- DDQ/tert-Butyl nitrite-catalyzed aerobic oxidation of diarylmethane sp3 C-H bonds
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An efficient 2,3-dichloro-5,6-dicyano-1,4-benzoquinone/tert-butyl nitrite-catalyzed aerobic oxidation of diarylmethane sp3 C-H bonds in the presence of acetic acid has been developed. Under the optimal reaction conditions, a number of diarylmethanes can be directly converted to their corresponding diarylketones in good to excellent yields. In addition, a plausible reaction mechanism has been investigated.
- Ma, Jiaqi,Hu, Zhiming,Li, Meichao,Zhao, Weijuan,Hu, Xinquan,Mo, Weimin,Hu, Baoxiang,Sun, Nan,Shen, Zhenlu
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- Eco-friendly Suzuki-Miyaura coupling of arylboronic acids to aromatic ketones catalyzed by the oxime-palladacycle in biosolvent 2-MeTHF
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Oxime-palladacycle catalyzed Suzuki-Miyaura cross-coupling reaction of acid chlorides and arylboronic acids to yield aryl ketones was developed. The remarkable benefit of this method is the use of water immiscible (practically) 2-MeTHF as solvent, which provides easy isolation of the crude reaction mixture just by separation of 2-MeTHF-water layers, and then evaporation of 2-MeTHF. Moreover, the use of relatively equal proportion of substrates and less generation of side products make the method highly atom economic.
- Mondal, Manoj,Bora, Utpal
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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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- Base free Suzuki acylation reactions of sodium (aryl trihydroxyborate) salts: A novel synthesis of substituted aryl ketones
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The first simple and efficient base free Pd(PPh3)4 catalysed synthesis of substituted aryl ketones from acyl chlorides and easily accessible sodium aryl trihydroxyborate salts in aqueous toluene is reported. The reaction conditions appeared versatile and tolerable to a variety of functional groups including, CF3, OMe, SMe, Br, NO2, F, OH and NH2 furnishing 25 examples of substituted aryl ketones in isolated yields of up to 96% in 24 h. Beside the high purity, the ease and convenience of the isolation compared to boronic acids, sodium aryl trihydroxyborate salts could be used subsequently without the addition of excess amount of an activator and are more user-friendly in terms of the use of accurate reaction stoichiometry.
- Sithebe, Siphamandla,Molefe, Patience
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- Exploring the Reducing Ability of Organic Dye (Acr+-Mes) for Fluorination and Oxidation of Benzylic C(sp3)-H Bonds under Visible Light Irradiation
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The excellent oxidizing capability of acridinium-based organic dye (Acr+-Mes) is fully studied in photoredox catalysis. However, its reducing ability is always considered weak for organic transformation. The reducing ability of Acr+-Mes is developed by Selectfluor to achieve effective fluorination and oxidation of benzylic C(sp3)-H bonds under visible light irradiation, which is not available for the direct use of oxidizing ability of excited Acr+-Mes. Mechanistic insights provided strong evidence for the oxidative quenching of Acr+-Mes.
- Xiang, Ming,Xin, Zhi-Kun,Chen, Bin,Tung, Chen-Ho,Wu, Li-Zhu
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- Pd(0)/C-catalyzed cross-couplings of acyl chlorides with triarylbismuths as atom-efficient sub-stoichiometric multi-coupling reagents
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Aromatic and hetero-aromatic acyl chlorides were efficiently cross-coupled with triarylbismuths as atom-efficient nucleophilic organometallic coupling reagents in sub-stoichiometric amounts using catalytic Pd(0)/C. Thus, the coupling reactions of various triarylbismuths with a variety of acyl chlorides furnished a plethora of both symmetrical/unsymmetrical aromatic and hetero-aromatic ketones in high yields.
- Rao, Maddali L.N.,Jadhav, Deepak N.,Venkatesh, Varadhachari
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- T-BuONa-Mediated Transition-Metal-Free Autoxidation of Diarylmethanes to Ketones
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Autoxidative sp3 C-H transformation of diarylmethanes has been demonstrated using O2-mediation by t-BuONa. This protocol enables an alternative route for the access to diaryl ketones from benzyl derivatives in good to excellent yields under mild reaction conditions, without transition metal catalysts or additional chemical oxidants.
- Li, Jiang-Sheng,Yang, Fan,Yang, Qian,Li, Zhi-Wei,Chen, Guo-Qin,Da, Yu-Dong,Huang, Peng-Mian,Chen, Chao,Zhang, Yuefei,Huang, Ling-Zhi
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- Polystyrene-supported Pd(II)–N-heterocyclic carbene complex as a heterogeneous and recyclable precatalyst for cross-coupling of acyl chlorides with arylboronic acids
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Palladium-catalysed cross-coupling reaction of aroyl chlorides with arylboronic acids was achieved in the presence of polystyrene-supported palladium(II)–N-heterocyclic carbene complex, using K2CO3 in acetone–water, providing diaryl ketones in high yields. Furthermore, the heterogeneous catalyst could be reused up to four times without significant loss of activity.
- Movassagh, Barahman,Hajizadeh, Fatemeh,Mohammadi, Elmira
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- Agglomeration of Pd0 nanoparticles causing different catalytic activities of Suzuki carbonylative cross-coupling reactions catalyzed by PdII and Pd0 immobilized on dopamine-functionalized magnetite nanoparticles
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Solvent-dispersible magnetite nanoparticles (Fe3O4) end-functionalized with amino groups were successfully prepared by a facile one-pot template-free method to immobilize PdII and Pd0 using a metal adsorption and reduction procedure. They were characterized by TEM, XRD, XPS, FT-IR and VSM. Interestingly, the PdII catalyst exhibited better catalytic activity for carbonylative cross-coupling reactions than the Pd0 catalyst. According to the catalytic activities of a variety of arylboronic acids and aryl iodides catalyzed by two kinds of Pd catalysts, the proposed reaction mechanism of Suzuki carbonylative cross-coupling reactions using the Pd catalyst was also inferred. More importantly, agglomeration of Pd0 nanoparticles was obviously observed in the TEM images of the catalysts after reactions. Therefore, agglomeration of Pd0 nanoparticles should be considered as a significant reason for different catalytic activities of the reactions catalyzed by immobilized PdII and Pd0 catalysts. Furthermore, the PdII catalyst revealed high efficiency and stability during recycling stages.
- Long, Yu,Liang, Kun,Niu, Jianrui,Tong, Xin,Yuan, Bing,Ma, Jiantai
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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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- Dirhodium(II)-Catalyzed Cross-Coupling Reactions of Aryl Aldehydes with Arylboronic Acids in Water
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In this report, dirhodium(II) catalysts with axial phosphanes ligands were employed to catalyze cross-coupling reactions of aromatic aldehydes with arylboronic acids to generate ketones in neat water. The overall reaction is proposed to occur through a cascade process involving the dirhodium-catalyzed addition of boronic acids to aldehydes followed by the dehydrogenative oxidation of alcohols.
- Kuang, Yi,Wang, Yuanhua
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- A zeolite imidazolate framework ZIF-8 catalyst for Friedel-Crafts acylation
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A zeolite imidazolate framework, ZIF-8, was synthesized and characterized by dynamic laser light scattering, X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, Fourier transform infrared, atomic absorption spectrophotometry, and nitrogen adsorption measurements. The ZIF-8 was highly crystalline and porous with a surface area of over 1600 m2/g. Friedel-Crafts acylation of anisole and benzoyl chloride proceeded well in the presence of ZIF-8 (2-6 mol%) without the need for an inert atmosphere. The reaction afforded a selectivity of 93%-95% to the p-isomer. The solid catalyst can be separated from the reaction mixture by simple centrifugation and reused without significant degradation in catalytic activity. There was no leaching of active acid species into the reaction solution.
- Nguyen, Lien T.L.,Le, Ky K.A.,Phan, Nam T.S.
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- Ligandless heterogeneous palladium: An efficient and recyclable catalyst for Suzuki-type cross-coupling reaction
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A mild and efficient ligand-free Suzuki-type cross-coupling reaction of benzoyl chlorides and arylboronic acids catalyzed by heterogeneous Pd/C was developed. Benzoyl chlorides undergo cross-coupling with electronically diverse arylboronic acids to give biaryl ketones in excellent yield, under aqueous media and optimum temperature. The application of 3-‰mol% of 10-‰wt% Pd/C to the cross-coupling delivers utmost efficiency, and could be reused up to many consecutive cycles without any loss in activity. This method proceeds under aqueous media and a recyclable catalytic system, offering an environmentally benign alternative to the existing protocols.
- Mondal, Manoj,Bora, Utpal
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- A phosphine-free carbonylative cross-coupling reaction of aryl iodides with arylboronic acids catalyzed by immobilization of palladium in MCM-41
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The phosphine-free heterogeneous carbonylative cross-coupling of aryl iodides with arylboronic acids under an atmospheric pressure of carbon monoxide was achieved in anisole at 80 °C in the presence of a 3-(2-aminoethylamino) propyl-functionalized MCM-41-immobilized palladium(ii) complex [MCM-41-2N-Pd(ii)], yielding a variety of unsymmetrical biaryl ketones in good to high yield. This heterogeneous palladium catalyst exhibited higher activity and selectivity than PdCl2(PPh3)2, can be recovered and recycled by a simple filtration of the reaction solution, and used for at least 10 consecutive trials without any decrease in activity. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
- Cai, Mingzhong,Peng, Jian,Hao, Wenyan,Ding, Guodong
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- Preparation of recoverable Fe3O4@PANI-PdII core/shell catalysts for Suzuki carbonylative cross-coupling reactions
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We report on the synthesis, characterization and catalytic performance of a palladium-based superparamagnetic catalyst of Fe3O 4@polyaniline core/shell microspheres (Fe3O 4@PANI-PdII). The material was characterized by TEM, FT-IR, vibrating sample magnetometry (VSM), XRD, and XPS. The catalyst showed high activity for the carbonylative cross-coupling reaction of aryl iodide with arylboronic acid. Moreover it could selectively reduce the formation of a direct-coupling product. The newly developed catalyst could be recovered from the liquid phase easily by magnetic separation and recycled 5 times without any significant loss of activity. the Partner Organisations 2014.
- Zhu, Xiaohang,Niu, Jianrui,Zhang, Fengwei,Zhou, Jinghui,Li, Xinzhe,Ma, Jiantai
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- Envirocat EPIC(R) as a novel catalyst for acylation of anisole using benzoic acids
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Friedel-Crafts acylation of anisole has been carried out using Envirocat EPIC(R) as a novel heterogenous catalyst and benzoic acids under reflux condition. This method is suitable for regioselective acylation of activated aromatics with benzoic acids having electron-donating substituents.
- Bandgar,Sadavarte
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- Phosphine-Free, Heterogeneous Palladium-Catalyzed Atom-Efficient Carbonylative Cross-Coupling of Triarylbismuths with Aryl Iodides: Synthesis of Biaryl Ketones
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A novel and highly efficient heterogeneous palladium-catalyzed carbonylative cross-coupling of aryl iodides with triarylbismuths has been developed that proceeds smoothly at atmospheric CO pressure and provides a general and powerful tool for the preparation of various valuable biaryl ketones with high atom economy, good to excellent yield, and recyclability of the catalyst. The reaction is the first example of Pd-catalyzed carbonylative cross-coupling for the construction of biaryl ketones using triarylbismuths as substrates.
- Hao, Wenyan,Liu, Haiyi,Yin, Lin,Cai, Mingzhong
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- 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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- Tunable aryl imidazolium recyclable ionic liquid with dual br?nsted-lewis acid as green catalyst for friedel-crafts acylation and thioesterification
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Unique tunable aryl imidazolium ionic liquids successfully catalyzed Friedel-Crafts acylation and thioesterification in sealed tubes. These reactions can form a C-C bond and a C-S bond with high atom economy. Ionic liquids exhibited high activity and catalyzed essential reactions with good to excellent yields while retaining their catalytic activities for recycling.
- Chen, Wen-Tin,Chou, Shih-Huan,Ho, Wen-Yueh,Hung, Ming-Wei,Lin, Michelle,Lin, Wesley,Lin, Yi-Jyun,Luo, Shun-Yuan,Reddy, Daggula Mallikarjuna,Thul, Mayur,Wu, Hsin-Ru,Wu, Yao-Peng
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- Facile preparation of 5-alkyl-1-aryltetrazoles with arenes, acyl chlorides, hydroxylamine, and diphenylphosphoryl azide
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Successive treatment of arenes with acyl chlorides and AlCl3, the addition of water and removal of solvent, the reaction with NH2OH?HCl and K2CO3, and the reaction with diphenylphosphoryl azide and DBU under warming conditions gave the corresponding 5-alkyl-1-aryltetrazoles efficiently in good to moderate yields. The present method is one-pot transformation of arenes into 5-alkyl-1-aryltetrazoles using the Friedel-Crafts acylation and the Beckmann rearrangement under transition-metal-free conditions.
- Shibasaki, Kaho,Togo, Hideo
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p. 1816 - 1830
(2020/11/19)
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- Palladium-Catalyzed Amide N-C Hiyama Cross-Coupling: Synthesis of Ketones
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N-Acylglutarimides and arylsiloxanes reacted in the presence of Pd(OAc)2/PCy3, Et3N·3HF, and LiOAc to provide the corresponding arylketones in good yields. Aryl-, vinyl-, and alkyl-substituted N-acylglutarimides showed good activity in the coupling reactions of arylsiloxanes. The reaction had a broad substrate scope and showed good functional group tolerance. N-Benzoylsuccinimide and N-protected N-phenylbenzamides showed good activities in coupling reactions with phenylsiloxane. The employment of CuF2 as an activor afforded the decarbonylative products at 160 °C.
- Idris, Muhammad Aliyu,Lee, Sunwoo
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supporting information
p. 9190 - 9195
(2020/11/18)
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- 5-Bromo-norborn-2-en-7-one derivatives as a carbon monoxide source for palladium catalyzed carbonylation reactions
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Norbornenone (5b), obtained from the reaction of 2,5-dimethyl-3,4-diphenylcyclopentadienone dimer (3) with bromomaleic anhydride (4b), provides an excellent base-triggered source of carbon monoxide for palladium-catalysed carbonylation reactions. Aminocarbonylation, ketoamide synthesis, and Suzuki-Miyaura reactions of aryl iodides carried out in a two-chamber reaction vessel gave good to excellent yields of carbonylated products.
- Payne, China M.,Cho, Kyulee,Larsen, David S.
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p. 30736 - 30740
(2019/10/19)
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- Method for preparing diarylketone compound through efficient catalysis of pyridine palladium
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According to the invention, a method for preparing a diarylketone compound through efficient catalysis of pyridine palladium is provided, wherein aryl phenylboronic acid, iodobenzene compounds and carbon monoxide are used as raw materials, potassium carbonate or potassium hydroxide is used as alkali, pyridine palladium or 3-chloropyridine palladium is used as a catalyst, and the diaryl compound isprepared at high efficiency and yield. The method provided by the invention has the advantages of small catalyst dosage, high catalytic activity, stability to air, simple operation, short reaction time and high atom economy, opens up a low-cost, green and efficient way for preparation of the diarylketone compound, and has broad application prospects.
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Paragraph 0033; 0035-0039
(2019/12/02)
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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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- Ligand-free Palladium-Catalyzed Carbonylative Suzuki Coupling of Aryl Iodides in Aqueous CH3CN with Sub-stoichiometric Amount of Mo(CO)6 as CO Source
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A new method for the synthesis of diaryl and heterodiaryl ketones has been established based on the palladium-catalyzed carbonylative Suzuki coupling approach with sub-stoichiometric Mo(CO)6 as CO source. Using 0.5 mol% of Pd(TFA)2 as catalyst, 0.5 equivalent of Mo(CO)6 as solid carbonyl reagent and 3 equivalent of K3PO4 as base, a wide range of functionalized (hetero)aryl iodides and (hetero)aryl boronic acids could smoothly proceed the carbonylative cross-coupling reaction in aqueous CH3CN at 50 °C, affording the corresponding ketones in good to excellent yields. The newly developed method was easy to operate under mild conditions with high efficiency. (Figure presented.).
- Sun, Nan,Sun, Qingxia,Zhao, Wei,Jin, Liqun,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
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p. 2117 - 2123
(2019/03/28)
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- Hydrogen bond directed aerobic oxidation of amines via photoredox catalysis
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An application of H-bonding interactions for directing the α-C-H oxidation of amines to amides and amino-ketones catalyzed by an organic photocatalyst is reported. The high efficiency of this method is demonstrated by the aerobic oxidation of pyrrolidines, diarylamines and benzylamines bearing urea groups with high yields and a wide substrate scope.
- Wang, Hongyu,Man, Yunquan,Wang, Kaiye,Wan, Xiuyan,Tong, Lili,Li, Na,Tang, Bo
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supporting information
p. 10989 - 10992
(2018/10/08)
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- Hydrogen bond donor solvents enabled metal and halogen-free Friedel–Crafts acylations with virtually no waste stream
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We have developed a metal and halogen-free Friedel–Crafts acylation protocol with virtually no waste stream generation. We propose a hydrogen bonding donor solvent will form a hydrogen bonding network and may provide significant rate enhancement for Friedel–Crafts reactions. Trifluoroacetic acid is one of the strongest H-bond donor solvents, which is also volatile and can be easily recovered by distillation without need for reaction workup. Our protocol is a ‘green’ Friedel–Crafts acylation process: 1) the catalyst can be recovered and reused; 2) using halogen free starting material (carboxylic acids anhydride or carboxylic acids); 3) no need for aqueous reaction work-up; 4) minimum or no waste steam generation.
- Liu, Guangchang,Xu, Bo
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supporting information
p. 869 - 872
(2018/02/09)
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- Palladium-Catalyzed Ligand-Free Decarboxylative Coupling of α- Oxocarboxylic Acid with Aryl Diazonium Tetrafluoroborate: An Access to Unsymmetrical Diaryl Ketones
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Diaryl ketones are of much importance in organic synthesis as versatile intermediates and in industry for their useful properties. A mild and efficient palladium-catalyzed traditional ligand-free decarboxylative coupling of aryl α-keto carboxylic acid with aryl diazonium fluoroborate has been developed. A series of unsymmetrical diaryl ketones has been synthesized in moderate to good yields using this procedure. A radical pathway involving the acyl radical has been suggested.
- Panja, Subir,Maity, Pintu,Ranu, Brindaban C.
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p. 12609 - 12618
(2018/10/20)
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- Pd-Catalyzed Suzuki–Miyaura Cross-Coupling of Arylboronic Acids and α-Iminonitriles through C–CN Bond Activation
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A Pd-catalyzed Suzuki–Miyaura cross-coupling reaction between arylboronic acids and α-iminonitriles has been developed. The reaction proceeds through selective activation of the C–CN bond, tolerates a wide range of substituents, and delivers the versatile ketone products in moderate to excellent yields.
- Liu, Kui,Tao, Shou-Wei,Qian, Chun,Zhu, Yong-Ming
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supporting information
p. 4769 - 4775
(2018/09/06)
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- Kinetic studies on tetrabutylammonium bromochromate oxidation of some mono-and di-substituted benzhydrols
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The oxidation of 12 mono- and di-substituted benzhydrols (BH) by tetrabutylammonium bromochromate (TBABC) have been studied in aqueous acetic acid medium. Absence of any effect of added acrylonitrile on the reaction discounts the possibility of a one-electron oxidation, leading to the formation of free radicals. The tetrabutylammonium bromochromate oxidation of 12 mono- and di-substituted benzhydrols complies with the isokinetic relationship and Hammett relationship. The overall mechanism is proposed to involve a cyclic concerted symmetrical transition state leading to the product.
- Hemalatha,Asghar, Basim H.,Mansoor, S Sheik
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p. 821 - 826
(2018/03/13)
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- A Zwitterionic Palladium(II) Complex as a Precatalyst for Neat-Water-Mediated Cross-Coupling Reactions of Heteroaryl, Benzyl, and Aryl Acid Chlorides with Organoboron Reagents
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The Suzuki–Miyaura cross-coupling (SMC) reactions of several heteroaryl chlorides, benzyl chlorides, and aryl acid chlorides with (hetero)arylboron reagents have been investigated in the presence of [Pd(HL1)(PPh3)Cl2] (I) [HL1 = 3-[(2,6-diisopropylphenyl)-1-imidazolio]-2-quinoxalinide] as catalyst and K2CO3 as base in neat water. The synthesis of the heterocycle-containing biaryls required the addition of 2 mol-% of a phosphine ligand (PPh3 or X-Phos). A combination of more than 115 substrates were screened and it was found that I is a versatile catalyst that can produce heterocycle-containing biaryls, diarylmethanes, and benzophenones in moderate-to-excellent yields.
- Ramakrishna, Visannagari,Rani, Morla Jhansi,Reddy, Nareddula Dastagiri
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p. 7238 - 7255
(2018/01/01)
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- A kind of alkali to promote self-oxidation of diaryl alkane preparation diarylketones method (by machine translation)
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The invention discloses a kind of alkali to promote self-oxidation of diaryl alkane preparation diarylketones method. The method is that the diaryl paraffins compound is dissolved in an organic solvent in the drying of, the addition of a base, in the 25 - 80o C reaction under air or oxygen atmosphere for 0.5 - 5 hours, to obtain diarylketones; said two aryl paraffins compound and alkali molar ratio of 1:1 - 1:3. The method overcomes the need in the prior art strong acid or expensive metal reagent or a strong oxidizing agent and the like, has the following advantages: 1) to oxygen as the oxidizing agent, avoids the use of strong or expensive chemical oxidizing agent; 2) transition metal-free catalyst, avoids the heavy metal ion in the product; 3) the process is simple, low cost, wide range of the substrate, friendly to the environment. The synthesis method disclosed in this invention in the preparation of diarylketones industrialization of the play an important role in the production. (by machine translation)
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Paragraph 0019
(2017/08/28)
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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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- Method for preparing fenofibrate key intermediate 4-chloro-4'-hydroxybenzophenone
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The invention relates to a method for catalytic synthesis of fenofibrate key intermediate 4-chloro-4'-hydroxybenzophenone by taking anisole and parachlorobenzoyl chloride as starting materials and taking novel magnetic nano-particle load lewis acid as a catalyst. The novel magnetic nano-particle load lewis acid is adopted as the catalyst. The method has the advantages that 1) the magnetic nano-particle load lewis acid catalyst is small in dosage and can be recycled; 2) the reaction time is greatly shortened, and reaction conversion rate and yield are improved; 3) the magnetic nano-particle load lewis acid catalyst is quickly separated and recycled easily, the process is simple, and the production cost is relatively low.
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Paragraph 0048; 0050; 0052; 0054; 0056; 0057; 0058; 0060; 00
(2017/08/25)
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- The second aryl ketone compounds
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The invention provides a synthetic method for diaryl ketone compounds. The method comprises the following steps: adding ester derivatives of raw material diaryl methanol, DDQ and water into an organic solvent, carrying out stirring, then carrying out heating to 110 to 140 DEG C and carrying out reaction for 0.5 to 12 h, and subjecting obtained reaction liquid to after-treatment so as to obtain the diaryl ketone compounds, wherein the ester derivatives of the raw material diaryl methanol have a structural formula as shown in a formula (V), (VI), (VII) or (VIII), and one-to-one correspondingly obtained products have the structural formula as shown in the formula (I), (II), (III) or (IV). The synthetic method for the diaryl ketone compounds provided by the invention has the advantages of simple, convenient and safe operation, mild reaction conditions and high product selectivity.
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Paragraph 0067; 0068
(2017/08/24)
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- Ruthenium Hydride Complex Supported on Gold Nanoparticle Cored Triazine Dendrimers for C-C Coupling Reactions
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In this work, the unusual ability of a ruthenium hydride catalyst, [RuHCl(PPh3)3CO], supported on gold nanoparticle cored triazine dendrimers in the Suzuki-Miyaura cross-coupling reaction and also in the synthesis of diaryl ketones is reported. [Ru-H@AuNPs-TD] was characterized by Fourier transform infrared spectroscopy, CHNS, TEM, SEM, ICP, and TGA analyses. The ruthenium hydride catalyst was used as a heterogeneous catalyst for the C-C coupling reactions of aryl halides with phenylboronic acids, and the biphenyl derivatives were produced in good to excellent yields. On the other hand, this catalytic system was applied for synthesis of diaryl ketones by the reaction of phenylboronic acids with substituted benzaldehydes. Moreover, this catalyst can be well-dispersed in the reaction medium, conveniently separated from the reaction mixture, and reused several times without significant loss of its activity.
- Daneshvar, Anahita,Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiollah,Mohammadpoor-Baltork, Iraj,Khalili, Akram
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p. 1747 - 1755
(2016/07/06)
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- Synthesis and biological evaluation of novel 4-hydroxytamoxifen analogs as estrogen-related receptor gamma inverse agonists
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Estrogen-related receptor gamma (ERRγ) has recently been recognized as an attractive target for treating inflammation, cancer, and metabolic disorders. Herein, we discovered and demonstrated the in vitro pharmacology as well as the absorption, distribution, metabolism, excretion, and toxicity (ADMET) properties of chemical entities that could act as highly selective inverse agonists for ERRγ. The results were comparable to those for GSK5182 (4), a leading ERRγ inverse agonist ligand. Briefly, the half-maximal inhibitory concentration (IC50) range of the synthesized compounds for ERRγ was 0.1-10 μM. Impressively, compound 24e exhibited potency comparable to 4 but was more selective for ERRγ over three other subtypes: ERRα, ERRβ, and estrogen receptor α. Furthermore, compound 24e exhibited a superior in vitro ADMET profile compared to the other compounds. Thus, the newly synthesized class of ERRγ inverse agonists could be lead candidates for developing clinical therapies for ERRγ-related disorders.
- Kim, Jina,Chin, Jungwook,Im, Chun Young,Yoo, Eun Kyung,Woo, Seoyeon,Hwang, Hee Jong,Cho, Joong-Heui,Seo, Kyung-Ah,Song, Jaeyoung,Hwang, Hayoung,Kim, Kyung-Hee,Kim, Nam Doo,Yoon, Suk Kyoon,Jeon, Jae-Han,Yoon, Seung-Yun,Jeon, Yong Hyun,Choi, Hueng-Sik,Lee, In-Kyu,Kim, Seong Heon,Cho, Sung Jin
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p. 338 - 352
(2016/07/06)
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- Diaryl a ketone compound catalytic oxidation synthesis method
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The invention provides a catalytic oxidation synthesis method of a diaryl ketone compound. In an organic solvent, ester derivatives of diaryl methanol are used as reaction substrates, DDQ and TBN are used as catalysts, oxygen is used as an oxidant, so as to react for 1 to 12 h under the conditions of oxygen pressure of 0.1 to 0.4 MPa and temperature of 110 to 140 DEG C, and post processing is performed on reaction liquid, so as to obtain a product of the diaryl ketone compound; structural formulas of the ester derivatives of the diaryl methanol as the reaction substrates are shown in the formulas (V), (VI), (VII) or (VIII), and structural formulas of products which are correspondingly obtained one by one are shown in the formulas (I), (II), (III) or (IV). The catalytic oxidation synthesis method has the advantages of simplicity, convenience and safety in operation, mild reaction condition, high product selectivity and environmental friendliness.
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Paragraph 0067-0068
(2020/05/05)
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- Synthetic method of fenofibrate drug intermediate 4-chloro-4'-hydroxybenzophenone
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The invention relates to a synthetic method of fenofibrate drug intermediate 4-chloro-4'-hydroxybenzophenone. The synthetic method comprises the following steps of adding 500ml of methylamine solution, 0.34 to 3.36mol of anisole, 0.36 to 0.37 mol of cuprous chloride into a reactor provided with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, controlling the stirring speed to be 160 to 190 rpm, controlling the solution temperature to be 35 to 40 DEG C, dropwise adding 0.35mol of p-chlorobenzamide (3), rising the solution temperature to be 45 to 50 DEG C after completion of addition, keeping the stirring speed and reacting for 7 to 8h, pouring reaction liquid into a sodium bisulfite solution, keeping the solution temperature to be 3 to 5 DEG C, separating out an organic layer, extracting a water layer with the methylamine solution for 6 to 8 times, combining with the organic layer, then steaming out methylamine to obtain an intermediate (4), adding 300ml of hexane, rising the solution temperature to be 80 to 85 DEG C for dehydration, lowering the solution temperature to be 60 DEG C, adding 0.6 mol of cuprous chloride, performing a reflux reaction for 2 to 3h, steaming out the hexane, lowering the solution temperature to be 5 to 9 DEG C, adding 200ml of potassium bicarbonate solution, controlling the stirring speed to be 200 to 260 rpm, filtering, washing with a salt solution, and performing dehydration with a dehydrant, so as to obtain the 4-Chloro-4'-hydroxybenzophenone.
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Paragraph 0015; 0016
(2016/11/17)
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- Iron-Catalyzed Acylation of Polyfunctionalized Aryl- and Benzylzinc Halides with Acid Chlorides
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FeCl2 (5 mol %) catalyzes a smooth and convenient acylation of functionalized arylzinc halides at 50 °C (2-4 h) and benzylic zinc chlorides at 25 °C (0.5-4 h) with a variety of acid chlorides leading to polyfunctionalized diaryl and aryl heteroaryl ketones.
- Benischke, Andreas D.,Leroux, Marcel,Knoll, Irina,Knochel, Paul
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supporting information
p. 3626 - 3629
(2016/08/16)
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- Synthesis and biological evaluation of negative allosteric modulators of the Kv11.1(hERG) channel
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We synthesized and evaluated a series of compounds for their allosteric modulation at the Kv11.1 (hERG) channel. Most compounds were negative allosteric modulators of [3H]dofetilide binding to the channel, in particular 7f, 7h-j and 7p. Compounds 7f and 7p were the most potent negative allosteric modulators amongst all ligands, significantly increasing the dissociation rate of dofetilide in the radioligand kinetic binding assay, while remarkably reducing the affinities of dofetilide and astemizole in a competitive displacement assay. Additionally, both 7f and 7p displayed peculiar displacement characteristics with Hill coefficients significantly distinct from unity as shown by e.g., dofetilide, further indicative of their allosteric effects on dofetilide binding. Our findings in this investigation yielded several promising negative allosteric modulators for future functional and clinical research with respect to their antiarrhythmic propensities, either alone or in combination with known Kv11.1 blockers.
- Yu, Zhiyi,Van Veldhoven, Jacobus P.D.,'T Hart, Ingrid M.E.,Kopf, Adrian H.,Heitman, Laura H.,Ijzerman, Adriaan P.
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supporting information
p. 50 - 59
(2015/11/23)
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- SMALL MOLECULE LFA-1 INHIBITORS
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The present invention relates to novel compounds which are capable of inhibiting the interaction of LFA-1 with its counter ligands.
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Page/Page column 120; 121
(2016/01/01)
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- Transition-metal-free, ambient-pressure carbonylative cross-coupling reactions of aryl halides with potassium aryltrifluoroborates
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We disclose an unprecedented transition-metal-free carbonylative cross coupling of aryl halides with potassium aryl trifluoroborates even at atmospheric pressure of carbon monoxide. This protocol is efficient, operationally simple, and shows wide scope with regard to both aryl halides and potassium aryl trifluoroborates containing a series of active functional groups.
- Jin, Fengli,Han, Wei
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supporting information
p. 9133 - 9136
(2015/06/08)
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- UV light-mediated difunctionalization of alkenes through aroyl radical addition/1,4-/1,2-Aryl shift cascade reactions
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UV light-mediated difunctionalization of alkenes through an aroyl radical addition/1,4-/1,2-aryl shift has been described. The resulted aroyl radical from a photocleavage reaction added to acrylamide compounds followed by cyclization led to the formation of oxindoles, whereas the addition to cinnamic amides aroused a unique 1,4-aryl shift reaction. Furthermore, the difunctionalization of alkenes of prop-2-en-1-ols was also achieved through aroyl radical addition and a sequential 1,2-aryl shift cascade reaction.
- Zheng, Lewei,Huang, Hongli,Yang, Chao,Xia, Wujiong
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p. 1034 - 1037
(2015/03/30)
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- Stabilizing PdII on hollow magnetic mesoporous spheres: A highly active and recyclable catalyst for carbonylative cross-coupling and Suzuki coupling reactions
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A hollow magnetic mesoporous silica sphere (HMMS) catalyst has been synthesized using polystyrene microspheres as a chemical template. The catalyst was characterized by TEM, XRD, XPS and vibrating sample magnetometry (VSM). The catalyst shows high activity for the carbonylative cross-coupling reaction of aryl iodides with arylboronic acids and Suzuki coupling reactions. The newly developed catalyst is easy to recover by magnetic separation from the liquid phase of the reaction and can be recycled. Importantly, the catalyst revealed high efficiency and high stability under the reaction conditions and during recycling stages.
- Niu, Jianrui,Liu, Mengmeng,Wang, Peng,Long, Yu,Xie, Miao,Li, Rong,Ma, Jiantai
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p. 1471 - 1476
(2014/05/06)
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- Preparation of recoverable Fe3O4/PPy-PdII catalysts for carbonylative cross-coupling reactions
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The hierarchical porous Fe3O4/PPy-PdII catalyst has been synthesized using Fe3O4 microspheres both as chemical template and oxidant source under sonication. The catalyst characterized by TEM, XRD, FT-IR, XPS and vibrating sample magnetometry (VSM). The catalyst showed high reactivity for the carbonylative cross-coupling reaction of aryl iodides with arylboronic acids. This newly developed catalyst could be easily recovered and revealed high efficiency and high stability under the reaction conditions and during recycling stages.
- Niu, Jianrui,Xie, Miao,Zhu, Xiaohang,Long, Yu,Wang, Peng,Li, Rong,Ma, Jiantai
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p. 247 - 252
(2014/07/07)
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- Palladium-catalyzed cross-coupling of 2-aryl-1,3-dithianes
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Palladium-catalyzed cross-coupling of aryl bromides with 2-aryl-1,3-dithianes is described. This methodology takes advantage of the relatively acidic benzylic proton of the dithiane, allowing it to act as a competent, polarity-reversed transmetalation reagent. This unique approach affords the ability to employ an orthogonal deprotection strategy, and practical routes to both diaryl ketones and diarylmethanes are illustrated. Cross-coupling of a range of aryl dithianes with aryl bromides, including scope and current limitations, is presented.
- Dockrey, Summer A. Baker,Makepeace, Alicia K.,Schmink, Jason R.
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p. 4730 - 4733
(2015/04/27)
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- One-pot synthesis of diarylmethanones through palladium-catalyzed sequential coupling and aerobic oxidation of aryl bromides with acetophenone as a latent carbonyl donor
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A one-pot palladium-catalyzed synthesis of symmetrical and unsymmetrical diarylmethanones using acetophenone and aryl bromides as raw materials has been developed. In this reaction, acetophenone acts as a latent carbonyl donor and two pathways of palladium-catalyzed sequential coupling and aerobic oxidation are identified. The reaction is applicable to a spectrum of substrates and delivers the products in moderate to good yields. This method can be used for the synthesis of ketoprofen, a nonsteroidal anti-inflammatory drug, in a two-step procedure and 45% overall yield.
- Wang, Xing,Liu, Fu-Di,Tu, Hai-Yang,Zhang, Ai-Dong
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p. 6554 - 6562
(2014/08/05)
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- Efficient and fast method for the preparation of Diaryl Ketones at room temperature
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Palladium-catalyzed cross-coupling reaction of arylboronic acids with acid chlorides at room temperature under phosphine-free conditions affords the corresponding aromatic ketones in excellent yields within short times. This synthetic method overcomes common disadvantages of Friedel-Crafts acylation procedures and is compatible with both electron-donating and electron-withdrawing substituents on the aryl ring of the acyl chlorides. Georg Thieme Verlag Stuttgart New York.
- Hajipour, Abdol Reza,Pourkaveh, Raheleh
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p. 1101 - 1105
(2014/05/20)
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- Preparation of Recoverable Pd Catalysts for Carbonylative Cross-Coupling and Hydrogenation Reactions
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We report on the synthesis, characterization and catalytic performance of new, supported PdII and Pd0 catalysts. The catalysts are characterized by TEM, XRD, FTIR, X-ray photoelectron spectroscopy, and vibrating sample magnetometry. The catalysts are found to be active in both forms, PdII and Pd0, for the carbonylative cross-coupling reaction of aryl iodides with arylboronic acids, and for the hydrogenation of aromatic nitro- and unsaturated compounds. The newly developed catalysts are prepared by a synthetic strategy that is similar to the one used for other supported catalysts but are easier to recover-they can be recycled by magnetic separation from liquid phase reactions-and can be used for at least 5 consecutive trials without any decrease in activity.
- Niu, Jian-Rui,Huo, Xing,Zhang, Feng-Wei,Wang, Hai-Bo,Zhao, Ping,Hu, Wu-Quan,Ma, Jiantai,Li, Rong
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p. 349 - 354
(2013/03/13)
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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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- Iodine-catalyzed disproportionation of aryl-substituted ethers under solvent-free reaction conditions
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Iodine was demonstrated to be an efficient catalyst for disproportionation of aryl-substituted ethers under solvent-free reaction conditions. Variously substituted 1,1,1′,1′-tetraaryldimethyl ethers were transformed into the corresponding diarylketone and diarylmethane derivatives. I 2-catalyzed transformation of 4-methoxyphenyl substituted ethers yielded mono- and dialkylated Friedel-Crafts products as well. Treatment of trityl alkyl and trityl benzyl ethers with a catalytic amount of iodine produced triphenylmethane and the corresponding aldehydes and ketones. The electron-donating substituents facilitated the reaction, while the electron-withdrawing groups retarded it; the difference in reactivity is not very high. Such an observation may be in favour of hydride transfer, predominantly from the less electron rich side of the ether with more stable carbocation formation. With the isotopic studies it was established that a substantial portion of the C-H bond scission took place in the rate-determining step, while the carbonyl oxygen atom originated from the starting ether, and not from the air. The transformation took place under air and under argon, and HI was not a functioning catalyst.
- Jereb, Marjan,Vrazic, Dejan
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p. 1978 - 1999
(2013/05/22)
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- A Palladium Bipyridyl Complex Grafted onto Nanosized MCM-41 as a Heterogeneous Catalyst for Negishi Coupling
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The Negishi coupling of aryl bromides or acyl chlorides with organozinc chlorides catalyzed by a palladium bipyridyl complex anchored on nanosized mobile crystalline material 41 (MCM-41) were investigated. The reactions proceeded smoothly with a very low catalyst loading in THF at 70°C for electron-deficient aryl bromides, which gave good to high yields of the Negishi coupling products. However, reactions in toluene at 110°C were required if electron-rich aryl bromides were employed. For acyl chlorides, the reactions could be performed in THF at 50°C and the corresponding ketones and ynones were obtained in high yields. After centrifugation, it was possible to easily recover the supported catalyst from the reaction mixture, and this could be reused several times without any retreatment or regeneration with only a slight decrease in activity.
- Wu, Wei-Yi,Lin, Tze-Chiao,Takahashi, Tamotsu,Tsai, Fu-Yu,Mou, Chung-Yuan
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p. 1011 - 1019
(2013/05/09)
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- A phosphane-free, atom-efficient cross-coupling reaction of triarylbismuths with acyl chlorides catalyzed by MCM-41-immobilized palladium complex
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The first phosphane-free, heterogeneous, atom-efficient cross-coupling reaction of triarylbismuths and acyl chlorides was achieved in N-methylpyrrolidone (NMP) with Bu3N as the base at 80 °C in the presence of 1.5 mol-% MCM-41-immobilized bidentate nitrogen palladium complex [MCM-41-2N-Pd(OAc)2, MCM = mobile crystalline material] to yield a variety of unsymmetrical biaryl ketones in good to excellent yields. This heterogeneous palladium catalyst exhibited a high activity, which was similar to that of Pd(PPh3)4. The catalyst can be recovered by a simple filtration of the reaction solution and recycled in at least 10 consecutive trials without any decrease in activity. Our system not only avoids the use of phosphane ligands, but also solves the basic problem of palladium catalyst recovery and reuse. The first phosphane-free, heterogeneous, atom-efficient cross-coupling reaction of triarylbismuth compounds and acyl chlorides was achieved in N-methylpyrrolidone with Bu3N as the base at 80 °C in the presence of 1.5 mol-% MCM-41-immobilized bidentate nitrogen palladium complex [MCM-41-2N-Pd(OAc)2] to yield a variety of unsymmetrical biaryl ketones in good to excellent yields. Copyright
- Zhao, Hong,Yin, Lin,Cai, Mingzhong
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p. 1337 - 1345
(2013/04/10)
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