in vitro and cell-based assays far superior to that of sLex. Through iterative medicinal chemistry, we identified analogues with improved P-selectin activity, decreased inhibition of dihydrooratate dehydrogenase, and acceptable CYP profiles. Lead compound 36 was efficacious in the rat AIA model of rheumatoid arthritis.
- Kaila, Neelu,Janz, Kristin,DeBernardo, Silvano,Bedard, Patricia W.,Camphausen, Raymond T.,Tam, Steve,Tsao, Desirée H.H.,Keith Jr., James C.,Nickerson-Nutter, Cheryl,Shilling, Adam,Young-Sciame, Ruth,Wang, Qin
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- Chemoenzymatic synthesis of enantiomerically pure 1,2-diols employing immobilized lipase in the ionic liquid [bmim]PF6
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Significantly enhanced enantioselectivity in the enzymatic kinetic resolution of 1,2-diols employing immobilized lipase from Pseudomonas cepacia (PS-C, 'Amano') results from the use of the ionic liquid [bmim]PF6 as reaction medium.
- Kamal, Ahmed,Chouhan, Gagan
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p. 8801 - 8805
(2007/10/03)
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- Chemoenzymatic synthesis of enantiomerically pure terminal 1,2-diols
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A new practical method for the enzymatic synthesis of 1,2-diols has been developed by employing a lipase catalyzed one-pot transesterification protocol. A series of substituted α-acetoxyphenylethanones 3a-g have been reduced to the corresponding alcohols under mild conditions employing sodium borohydride and moist neutral alumina, and further subjected for lipase catalyzed irreversible transesterification in the same pot to give mono- and diacetate diols (R)-4 and (S)-5, which on hydrolysis afforded terminal 1,2-diols, (R)- and (S)-6 in high enantiomeric excess.
- Kamal, Ahmed,Sandbhor, Mahendra,Ahmed, Kaleem,Adil,Shaik, Ahmad Ali
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p. 3861 - 3866
(2007/10/03)
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- Synthesis of α-acetoxy and formyloxy ketones by thallium(III) promoted α-oxidation
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Treatment of ketones with thallium(III) triflate in amide solvents at 60°C for 30 min followed by addition of small amounts of H2O cleanly provided the corresponding α-acyloxy ketones.
- Lee,Jin,Choi
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p. 956 - 957
(2007/10/03)
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- Conversion of Aldehydes to α-Acetoxymethyl Ketones: One-carbon Homologation with (Benzotriazol-1-yl)phenoxymethane
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Reaction of aldehydes with (benzotriazol-1-yl)phenoxymethyl anion afforded the corresponding addition products which, upon treatment with p-toluenesulfonic acid in acetic acid, yielded the corresponding α-acetoxymethylketones.
- Katritzky, Alan R.,Yang, Zhijun,Moutou, Jean-Luc
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p. 841 - 844
(2007/10/02)
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- Intramolecular Photocycloaddition of the C=C Double Bond to the CN Triple Bond Resulting in the Formation of a Novel Cyclic System
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Irradiation of a bichromophoric 1-(o-cyanobenzyloxy)-2-(p-methoxyphenyl)-2-butene (1a) in cyclohexane gave an isoquinoline derivative, 8-methoxy-6-methyl-11,13-dihydrobenzoxepinoisoquinoline (2a). The structure was determined by X-ray analysis. The formation of 2a can be accounted for by the initial cycloaddition of 1a in the excited singlet state between the C=C double bond and CN triple bond, followed by cleavage of the resulting azetine ring and recyclization.
- Sakuragi, Hirochika,Koyama, Toshiya,Sakurazawa, Mamoru,Yasui, Norimichi,Tokumaru, Katsumi,Ueno, Katsuhiko
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p. 1769 - 1772
(2007/10/02)
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- Reactions of Substituted Phenacyl Bromides with Various Bases: p-Methyl- and p-Methoxyphenacyl Bromide. II
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The products obtained from the reaction of p-methyl- and p-methoxyphenacyl bromide with various bases are described.
- Baghdadchi, Jamil,Chan, Albert P.,Hutchinson, James H.
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p. 973 - 974
(2007/10/02)
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- α-METHOXY KETONES BY THE REACTION OF TRIMETHYLSILYL ENOL ETHERS WITH LEAD TETRAACETATE IN METHANOL
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Trimethylsilyl enol ethers of acetophenone, 2-acetylthiophene and 2-acetylfuran react with lead tetraacetate in methanol at room temperature to give the α-methoxy ketones in good yields.
- Moriarty, Robert M.,Prakash, Indra,Penmasta, Raju
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p. 709 - 714
(2007/10/02)
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- Radical-Cations as Intermediates in the Oxidation of Alkenes by Metal Ions
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The formation of hydroxy acetates in the reaction of some alkenes with lead(IV), cobalt(III), and manganese(III) in acetic acid is demonstrated to involve the intermediacy of alkene radical-cations.A study employing a range of aryl-substituted alkenes has shown that there is an inverse relationship between the yield of hydroxy acetate and the ionisation potential of the organic substrate.The electron deficiency in the radical-cations derived from these alkenes appears to be localised on the double bond: no evidence could be obtained for reaction at the aromatic ring.The introduction of the chlorine atom into this ring had the effect of repressing electron-transfer in cobalt(III) and manganese(III) oxidations but not in those involving lead(IV).
- Norman, Julie A.,Thomas, C. Barry,Burrow, Michael J.
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p. 1087 - 1094
(2007/10/02)
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- The Contrast in the Reactions of Toluene-p-sulphonylhydrazones and Semicarbazones with the Acetates of Hg(II), Tl(III) and Pb(IV). Some Useful Regenerations of Carbonyl Compounds: Reactions of Mercuric Acetate with Nitrogen Compounds. Part 7.
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Thallium triacetate in acetic acid gave a clean regeneration of both aldehydes and ketones from their toluene-p-sulphonylhydrazones.The reagent also cleaved carbonyl compounds from semicarbazones at reflux temperatures in acetic acid with some interference from side reactions due to the vigorous conditions.Treatment of benzil monosemicarbazone with thallium triacetate gave 5,6-diphenyl-1,2,4-triazin-3-one and oxidation of benzil mono- and bis(toluene-p-sulphonyl) hydrazones gave a fragmentation of the hydrazone chain to a diazo species which was isolated in the former case and in the latter case cyclised to 1-(toluene-p-sulphonamido)-4,5-diphenyl-1,2,3-triazole.These reactions are compared with the corresponding reactions of mercuric acetate and lead tetraacetate and the mechanisms are discussed.The essential difference between the behaviour of the three isoelectronic reagents with hydrazone substrates lies in the lability of the hydrazone amino N-metal bond of an N-metallo intermediate and the influence of the charge on the metal on adjacent labile bonds.In the case of Tl(III) the redox step is intermolecular and involves solvent participation.
- Butler, Richard N.,Morris, Gerard J.,O'Donohue, Anne M.
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p. 808 - 820
(2007/10/02)
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