- Dirhodium-Catalyzed Enantioselective B?H Bond Insertion of gem-Diaryl Carbenes: Efficient Access to gem-Diarylmethine Boranes
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The scarcity of reliable methods for synthesizing chiral gem-diarylmethine borons limits their applications. Herein, we report a method for highly enantioselective dirhodium-catalyzed B?H bond insertion reactions with diaryl diazomethanes as carbene precursors. These reactions afforded chiral gem-diarylmethine borane compounds in high yield (up to 99 % yield), high activity (turnover numbers up to 14 300), high enantioselectivity (up to 99 % ee) and showed unprecedented broad functional group tolerance. The borane compounds synthesized by this method could be efficiently transformed into diaryl methanol, diaryl methyl amine, and triaryl methane derivatives with good stereospecificity. Mechanistic studies suggested that the borane adduct coordinated to the rhodium catalyst and thus interfered with decomposition of the diazomethane, and that insertion of a rhodium carbene (generated from the diaryl diazomethane) into the B?H bond was most likely the rate-determining step.
- Huang, Ming-Yao,Li, Xiao-Yu,Su, Yu-Xuan,Yang, Liang-Liang,Zhao, Yu-Tao,Zhu, Shou-Fei
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p. 24214 - 24219
(2021/10/07)
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- Transition-Metal-Free Regiospecific Aroylation of Nitroarenes Using Ethyl Arylacetates at Room Temperature
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A novel regiospecific C(sp3)-C(sp2) coupling between ethyl arylacetates and nitroarenes has been developed to deliver biaryl ketones in excellent yields. The protocol is metal-free, mild, and compatible with a number of functional groups on both of the reacting partners.
- Kumar, Promod,Sharma, Anup Kumar,Guntreddi, Tirumaleswararao,Singh, Rahul,Singh, Krishna Nand
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supporting information
p. 744 - 747
(2018/02/09)
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- Aerobic oxidative acylation of nitroarenes with arylacetic esters under mild conditions: Facile access to diarylketones
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A facile and regioselective base-mediated aerobic oxidative acylation of nitroarenes to access diarylketones under mild conditions has been developed. It features the use of bench-stable and readily available arylacetates as acyl surrogates, and the absence of transition-metals and synthetic oxidants. This protocol involves a cascade CDC/oxidative decarboxylation process.
- Li, Jiang-Sheng,Yang, Qian,Yang, Fan,Chen, Guo-Qin,Li, Zhi-Wei,Kuang, Yin-Jie,Zhang, Wei-Jing,Huang, Peng-Mian
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p. 140 - 145
(2017/12/27)
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- Diarylketone preparation method
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The invention discloses a diarylketone preparation method. According to the method, substituted nitrobenzene and aromatic acetic ester are dissolved in an organic solvent, alkali is added, the mixture is subjected to a reaction in the air or oxygen atmosphere at the temperature of 10-60 DEG C for 0.5-24 h, and diarylketone is obtained; the mole ratio of substituted nitrobenzene to aromatic acetic ester is (0.5:1)-(5:1), and the mole ratio of alkali to aromatic acetic ester is (1:1)-(5:1). The method overcomes defects caused by the adoption of strong acid or expensive metal reagents or strong oxidizers and the like in the prior art and has the advantages as follows: 1) with air as an oxidizer, use of strong or expensive chemical oxidizers is avoided; 2) no transition metal catalysts are used, so that the condition that heavy metal ions are left in a product is avoided; 3) without inductive groups, surplus steps of introduction of the inductive groups and removal of the inductive groups are avoided; 4) acylation of ortho positions or para positions of nitro-aromatic compounds is directly realized, which cannot be realized with a classic Friedel-Crafts acylation method. The synthesis method plays an important role in preparing diarylketone, particularly industrial production of acylation products of ortho positions or para positions of the nitro-aromatic compounds.
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Paragraph 0019; 0023
(2017/09/05)
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- At normal pressure fragrant ketone copper catalytic synthesis method
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The invention discloses a method of synthesizing diaryl ketone under normal pressure by virtue of copper catalysis. The method is as follows: in a solvent alcohol or aqueous liquor of alcohol, under action of alkali and acid, adding a copper catalyst, alkyl iodide, alkyl boric acid and carbon monoxide to directly carry out crossed coupling reaction to prepare diaryl ketone compounds. According to the invention, the method of preparing diaryl ketone compounds by carbonylation Suzuki coupling reaction has the advantages as follows: the catalyst is wide in source, cheap and small in toxicity; the reaction is free of ligand in reaction and good in activity; the reaction is carried out under the normal pressure and selectivity is high; a substrate source is wide and stable; functional group compatibility is good and scope of application for the substrate is wide; a reaction medium is environment-friendly and recyclable. Under the condition of optimizing reaction conditions, the target product separating yield is 95%.
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Paragraph 0032; 0033; 0038
(2017/07/14)
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- Benzosulfones as photochemically activated sulfur dioxide (SO2) donors
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Sulfur dioxide (SO2) is a gaseous environmental pollutant which is routinely used in industry as a preservative and antimicrobial. Recent data suggests that SO2 may have value as a therapeutic agent. However, due to its gaseous nature, localizing SO2 generation is challenging. Herein, various 1,3-dihydrobenzo[c]thiophene 2,2-dioxides (benzosulfones) were prepared as candidates for photochemically activated sulfur dioxide (SO2) generation. These compounds were found to be stable in buffer but were photolysed upon irradiation with UV light to generate SO2. Our data indicates that photolysis of benzosulfones depends on substituents, and that the presence of electron donating groups results in an enhanced yield of SO2. This journal is
- Malwal, Satish R.,Chakrapani, Harinath
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p. 2399 - 2406
(2015/03/04)
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- Iron-catalyzed carbonylative Suzuki reactions under atmospheric pressure of carbon monoxide
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The first highly effective iron-catalyzed carbonylative Suzuki reaction has been developed. Substrates with electron-donating or electron-withdrawing functionality, ortho-substitution, as well as active groups proceeded smoothly, affording desired products in high yields. This protocol is economical, environmentally benign and practical for the synthesis of biaryl ketones. This journal is the Partner Organisations 2014.
- Zhong, Yanzhen,Han, Wei
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supporting information
p. 3874 - 3877
(2014/04/03)
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- Copper-catalyzed carbonylative Suzuki coupling of aryl iodides with arylboronic acids under ambient pressure of carbon monoxide
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An efficient and ligandless nanocopper-catalyzed carbonylative cross-coupling of aryl iodides with arylboronic acids at ambient CO pressure in poly(ethylene glycol), has been developed. This protocol is general, practical, and recyclable, and offers an attractive alternative to the corresponding palladium-mediated carbonylative Suzuki process for the construction of biaryl ketone scaffolds.
- Cheng, Laijin,Zhong, Yanzhen,Ni, Zhuchao,Du, Hongyan,Jin, Fengli,Rong, Qi,Han, Wei
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p. 44312 - 44316
(2014/12/10)
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- Catalytic Friedel-Crafts acylation: Magnetic nanopowder CuFe 2O4 as an efficient and magnetically separable catalyst
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Catalytic regioselective Friedel-Crafts acylation of an array of anisoles/arenes with various acid chlorides using 5-20 mol % of magnetic nanopowder CuFe2O4 is reported. Unlike the conventional Friedel-Crafts reactions, which are catalyzed by moisture sensitive homogeneous catalysts/promoters, the nanopowder CuFe2O4 catalyst is moisture insensitive and the product/ketone-catalyst isolation is easily achieved using the magnetic properties of CuFe2O4.
- Parella, Ramarao,Naveen,Kumar, Amit,Babu, Srinivasarao Arulananda
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p. 1738 - 1742
(2013/03/28)
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- Copper-catalyzed arylation of arylboronic acids with aldehydes
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A novel copper-catalyzed arylation of arylboronic acids with aldehydes under oxygen atmosphere was achieved in the presence of Cu(OTf)2 and Xantphos, affording diaryl ketone derivatives in moderate to good yields. The efficiency of this reaction was demonstrated by the compatibility with fluoro, bromo, chloro, nitro, -methylsulfonyl, and trifluoromethyl groups. Georg Thieme Verlag Stuttgart ? New York.
- Zheng, Hanmei,Ding, Jinchang,Chen, Jiuxi,Liu, Miaochang,Gao, Wenxia,Wu, Huayue
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experimental part
p. 1626 - 1630
(2011/08/03)
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- One-pot synthesis of diaryl ketones from aldehydes via palladium-catalyzed reaction with aryl boronic acids
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A Pd-catalyzed coupling-type reaction of aldehydes and organoboronic acids was achieved in the presence of P(1-nap)3, using Cs2CO3 in toluene, providing diaryl ketones with yields ranged from moderate to excellent. The efficiency of this reaction was demonstrated by the compatibility with nitro, cyano, trifluoromethyl, fluoro and chloro groups. Moreover, the rigorous exclusion of air/moisture is not required in these transformations.
- Qin, Changming,Chen, Jiuxi,Wu, Huayue,Cheng, Jiang,Zhang, Qiang,Zuo, Bing,Su, Weike,Ding, Jinchang
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p. 1884 - 1888
(2008/09/18)
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- Highly selective catalytic Friedel-Crafts acylation and sulfonylation of activated aromatic compounds using indium metal
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The Friedel-Crafts acylation of activated benzenes with various aromatic and aliphatic acid chlorides was studied in the presence of indium metal. The reaction was accomplished in high isolated yields under solvent or solvent-less conditions. The method is also applicable for preparing diaryl sulfones from aromatic compounds and aryl sulfonyl chlorides.
- Jang, Doo Ok,Moon, Kyung Soo,Cho, Dae Hyan,Kim, Joong-Gon
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p. 6063 - 6066
(2007/10/03)
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- Synthesis of Diaryl Ketones Catalyzed by Al2O 3-ZrO2/S2O82- Solid Superacid
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The acylation of a variety of aromatic compounds with benzoyl chloride or its derivatives and catalytic amounts of Al2O3-ZrO 2/S2O82- solid superacid affords the corresponding diaryl ketones in good to excellent yields 75-93% at appropriate temperature.
- Jin, Tong-Shou,Yang, Mi-Na,Feng, Guo-Liang,Li, Tong-Shuang
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p. 479 - 485
(2007/10/03)
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- Palladium-imidazolium-catalyzed carbonylative coupling of aryl diazonium ions and aryl boronic acids
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Palladium(II) acetate and N,N-bis-(2,6-diisopropylphenyl)dihydroimidazolium chloride (2 mol%) were used to catalyze the carbonylative coupling of aryl diazonium tetrafluoroborate salts and aryl boronic acids to form aryl ketones. Optimal conditions includ
- Andrus, Merritt B.,Ma, Yudao,Zang, Yunfu,Song, Chun
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p. 9137 - 9140
(2007/10/03)
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- Model Reaction on Parallel Formation and Ring Opening of Furans by Means of Diazocarbonyl Compounds
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In a photochemical decomposition reaction of the α-Diazoketone 1 in the presence of toluene ring-opening of the adjacent furanoyl substituent occurs as well as conversion of a norcaradiene intermediate thus forming the acetylenic olefinic aldehyde 4 and t
- Ruehl, Wolfgang,Boelsing, Friedrich,Hofer, Edgar
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p. 1487 - 1491
(2007/10/02)
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- Carboxylic Trifluoromethanesulfonic Anhydrides as Highly Effective Acylation Agents. - Perfluoroalkanesulfonic Acid Catalyzed Acylation of Arenes
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Arene- and alkanecarboxylic trifluoromethanesulfonic anhydrides 2 and 5 are highly effective acylation agents, which react without Friedel-Crafts catalysts even with deactivated aromatics to yield aryl ketones 3 and 6, respectively.Acylation of arenes with carbonyl chlorides 4 and catalytic amounts of perfluoroalkanesulfonic acid gives ketones 3 and 6, resp., in good yields.Under similar conditions other strong Broensted acids show a considerably smaller degree of catalytic effect.
- Effenberger, Franz,Sohn, Erich,Epple, Gerhard
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p. 1195 - 1208
(2007/10/02)
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