- Decarboxylative Oxyacyloxylation of Propiolic Acids: Construction of Alkynyl-Containing α-Acyloxy Ketones
-
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
-
p. 8216 - 8225
(2021/06/28)
-
- Sulfur-mediated difunctionalization of internal and terminal alkynes for the synthesis of α-acetoxy ketones
-
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
-
-
- PhI(OAc)2-promoted umpolung acetoxylation of enamides for the synthesis of α-acetoxy ketones
-
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
-
p. 761 - 768
(2017/06/05)
-
- Novel and efficient transformation of enamides into α-acyloxy ketones via an acyl intramolecular migration process
-
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
-
supporting information
p. 10070 - 10073
(2016/11/06)
-
- Iron-Catalyzed Dioxygenation of Alkenes and Terminal Alkynes by using (Diacetoxyiodo)benzene as Oxidant
-
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
-
supporting information
p. 3587 - 3596
(2016/01/25)
-
- Silver(I)-catalyzed reaction of terminal alkynes with (diacetoxyiodo) benzene: A convenient, efficient and clean preparation of α-acetoxy ketones
-
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
-
p. 5937 - 5944
(2013/07/27)
-
- Straightforward and highly efficient synthesis of α-acetoxy ketones through gold-catalyzed intermolecular oxidation of terminal alkynes
-
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
-
p. 2605 - 2611
(2013/09/24)
-
- AZETIDINONE COMPOUNDS AND MEDICAL USE THEREOF
-
Preparation of azetidinone compounds and medical use thereof are provided by the present invention. More particularly, azetidionne compounds, shown as formula (I), wherein R1, R2, R3, R4, R5and R
- -
-
Page/Page column 14; 15
(2012/06/30)
-
- Activity of 6-aryl-pyrrolo[2,3-d]pyrimidine-4-amines to Tetrahymena
-
A series 6-aryl-pyrrolo[2,3-d]pyrimidine-4-amines (43 compounds), some of which are epidermal growth factor tyrosine kinase inhibitors, were tested for their protozoal toxicity using an environmental Tetrahymena strain as model organism. The protozoacidal activity of the analogues was found to be highly dependent on a 4-hydroxyl group at the 6-aryl ring, and a chiral 1-phenylethanamine substituent in position 4. Further, the potency was affected by the aromatic substitution pattern of the phenylethanamine: the unsubstituted, the meta-fluoro and the para-bromo substituted derivatives had the lowest minimum protozoacidal concentrations (8-16 μg/mL). Surprisingly, both enantiomers were found to have high potency suggesting that this compound class could have several modes of action. No correlation was found between the compounds protozoacidal activity and the in vitro epidermal growth factor receptor tyrosine kinase inhibitory potency. This suggests that the observed antimicrobial effects are related to other targets. Testing towards a panel of kinases indicated several alternative modes of action.
- Kaspersen, Svein Jacob,Hoff, Bard Helge,Sundby, Eirik,Charnock, Colin
-
p. 35 - 41,7
(2020/07/30)
-
- Synthesis of α-hydroxyacetophenones
-
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
-
experimental part
p. 5144 - 5148
(2012/07/03)
-
- Iron-catalyzed ketonization of 2-aryl-1,1-dibromoalkenes with KOAc: Synthesis of α-acetoxy aryl ketones via a Michael-like addition process
-
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
-
experimental part
p. 571 - 574
(2012/01/13)
-
- Copper(II) and 2,2'-biimidazole-promoted novel reaction of 4,4,4-trifluoro-1-phenylbutane-1,3-diones with iodobenzene diacetate
-
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
-
experimental part
p. 294 - 298
(2010/10/21)
-
- Enzyme-catalysed approach to the preparation of triazole antifungals: synthesis of (-)-genaconazole
-
The work describes a new enzyme-mediated approach to optically active epoxide (2R,3S)-6, which is an important key intermediate in the preparation of single enantiomers of chiral azole antifungals. The conversion of (2R,3S)-6 into (-)-genaconazole is reported as an example of its synthetic relevance.
- Acetti, Daniela,Brenna, Elisabetta,Fuganti, Claudio,Gatti, Francesco G.,Serra, Stefano
-
experimental part
p. 2413 - 2420
(2010/03/24)
-
- Tetraarylphosphonium salts as soluble supports for oxidative catalysts and reagents
-
(Figure Presented) Tetraarylphosphonium (TAP)-supported DMSO, TEMPO, and DIB reagents were synthesized and used for the oxidation of alcohols, including Swern oxidation and for the R-acetoxylation of ketones. By taking advantage of the predictable solubility properties of the TAP unit, simple precipitation and filtration of the phosphonium moiety permit complete separation of the desired oxidation products. This paper describes the preparation of these three TAP-supported oxidative reagents and their activity in the aforementioned oxidative transformations. Furthermore, we have demonstrated that these reagents can be recycled directly when used in catalytic processes and following regeneration when used in stoichiometric processes. 2009 American Chemical Society.
- Roy, Marie-Noelle,Poupon, Jean-Christophe,Charette, Andre B.
-
supporting information; experimental part
p. 8510 - 8515
(2009/12/28)
-
- One-pot synthesis of α-formyloxy ketones from enolizable ketones
-
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
-
p. 338 - 345
(2008/04/01)
-
- Synthesis and biological evaluation of quinoline salicylic acids as P-selectin antagonists
-
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
-
-
- Iodobenzene-catalyzed α-acetoxylation of ketones. In situ generation of hypervalent (diacyloxyiodo)benzenes using m-chloroperbenzoic acid
-
Reported here for the first time is the iodobenzene-catalyzed α-oxidation of ketones, in which diacyloxy(phenyl)-λ3-iodanes generated in situ act as real oxidants of ketones and m-chloroperbenzoic acid serves as a terminal oxidant. Oxidation of a ketone with m-chloroperbenzoic acid in acetic acid in the presence of a catalytic amount of iodobenzene, BF3·Et2O, and water at room temperature under argon affords an α-acetoxy ketone in good yield. p-Methyl- and p-chloroiodobenzene also serve as efficient catalysts in this direct oxidation. We found that when the reaction was carried out in the absence of a catalytic amount of iodobenzene, Baeyer-Villiger oxidation of a ketone took place. It is noted that use of water and BF3·Et2O is crucial to the success of this α-acetoxylation. Copyright
- Ochiai, Masahito,Takeuchi, Yasunori,Katayama, Tomoko,Sueda, Takuya,Miyamoto, Kazunori
-
p. 12244 - 12245
(2007/10/03)
-
- Synthesis and Biological activity of new HMG-CoA reductase inhibitors. 3.1,2 lactones of 6-phenoxy-3,5-dihydroxyhexanoic acids
-
A group of 43 optically active sodium carboxylates (11a-qq and the corresponding lactones 4 were prepared from respective phenols 8 according to Schemes I-III. Phenols 8 were synthesized from commercially available compounds according to Schemes IV-IX. A
- Jendralla,Granzer,V Kerekjarto,Krause,Schacht,Baader,Bartmann,Beck,Bergmann,Kessler,Wess,Chen,Granata,Herchen,Kleine,Schussler,Wagner
-
p. 2962 - 2983
(2007/10/02)
-