- Method for preparing aldehyde ketone compound through olefin oxidation
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The invention provides a method for preparing an aldehyde ketone compound by olefin oxidation, which relates to an olefin oxidative cracking reaction in which oxygen participates. The method comprises the following specific steps: in the presence of a solvent and an oxidant, carrying out oxidative cracking on an olefin raw material to obtain a corresponding aldehyde ketone product. Compared with the traditional method, the method does not need to add any catalyst or ligand, does not need to use high-pressure oxygen, has the advantages of simple and mild reaction conditions, environment friendliness, low cost, high atom economy and the like, is wide in substrate application range and high in yield, and has a wide application prospect in the aspects of synthesis of aldehyde ketone medical intermediates and chemical raw materials.
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Paragraph 0019
(2021/04/07)
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- Poly(ethylene glycol) dimethyl ether mediated oxidative scission of aromatic olefins to carbonyl compounds by molecular oxygen
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A simple, and practical oxidative scission of aromatic olefins to carbonyl compounds using O2as the sole oxidant with poly(ethylene glycol) dimethyl ether as a benign solvent has been developed. A wide range of monosubstituted,gem-disubstituted, 1,2-disubstituted, trisubstituted and tetrasubstituted aromatic olefins was successfully converted into the corresponding aldehydes and ketones in excellent yields even with gram-scale reaction. Some control experiments were also conducted to support a possible reaction pathway.
- Yu, Tao,Guo, Mingqing,Wen, Simiaomiao,Zhao, Rongrong,Wang, Jinlong,Sun, Yanli,Liu, Qixing,Zhou, Haifeng
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p. 13848 - 13852
(2021/04/22)
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- Highly Selective and Divergent Acyl and Aryl Cross-Couplings of Amides via Ir-Catalyzed C-H Borylation/N-C(O) Activation
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Herein, we demonstrate that amides can be readily coupled with nonactivated arenes via sequential Ir-catalyzed C-H borylation/N-C(O) activation. This methodology provides facile access to biaryl ketones and biaryls by the sterically controlled Ir-catalyzed C-H borylation and divergent acyl and decarbonylative amide N-C(O) and C-C activation. The methodology diverts the traditional acylation and arylation regioselectivity, allowing us to directly utilize readily available arenes and amides to produce valuable ketone and biaryl motifs.
- Gao, Pengcheng,Szostak, Michal
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p. 6010 - 6015
(2020/07/30)
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- Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions
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Conversion of a wide range of N-Boc amides to aryl ketones was achieved with Grignard reagents via chemoselective C(O)-N bond cleavage. The reactions proceeded under catalyst-free conditions with different aryl, alkyl, and alkynyl Grignard reagents. α-Ketoamide was successfully converted to aryl diketones, while α,β-unsaturated amide underwent 1,4-addition followed by C(O)-N bond cleavage to provide diaryl propiophenones. N-Boc amides displayed higher reactivity than Weinreb amides with Grignard reagents. A broad substrate scope, excellent yields, and quick conversion are important features of this methodology.
- Sureshbabu, Popuri,Azeez, Sadaf,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
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p. 11823 - 11838
(2019/10/02)
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- Transition-Metal-Free Carbonylative Suzuki-Miyaura Reactions of Aryl Iodides with Arylboronic Acids Using N-Formylsaccharin as CO Surrogate
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Unprecedented, high yielding, transition-metal-free carbonylative Suzuki-Miyaura reactions of aryl iodides with arylboronic acids using N-formylsaccharin as CO surrogate have been developed. Notably, this general protocol was adapted to the synthesis of the triglyceride and cholesterol regulator drug, fenofibrate, and carbon-13 labeled biaryl ketone. (Figure presented.).
- Yu, Dezhong,Xu, Fangning,Li, Dan,Han, Wei
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supporting information
p. 3102 - 3107
(2019/05/21)
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- Kumada Arylation of Secondary Amides Enabled by Chromium Catalysis for Unsymmetric Ketone Synthesis under Mild Conditions
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The synthesis of aromatic ketones by chromium-catalyzed Kumada arylation of secondary amides with organomagnesium reagents is described. This reaction was enabled by using low-cost chromium(III) salt as a precatalyst, combined with trimethylsilyl chloride
- Chen, Changpeng,Liu, Pei,Luo, Meiming,Zeng, Xiaoming
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p. 5864 - 5868
(2018/05/29)
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- N-heterocyclic carbene palladium(II)-catalyzed Suzuki-Miyaura cross coupling of N-acylsuccinimides by C-N cleavage
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An easily prepared, well-defined N-heterocyclic carbene-palladium(II) complex was found to be an efficient catalyst for the Suzuki-Miyaura cross-coupling of N-acylsuccinimides with arylboronic acids via C-N bond activation. Under the optimal conditions, a
- Guo, Han,Guo, Jiarui,Jia, Dingli,Liu, Lantao,Wang, Hengjin,Wang, Tao,Zhang, Wen
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- Enhancing the Stability of Photogenerated Benzophenone Triplet Radical Pairs through Supramolecular Assembly
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Supramolecular assembly of urea-tethered benzophenone molecules results in the formation of remarkably persistent triplet radical pairs upon UV irradiation at room temperature, whereas no radicals were observed in solution. The factors that lead to emergent organic radicals are correlated with the microenvironment around the benzophenone carbonyl, types of proximal hydrogens, and the rigid supramolecular network. The absorption spectra of the linear analogues were rationalized using time-dependent density functional theory calculations on the crystal structure and in dimethyl sulfoxide, employing an implicit solvation model to describe structural and electronic solvent effects. Inspection of the natural transition orbitals for the more important excitation bands of the absorption spectra indicates that crystallization of the benzophenone-containing molecules should present a stark contrast in photophysical properties versus that in solution, which was indeed reflected by their quantum efficiencies upon solid-state assembly. Persistent organic radicals have prospective applications ranging from organic light-emitting diode technology to NMR polarizing agents.
- Dehaven, Baillie A.,Goodlett, Dustin W.,Sindt, Ammon J.,Noll, Niklas,De Vetta, Martina,Smith, Mark D.,Martin, Corey R.,González, Leticia,Shimizu, Linda S.
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supporting information
p. 13064 - 13070
(2018/10/09)
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- Acid fluorides as acyl electrophiles in suzuki–miyaura coupling
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The first palladium-catalyzed construction of ketones through Suzuki–Miyaura reaction by using acid fluorides is described. In contrast to typical acyl electrophiles such as acid chlorides, acid fluorides are uncommon acyl electrophiles to use in boron-based coupling reactions, probably due to a high level of stability toward nucleophiles. This first attempt to use acid fluorides as a coupling partner with boronic acids allowed highly functional group tolerance and a wide substrate scope while affording various ketones in effective yields.
- Ogiwara, Yohei,Sakino, Daisuke,Sakurai, Yuka,Sakai, Norio
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supporting information
p. 4324 - 4327
(2018/08/28)
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- Reactions catalyzed by a binuclear copper complex: Selective oxidation of alkenes to carbonyls with O2
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Terminal alkenes were selectively cleaved into ketones and aldehydes catalyzed by a binuclear copper catalyst bearing a simple salicylate ligand with O2 as the oxidant. The reaction was carried out under an atmosphere of O2 (balloon) with 0.5 mol% of catalyst and could be performed on a gram scale, providing a convenient and practical method for the cleavage of terminal alkenes into carbonyl compounds.
- Liu, Yuxia,Xue, Dong,Li, Chaoqun,Xiao, Jianliang,Wang, Chao
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p. 5510 - 5514
(2017/12/08)
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- N-Acylsuccinimides: Efficient acylative coupling reagents in palladium-catalyzed Suzuki coupling via C–N cleavage
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An acylative Suzuki coupling of activated amides with aryl boronic acids has been reported via palladium-catalyzed C–N bond cleavage. This protocol demonstrate amides can be activated by an atom-economic and cheap succinimide, which can be efficiently utilized to synthesize broad array of diaryl ketones in moderate to good yields.
- Cui, Ming,Chen, Zeyu,Liu, Tingting,Wang, Hui,Zeng, Zhuo
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p. 3819 - 3822
(2017/09/15)
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- Palladium-Catalyzed Denitrogenative Synthesis of Aryl Ketones from Arylhydrazines and Nitriles Using O2 as Sole Oxidant
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An efficient and simple palladium-catalyzed approach for the synthesis of aryl ketones from low-cost nitriles and arylhydrazines using molecular oxygen (O2) as sole oxidant via C-N bond cleavage is reported. Various aryl ketones were synthesized in moderate to good yields under mild conditions. A possible mechanism involving the PdII/Pd0 catalytic cycle process is depicted, and a cationic palladium intermediate was detected by ESI-MS.
- Wang, Xu,Huang, Yubing,Xu, Yanli,Tang, Xiaodong,Wu, Wanqing,Jiang, Huanfeng
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p. 2211 - 2218
(2017/02/26)
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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 0026; 0027; 0030
(2017/07/14)
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- At normal pressure fragrant ketone nickel catalytic synthesis method
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The invention discloses a method for synthesizing diarylketone under the catalysis of nickel at normal pressure. The method comprises the steps of enabling aryl iodide, arylboronic acid and carbon monoxide to be subjected to direct cross-coupling reaction in a solvent polyethylene glycol or a water solution of polyethylene glycol under the catalysis of a nickel catalyst and the combined action of alkaline and acid at normal pressure to prepare a diarylketone compound. The method has the advantages of wide catalyst source, low price, little toxicity, reaction at normal pressure, high selectivity, no need of ligands in reaction, good activity, good functional group compatibility, wide substrate application range, wide substrate source, stable substrate, green and recyclable reaction medium and the like. The separation yield of target products is up to 93% under an optimized reaction condition.
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Paragraph 0003; 0017; 0020-0026
(2017/08/02)
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- Palladium-catalyzed coupling of benzoyl halides with aryltrifluorosilanes leading to diaryl ketones
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Acyl-aryl Hiyama coupling of acyl halides with arylsilanes has been achieved by employing a palladium/phosphine catalyst system. A variety of acyl chlorides and fluorides can be applied for coupling with arylsilicon reagents, and unsymmetrical benzophenone derivatives can be prepared using this protocol.
- Ogiwara, Yohei,Maegawa, Yuki,Sakino, Daisuke,Sakai, Norio
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supporting information
p. 790 - 792
(2016/07/16)
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- Iron-catalyzed carbonylation of aryl halides with arylborons using stoichiometric chloroform as the carbon monoxide source
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A general iron-catalyzed carbonylative Suzuki-Miyaura coupling of aryl halides with arylborons is reported, using stoichiometric CHCl3 as the CO source. The high efficiency, economy, selectivity, and operational simplicity of this transformation make this method a valuable tool in organic synthesis. Importantly, the presented strategy allows effective 13C labeling simply by using the commercially available 13C-labeled CHCl3. On the basis of the initial mechanistic exploration, an aryl radical intermediate is proposed in the present carbonylation process.
- Zhao, Hongyuan,Du, Hongyan,Yuan, Xiaorong,Wang, Tianjiao,Han, Wei
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supporting information
p. 5782 - 5787
(2016/11/06)
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- A Convenient Palladium-Catalyzed Carbonylative Suzuki Coupling of Aryl Halides with Formic Acid as the Carbon Monoxide Source
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A practical palladium-catalyzed carbonylative Suzuki coupling of aryl halides under carbon monoxide gas-free conditions has been developed. Here, formic acid was utilized as the carbon monoxide source for the first time with acetic anhydride as the additive. A variety of diarylketones were produced in moderate to excellent yields from the corresponding aryl halides and arylboronic acids.
- Qi, Xinxin,Jiang, Li-Bing,Li, Hao-Peng,Wu, Xiao-Feng
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supporting information
p. 17650 - 17656
(2015/12/05)
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- Ortho C-H acylation of aryl iodides by palladium/norbornene catalysis
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Reported herein is a palladium/norbornene-catalyzed ortho-arene acylation of aryl iodides by a Catellani-type C-H functionalization. This transformation is enabled by isopropyl carbonate anhydrides, which serve as both an acyl cation equivalent and a hydride source. Double (re)agent: A palladium/norbornene-catalyzed ortho-acylation of aryl iodides was developed, and is enabled by isopropyl carbonate anhydrides, which function as both an acyl cation equivalent and a hydride source. This reaction exhibits excellent functional-group compatibility and broad substrate scope. Heterocycle moieties can be tolerated on both the aryl and acyl partners. FG=functional group.
- Dong, Zhe,Wang, Jianchun,Ren, Zhi,Dong, Guangbin
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p. 12664 - 12668
(2015/10/28)
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- Palladium nanoparticles immobilized onto supported ionic liquid-like phases (SILLPs) for the carbonylative Suzuki coupling reaction
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Crosslinked polymeric materials based on poly(ionic liquid)s, also named supported ionic liquid-like phases (SILLPs) were prepared by copolymerization of dication imidazole ionic liquids with divinylbenzene (DVB). Using the SILLPs-related polymeric materials as supports, palladium (Pd) metal nanoparticles were immobilized and stabilized, which can efficiently catalyze the carbonylative Suzuki coupling reaction of aryl iodides with aryl boronic acids, affording the corresponding products in good to excellent yields. The Pd nanoparticles immobilized onto SILLPs were characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TG), and X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR). The size and dispersion of the Pd nanoparticles supported on polymers are influenced possibly by varying the contents of the ionic liquid units and the introduction of amine groups. Furthermore, hot filtration and mercury poisoning tests indicated that the palladium species leached into the solvent during the reaction and returned to the polymers after the reaction was completed. In addition, the catalyst was easily recovered from the reaction mixture by filtration and reused over five consecutive cycles without a significant decrease in its activity. This journal is
- Jiao, Nianming,Li, Zelong,Wang, Yan,Liu, Jianhua,Xia, Chungu
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p. 26913 - 26922
(2015/03/30)
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- Palladium-Catalyzed Synthesis of Biaryl Ketones via tert -Butyl Isocyanide Insertion
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A simple and efficient palladium-catalyzed carbonylative Suzuki coupling via tert-butyl isocyanide insertion has been developed, which demonstrates the utility of isocyanides in intermolecular C-C bond construction. This methodology provides a novel pathway for the synthesis of diaryl ketones in moderate to good yields. The approach is tolerant to a wide range of substrates and applicable to library synthesis. A possible reaction mechanism was proposed based on the experimental results. Georg Thieme Verlag Stuttgart. New York.
- Chen, Zhong,Duan, Huaqing,Jiang, Xiao,Wang, Jinmei,Zhu, Yongming,Yang, Shilin
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supporting information
p. 1425 - 1430
(2014/06/23)
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- In situ generation of palladium nanoparticles: Ligand-free palladium catalyzed pivalic acid assisted carbonylative Suzuki reactions at ambient conditions
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Highly selective carbonylative Suzuki reactions of aryl iodides with arylboronic acids using an in situ generated nanopalladium system furnished products in high yields. The reactions were performed under ambient conditions and in the absence of an added ligand. The key to success is the addition of pivalic acid, which can effectively suppress undesired Suzuki coupling. The synthesis can be easily scaled up, and the catalytic system can be reused up to nine times. The nature of the active catalytic species are discussed.
- Zhou, Qing,Wei, Shaohua,Han, Wei
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p. 1454 - 1460
(2014/03/21)
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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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- 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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- In situ generated nickel nanoparticle-catalyzed carbonylative Suzuki reactions of aryl iodides with arylboronic acids at ambient CO pressure in poly(ethylene glycol)
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A general in situ generated nickel nanoparticle-catalyzed carbonylative Suzuki reactions of aryl iodides with arylboronic acids at atmospheric CO pressure in poly(ethylene glycol) has been demonstrated. A wide range of aryl iodides and arylboronic acids can be coupled to the corresponding biarylketones with high yields even in the absence of an added ligand and at low catalyst loading. The nature of the active catalytic species is discussed. This journal is
- Zhong, Yanzhen,Gong, Xinxing,Zhu, Xiaoshu,Ni, Zhuchao,Wang, Haoyang,Fu, Jinglin,Han, Wei
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p. 63216 - 63220
(2015/02/19)
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- DMC mediated one pot synthesis of biaryl ketones from aryl carboxylic and boronic acids
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Synthesis of biaryl ketones has been realized from aryl carboxylic acids in the presence of DMC, facilitated by palladium catalyst under thermal condition. This methodology gives the introduction of carbonyl functionality in one pot from corresponding ary
- Pathak, Arunendra,Rajput, Chatrasal S.,Bora, Pushkar S.,Sharma, Somesh
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p. 2149 - 2150
(2013/05/08)
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- NHC-Pd(II)-Im (NHC=N-heterocyclic carbene, Im=1-methylimidazole) complex catalyzed coupling reaction of arylboronic acids with carboxylic acid anhydrides in water
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A well-defined N-heterocyclic carbene (NHC)-palladium chloride-imidazole complex exhibited high catalytic activity in the coupling reaction of arylboronic acids with carboxylic acid anhydrides in pure water under mild conditions. Under the optimal conditions, all reactions gave the desired coupling products in moderate to high yields.
- Lin, Xiao-Fang,Li, Yao,Li, Shuang-Yan,Xiao, Zheng-Kang,Lu, Jian-Mei
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experimental part
p. 5806 - 5809
(2012/09/08)
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- Imidazole-coordinated monodentate NHC-Pd(II) complex derived from proline and its application to the coupling reaction of arylboronic acids with carboxylic acid anhydrides in water at room temperature
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Cleavage of a C-N bond of imidazolium salt derived from N-phenyl-substituted proline was observed in this laboratory. A novel imidazole-coordinated monodentate NHC-Pd(II) complex 5 was obtained as the sole product in good yield in the reaction of imidazolium salt 4 with Pd(OAc) 2 in refluxing THF. The structure of complex 5 was determined unambiguously by an X-ray diffraction. The complex was found to be a good catalyst in the cross-coupling reaction of arylboronic acids with carboxylic acid anhydrides in water at room temperature. Copyright
- Shen, Xiao-Bao,Gao, Ting-Ting,Lu, Jian-Mei,Shao, Li-Xiong
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experimental part
p. 497 - 501
(2012/05/04)
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- Photoinduced C-Br homolysis of 2-bromobenzophenones and Pschorr ring closure of 2-aroylaryl radicals to fluorenones
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(Chemical Equation Presented) A variety of diversely substituted 2-aroylaryl radicals, generated by photoinduced homolysis of 2-bromoarylketones, is shown to undergo Pschorr cyclization to yield fluorenones in moderate to excellent yields. The photochemical results illustrate that the substituents in the two phenyl rings of the 2-bromobenzophenone skeleton exert a dramatic influence on the reactivity of the derived 2-aroylaryl radicals. The disubstitution by methoxy groups in the radical ring renders the aryl σ-radical highly electrophilic and unreactive for hydrogen abstraction and cyclization. On the other hand, the substituents in the non-radical ring that strongly stabilize the hydrofluorenyl π-radical, formed subsequent to the attack of the 2-aroylaryl radical on the non-radical ring, promote cyclization to furnish fluorenones in excellent isolated yields.
- Moorthy, Jarugu Narasimha,Samanta, Subhas
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p. 9786 - 9789
(2008/03/17)
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- Friedel-Crafts Acylation of Arenes Catalysed by Bromopentacarbonylrhenium(I)
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The intermolecular Friedel-Crafts acylation of aromatic compounds (such as toluene, m-xylene, and anisole) with various acid chlorides proceeds by using a catalytic amount of bromopentacarbonylrhenium(I) to afford aryl ketones.Intramolecular acylation is also catalyzed by the above-mentioned catalyst to give indanone and tetralone derivatives.
- Kusama, Hiroyuki,Narasaka, Koichi
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p. 2379 - 2384
(2007/10/03)
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