16574-52-0Relevant articles and documents
An iodine(iii) mediated oxidative rearrangement of enamines: efficient synthesis of α-amino ketones
Yadagiri, Dongari,Anbarasan, Pazhamalai
, p. 14203 - 14206 (2015)
An iodine(iii)-mediated, group-selective oxidative rearrangement of β,β-diarylenamines to α-amino ketones has been accomplished with excellent yield. The developed reaction involves the initial oxidation of enamine to an α-acyloxyimine intermediate and concomitant semipinacol rearrangement.
Systematic Evaluation of 1,2-Migratory Aptitude in Alkylidene Carbenes
Dale, Harvey J. A.,Nottingham, Chris,Poree, Carl,Lloyd-Jones, Guy C.
supporting information, p. 2097 - 2107 (2021/02/01)
Alkylidene carbenes undergo rapid inter- and intramolecular reactions and rearrangements, including 1,2-migrations of β-substituents to generate alkynes. Their propensity for substituent migration exerts profound influence over the broader utility of alkylidene carbene intermediates, yet prior efforts to categorize 1,2-migratory aptitude in these elusive species have been hampered by disparate modes of carbene generation, ultrashort carbene lifetimes, mechanistic ambiguities, and the need to individually prepare a series of 13C-labeled precursors. Herein we report on the rearrangement of 13C-alkylidene carbenes generated in situ by the homologation of carbonyl compounds with [13C]-Li-TMS-diazomethane, an approach that obviates the need for isotopically labeled substrates and has expedited a systematic investigation (13C{1H} NMR, DLPNO-CCSD(T)) of migratory aptitudes in an unprecedented range of more than 30 alkylidene carbenes. Hammett analyses of the reactions of 26 differentially substituted benzophenones reveal several counterintuitive features of 1,2-migration in alkylidene carbenes that may prove of utility in the study and synthetic application of unsaturated carbenes more generally.
Transition-metal-free carbonylation of aryl halides with arylboronic acids by utilizing stoichiometric CHCl3 as the carbon monoxide-precursor
Xu, Fangning,Li, Dan,Han, Wei
supporting information, p. 2911 - 2915 (2019/06/18)
Under transition-metal-free conditions, carbonylative Suzuki couplings of aryl halides with arylboronic acid using stoichiometric CHCl3 as the carbonyl source has been developed. The simple, efficient, and environmentally benign method was successfully applied to the synthesis of Fenofibric acid, naphthyl phenstatin, and carbon-13 labeled biaryl ketone.
At normal pressure fragrant ketone nickel catalytic synthesis method
-
Paragraph 0003; 0017; 0027-0033, (2017/08/02)
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.
In situ generated nickel nanoparticle-catalyzed carbonylative Suzuki reactions of aryl iodides with arylboronic acids at ambient CO pressure in poly(ethylene glycol)
Zhong, Yanzhen,Gong, Xinxing,Zhu, Xiaoshu,Ni, Zhuchao,Wang, Haoyang,Fu, Jinglin,Han, Wei
, p. 63216 - 63220 (2015/02/19)
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
Practical one-pot preparation of ketones from aryl and alkyl bromides with aldehydes and DIH via Grignard reagents
Dohi, Souya,Moriyama, Katsuhiko,Togo, Hideo
experimental part, p. 6557 - 6564 (2012/08/27)
Various diaryl ketones, alkyl aryl ketones, and dialkyl ketones were efficiently prepared in good yields by the reactions of the Grignard reagents derived from aryl or alkyl bromides, followed by the reactions with aromatic or aliphatic aldehydes and the subsequent treatment with 1,3-diiodo-5,5- dimethylhydantoin and K2CO3, in a one-pot method. The same treatment of aromatic bromides bearing electron-withdrawing groups, such as ester, nitrile, ketone, and nitro groups with i-PrMgCl·LiCl or PhMgCl instead of Mg, also provided the corresponding diaryl and alkyl aryl ketones in good yields. The above methods are simple and practical transition-metal-free methods for the preparation of various diaryl ketones and alkyl aryl ketones bearing electron-rich aromatic groups and electron-deficient aromatic groups, as well as dialkyl ketones.
AlCl3-mediated defluorinative diarylhydroxylation transformation of CF3: Chemoselective arylation of CF3 and chlorocarbonyl groups attached to aromatic rings
Okamoto, Akiko,Kumeda, Kazuhiro,Yonezawa, Noriyuki
scheme or table, p. 124 - 125 (2010/05/18)
The CF3 group in 4-trifluoromethylbenzoyl chloride is efficiently diarylated and converted, into a diarylhydroxymethyl group by treatment with AlCl3 in the presence of an excess amount of halobenzene (C6H5X; X = F, Cl, and Br). The diarylation is followed by arylation of the chlorocarbonyl group to afford triarylated products, diarylhydroxymethylated benzophenones. The employment of TfOH in place of AlCl3 promotes the exclusive arylation of the chlorocarbonyl group leaving the CF3 group unchanged, to afford selectively 4-trifluoromethylbenzophenones, which then undergo diarylhydroxymethylation with the aid of AlCl3.
A novel Br?nsted acid catalyst for Friedel-Crafts acylation
Posternak, Anna G.,Garlyauskayte, Romute Yu.,Yagupolskii, Lev M.
supporting information; body text, p. 446 - 447 (2009/05/27)
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
Synthesis, labelling and first evaluation of [18F]R91150 as a serotonin 5-HT2A receptor antagonist for PET
Muehlhausen, Ute,Ermert, Johannes,Coenen, Heinz H.
experimental part, p. 13 - 22 (2009/04/18)
In psychiatric disorders such as anxiety, depression and schizophrenia, 5-HT2A receptors play an important role. In order to investigate them in vivo there is an increasing interest in selective and high-affinity radioligands for receptor binding studies using positron emission tomography (PET). Since available radioligands have disadvantages, R91150, which is a selective and high-affinity ligand for 5-HT2A receptors, was labelled with fluorine-18. This was accomplished in six steps via 4-[ 18F]fluorophenol and 1-(3-bromopropoxy)-4-[18F] fluorobenzene within 190 min starting from no-carrier-added [ 18F]fluoride. The overall radiochemical yield was 3.8±2% and the specific activity was at least 335 GBq/μmol at the end of the synthesis. First ex vivo studies in mice proved the uptake of [18F]R91150 in the brain. Radiometabolite studies revealed no radiometabolites in the brain, whereas in the plasma at least two could be detected 30 min p.i. Further preclinical studies are encouraged to evaluate the potential of this new 5-HT2A ligand as a radiotracer for PET. Copyright
Electrophilic aromatic aroylation with CF3-bearing arenecarboxylic acid derivatives: Reaction behavior and acidic mediator dependence
Akiko, Okamoto,Katsuya, Maeyama,Hideaki, Oike,Noriyuki, Yonezawa
, p. 2701 - 2715 (2008/02/12)
Triflic acid (TfOH) has been proven to be effective as a tolerant acidic mediator in electrophilic aromatic aroylation with CF3-bearing aroyl chlorides. The TfOH-mediated aroylation of fluorobenzene proceeds with high selectivity to give CF3-bearing aryl fluorophenyl ketones in good yields, which are hardly obtained with the aid of AlCl3 or direct condensation reagents. Copyright Taylor & Francis Group, LLC.
