- 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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supporting information
p. 24214 - 24219
(2021/10/07)
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- Synthesis, structure, and characterization of picolyl- and benzyl-linked biphenyl palladium N-heterocyclic carbene complexes and their catalytic activity in acylative cross-coupling reactions
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N-heterocyclic carbene ligands with picolyl (L1H2Br2, L3H2Br2) and benzyl (L2H2Br2, L4H2Br2) linked biphenyl backbone were synthesized and characterized. Their palladium(II) complexes [PdL1]Br2 (1), [PdL2Br2] (2), [PdL3]Br2 (3), and [PdL4Br2] (4) were synthesized by direct method using Pd(OAc)2. All complexes (1–4) were characterized by CHN analysis, electrospray ionization-MS, nuclear magnetic resonance, and single-crystal X-ray diffraction. Molecular structures confirm the distorted square planar geometry around the Pd(II) center. All of them showed good catalytic activity in acylative Suzuki cross coupling of phenyl boronic acid with benzoyl chloride to afford benzophenone in good yields.
- Muniyappan, Nalluchamy,Sabiah, Shahulhameed
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- METALLOENZYME INHIBITOR COMPOUNDS
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Provided are compounds having HDAC6 modulating activity, and methods of treating diseases, disorders or symptoms thereof mediated by HDAC6.
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Page/Page column 239-240
(2018/09/28)
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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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- Transition metal-free Suzuki type cross-coupling reaction for the synthesis of dissymmetric ketones
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A simple, efficient and metal-free route for the synthesis of dissymmetric ketones through Suzuki type cross-coupling reaction has been established. This strategy signifies an attractive, cost-effective and operationally convenient tool for the synthesis of a wide range of dissymmetric ketones. Although conventional routes for the synthesis of ketones have been widely used, the potential challenge with these methods is functional group tolerance. The reported metal-free method represents a reaction with moderate functional group tolerance. The procedure is operationally convenient and shows broad substrate scope with good to excellent product yields.
- Jadhav, Sanjay,Rashinkar, Gajanan,Salunkhe, Rajashri,Kumbhar, Arjun
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supporting information
p. 3201 - 3204
(2017/07/27)
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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; 0027-0033
(2017/08/02)
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- KCC-1 supported palladium nanoparticles as an efficient and sustainable nanocatalyst for carbonylative Suzuki-Miyaura cross-coupling
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This work reports a cost-effective and sustainable protocol for the carbonylative Suzuki-Miyaura cross-coupling reaction catalyzed by palladium nanoparticles (Pd NPs) supported on fibrous nanosilica (KCC-1). Under mild reaction conditions, the KCC-1-PEI/Pd catalytic system showed a turnover number (TON) 28-times and a turnover frequency (TOF) 51-times higher than the best supported Pd catalyst reported in the literature for the carbonylative cross-coupling between 4-iodoanisole and phenylboronic acid, as a test reaction. Also, the catalyst could be recycled up to ten times with a marginal loss in activity after the eighth cycle. The high activity of the catalyst can be attributed to the fibrous nature of the KCC-1 support and PEI functionalization provided the enhanced stability.
- Gautam, Prashant,Dhiman, Mahak,Polshettiwar, Vivek,Bhanage, Bhalchandra M.
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supporting information
p. 5890 - 5899
(2016/11/06)
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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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- Synthesis of 4β-N-polyaromatic substituted podophyllotoxins: DNA topoisomerase inhibition, anticancer and apoptosis-inducing activities
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A new class of 4β-N-polyaromatic substituted podophyllotoxin congeners have been synthesized and evaluated for their DNA topoisomerase-II (topo-II) inhibition as well as anticancer potential in some human cancer cell lines. The ease of synthesis and inter
- Kamal, Ahmed,Kumar, B. Ashwini,Suresh, Paidakula,Agrawal, Satyam Kumar,Chashoo, Gousia,Singh, Shashank K.,Saxena
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experimental part
p. 8493 - 8500
(2011/02/24)
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- A novel Br?nsted acid catalyst for Friedel-Crafts acylation
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Bis(trifluoroalkylsulfonylimino)trifluoromethanesulfonic acid has demonstrated remarkable catalytic ability in the electrophilic acylation of aromatic substrates. Various perfluoroalkyl substituted aroyl chlorides are employed in Friedel-Crafts acylation typically using 1 mol % of catalyst. Crown Copyright
- Posternak, Anna G.,Garlyauskayte, Romute Yu.,Yagupolskii, Lev M.
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supporting information; body text
p. 446 - 447
(2009/05/27)
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- Cesium hydroxide-promoted aerobic oxidation of sec-aromatic alcohols
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A CsOH-promoted aerobic oxidation of sec-aromatic alcohols has been developed, using air as a free and clean oxidant, and providing aryl ketones in good to excellent yields.
- Zhang, Weiwei,Liu, Miaochang,Wu, Huayue,Ding, Jinchang,Cheng, Jiang
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p. 5336 - 5338
(2008/12/22)
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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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- PYRIMIDINE DERIVATIVES FOR TREATMENT OF HYPERPROLIFERATIVE DISORDERS
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Pyrimidine derivatives of formula (I), pharmaceutical compositions containing these compounds, and methods of using these compounds in treatment of hyperproliferative diseases such as cancer are disclosed and claimed.
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Page/Page column 46
(2010/11/23)
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- PYRIMIDINE DERIVATIVES FOR TREATMENT OF HYPERPROLIFERATIVE DISORDERS
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Pyrimidine derivatives of formula (I) in which J and Y represent aromatic or heteroaromatic rings; R2, G, G', and G" represent substituent groups and R2a represents H or halogen; L represents a linking group; and M represents CH or N. Pharmaceutical compositions containing these compounds, and methods of using these compounds in treatment of hyperproliferative diseases such as cancer are also disclosed and claimed.
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Page/Page column 60-61
(2008/06/13)
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- Method for acylation or sulphonylation of an aromatic compound
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The present invention relates to a process for the acylation or sulphonylation of an aromatic compound. More particularly, the invention relates to a process for the acylation or sulphonylation of an activated or deactivated aromatic compound. The invention is applied to the preparation of aromatic ketones or sulphones. The process for the acylation or sulphonylation of an aromatic compound which consists in reacting at least one aromatic compound with an acylating or sulphonylating agent, in the presence of a Friedel-Crafts catalyst is characterized in that the acylation or sulphonylation reaction is carried out in liquid phase under microwave irradiation.
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Page column 19
(2008/06/13)
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- Preparation process of fluorine substituted aromatic compound
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A preparation process of a fluorine substituted aromatic compound comprising reacting an alkali metal or alkali earth metal salt of an aromatic compound having a hydroxy group with an organic fluorinating agent is disclosed. As a representative fluorinating agent, a bis-dialkylamino-difluoromethane compound, for example, 2,2′-difluoro-1,3-dimethylimidazolidine, is exemplified. According to the process, an industrially useful fluorinated aromatic compound, for example, a fluorobenzene, a fluorine substituted benzophenone, a fluorine substituted diarylsulfone can be prepared with ease in economy without specific equipment.
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- 2-(substituted-phenyl)amino-imidazoline derivatives
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This invention relates to IP receptor antagonists selected from the group of compounds represented by Formula I: where:R1 is a group represented by formula (A), (B) or (C); and other substituents as defined in the specification, and their pharmaceutically acceptable salts or crystal forms thereof; and pharmaceutical compositions containing them; and methods for their use as therapeutic agents.
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- The formation of 4,4′-difluorobenzophenone from 4,4′-dinitrodiphenylmethane
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The novel one pot oxidation/fluorodenitration of 4,4′-dinitrodiphenylmethane to form 4,4′-difluorobenzophenone has been achieved using tetramethylammonium fluoride in N,N-dimethylacetamide.
- Adams, Dave J.,Clark, James H.,McFarland, Heather
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p. 127 - 129
(2007/10/03)
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- Studies on the Insecticidal Activities of Some New N-Benzoyl-N'-Arylureas
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This paper reports the synthesis and the insecticidal activities of some N-benzoyl-N'-arylureas 4-arylsubstituted with alkylated or halogenated aroyl moieties. The compounds, tested against some representative insect species, displayed very high activity against Aedes aegypti, especially the halosubstituted derivatives. None of the newly synthesized compounds showed genotoxic activity in the Bacillus subtilis rec-assay and in the Salmonella-microsome test.
- Carmellino, Maria L.,Pagani, Giuseppe,Pregnolato, Massimo,Terreni, Marco,Caprioli, Vincenzo,Zani, Franca
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p. 227 - 236
(2007/10/03)
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- Preparation of 4-fluorophenol and 4-fluorobenzoic acid by the Baeyer-Villiger reaction
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The possibility of preparing 4-fluorophenol or 4-fluorobenzoic acid via the Baeyer-Villiger reaction starting from unsymmetrical fluoroaryl ketones is disscussed.Several unsymmetrical 4-fluorobenzophenones having different substituents in the fluorine-free aryl group were prepared and converted to esters by treatment with peracetic acid.The electrophilicity of the substituents influenced the molecular structure of the ester formed as a result of a carbon-to-oxygen migration, and hence 4-fluorophenol or 4-fluorobenzoic acid formation.Electron-withdrawing substituents favoured the formation of 4-fluorophenol in good yields, while electron-donating substituents formed 4-fluorobenzoic acid preferentially.
- Conte, L.,Napoli, M.,Gambaretto, J. P.,Guerrato, A.,Carlini, F. M.
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- DNA-Direcred Alkylating Agents. 4. 4-Anilinoquinoline-Based Minor Groove Directed Aniline Mustards
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A series of 4-anilinoquinoline-linked aniline mustards of widely varying mustard reactivity were prepared and evaluated for their antitumor activity.The compounds were designed as minor groove binding agents, where the aniline mustard ring is itself part of the DNA-binding ligand.While there was a general trend for cytotoxicity to correlate with mustard reactivity, this was much less pronounced than with untargeted mustards.The compounds were much more cytotoxic than the parent diols, and were also at least 10-fold more cytotoxic than the corresponding aniline mustards themselves.Comparative cell line studies suggested that the mechanism of cytotoxicity varied with mustard reactivity.The most reactive mustards cross-linked DNA, while cell killing by the less reactive compounds appeared to be by the formation of bulky monoadducts.The compounds were active but not particularly dose-potent against P388 leukemia in vivo.The modest potency may be related to their poor aqueous solubility, since the more soluble methyl quarternary salts were equally active at much lower doses.
- Gravatt, G. Lance,Baguley, Bruce C.,Wilson, William R.,Denny, William A.
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p. 1552 - 1560
(2007/10/02)
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