- Palladium nanoparticles on amino-modified silica-catalyzed C–C bond formation with carbonyl insertion
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Abstract: A practical and heterogeneously catalyzed Stille, homo-coupling, and Suzuki carbonylation reaction has been reported using Pd nanoparticles supported on amino-vinyl silica-functionalized magnetic carbon nanotube (CNT@Fe3O4@SiO2-Pd) for the efficient synthesis of symmetrical and unsymmetrical diaryl ketones from aryl iodides. A wide variety of symmetrical and unsymmetrical diaryl ketones were obtained in high yields under CO gas-free conditions using Mo(CO)6 as an efficient carbonyl source. Considering the atom economy of Ph3SnCl, less than an equimolar amount can be applied in Stille transformation, which is of great importance due to the toxicity of organotin derivatives. Moreover, no phosphine ligand and external reducing agent were necessary in these coupling carbonylation reactions. This heterogeneous Pd catalyst offers high activity with very low palladium leaching. Finally, the catalyst can be reused and recycled for six steps without loss in activity, exhibiting good example of sustainable methodology. Graphic abstract: [Figure not available: see fulltext.].
- Etemadi-Davan, Elham,Khalili, Dariush,Banazadeh, Ali Reza,Sadri, Ghazal,Arshad, Pourya
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p. 1891 - 1903
(2021/02/01)
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- Photo-induced phosphorus radical involved semipinacol rearrangement reaction: Highly synthesis of γ-oxo-phosphonates
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Hydroxyphosphoric acids display the unique biological activities, and they have some attractive prospects as clinical drug moleculars. Herein, a new approach for the synthesis of γ-oxo-phosphonates (the precursor of hydroxyphosphoric acid) has been established through the semipinacol rearrangement tactic involved the photo-induced phosphorus radical process. Most important, this transformation is avoid of the external oxidants, and occurs very well under the sunlight irradiation, meanwhile the γ-oxo-phosphonate was easily derivatized to obtain γ-hydroxyphosphoric acid, thus highlights the synthesis value of this method.
- Wang, Chunhai,Huang, Xiaoling,Liu, Xueting,Gao, Suqian,Zhao, Bin,Yang, Shangdong
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p. 677 - 680
(2019/08/27)
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- Sodium Methyl Carbonate as an Effective C1 Synthon. Synthesis of Carboxylic Acids, Benzophenones, and Unsymmetrical Ketones
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Reported is the synthesis of carboxylic acids, symmetrical ketones, and unsymmetrical ketones with selectivity achieved by exploiting the differential reactivity of sodium methyl carbonate with Grignard and organolithium reagents.
- Hurst, Timothy E.,Deichert, Julie A.,Kapeniak, Lucas,Lee, Roland,Harris, Jesse,Jessop, Philip G.,Snieckus, Victor
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supporting information
p. 3882 - 3885
(2019/06/07)
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- Method for preparing symmetric diarylketone through catalytic oxidative carbonylation
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The invention discloses a method for preparing symmetric diarylketone of a formula (I) as shown in the description. The method comprises the following steps: mixing arylboronic acid (II) (Ar-B(OH)2 (II)), a palladium catalyst, a promoter and an organic solvent in a reactor, introducing air and CO having a volume ratio of (7-19):1, reacting under the conditions of a pressure of 1-6 atm and a temperature of 30-80 DEG C for 8-16 hours, and performing after-treatment on the reaction solution, thereby obtaining the product symmetric diarylketone. According to the method disclosed by the invention,the air directly serves as an oxidizing agent to replace the O2 to be applied to oxidative carbonylation of the arylboronic acid, and the ratio of the air to CO is beyond an explosion limit. Therefore, the catalytic system is safe and economic. The palladium catalyst is small in dosage and simple in separation and can be recycled for several times. The method disclosed by the invention is mild inreaction condition, excellent in substrate suitability and high in yield.
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-
Paragraph 0023; 0024; 0025; 0026; 0028
(2019/03/08)
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- Nickel-Catalyzed Molybdenum-Promoted Carbonylative Synthesis of Benzophenones
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A nickel-catalyzed molybdenum-promoted carbonylative coupling reaction for the synthesis of benzophenones from aryl iodides has been developed. Various substituted diaryl ketones were synthesized in moderate to excellent yields under CO-gas-free conditions. A synergetic effect of both nickel and molybdenum has been observed, which is also responsible for the success of this transformation.
- Peng, Jin-Bao,Wu, Fu-Peng,Li, Da,Qi, Xinxin,Ying, Jun,Wu, Xiao-Feng
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p. 6788 - 6792
(2018/06/04)
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- Palladium-Catalyzed Carbonylative Homocoupling of Aryl Iodides for the Synthesis of Symmetrical Diaryl Ketones with Formic Acid
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A convenient method for the palladium-catalyzed carbonylative homocoupling of aryl iodides was developed. With formic acid as the CO source, various symmetrical diaryl ketones were synthesized in moderate to good yield in the presence of a palladium catalyst.
- Wu, Fu-Peng,Peng, Jin-Bao,Qi, Xinxin,Wu, Xiao-Feng
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p. 173 - 177
(2017/11/27)
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- Co(III)-Catalyzed Synthesis of Quinazolines via C-H Activation of N-Sulfinylimines and Benzimidates
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C-H activation of arenes has been established as an important strategy for heterocycle synthesis via annulations between arenes and unsaturated coupling partners. However, nitriles failed to act as such a coupling partner. Dioxazolones have been employed as a synthon of nitriles, and subsequent coupling with arenes such as N-sulfinylimines and benzimidates bearing a functionalizable directing group provided facile access to two classes of quinazolines under Co(III)-catalysis.
- Wang, Fen,Wang, He,Wang, Qiang,Yu, Songjie,Li, Xingwei
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supporting information
p. 1306 - 1309
(2016/04/01)
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- Ligand-Free Palladium-Catalyzed Oxidative Carbonylative Homocoupling of Arylboron Reagents at Ambient Pressure
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Arylboronic acids or potassium aryltrifluoroborates were readily oxidatively carbonylated to their corresponding diaryl ketones in high yields with high selectivities by ligand-free palladium-catalyzed homocoupling at atmospheric pressure. This novel method employs molecular oxygen or iodine as the oxidant and offers an attractive alternative to transition-metal-based oxidant systems.
- Zhao, Hongyuan,Han, Wei
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supporting information
p. 4279 - 4283
(2016/09/14)
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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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- Palladium-catalyzed oxidative carbonylation for the synthesis of symmetrical diaryl ketones at atmospheric co pressure
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A mild and efficient synthesis of symmetrical diaryl ketones by palladium-catalyzed oxidative carbonylation of arylboronic acids with carbon monoxide at atmospheric pressure is reported. Georg Thieme Verlag Stuttgart New York.
- Li, Yang,Lu, Wei,Xue, Dong,Wang, Chao,Liu, Zhao-Tie,Xiao, Jianliang
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supporting information
p. 1097 - 1100
(2014/05/20)
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- Pd/Cu-cocatalyzed aerobic oxidative carbonylative homocoupling of arylboronic acids and CO: A highly selective approach to diaryl ketones
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A highly selective Pd/Cu-cocatalyzed aerobic oxidative carbonylative homocoupling of arylboronic acids has been developed. This method employs a simple catalytic system, readily available boronic acids as the substrates, molecular oxygen as the oxidant, and 1 atm of CO/O2, which makes this method practical for further applications.
- Ren, Long,Jiao, Ning
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supporting information
p. 2411 - 2414
(2014/10/15)
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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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- Rh-catalyzed carbonylation of arylzinc compounds yielding symmetrical diaryl ketones by the assistance of oxidizing agents
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Carbonylative homocoupling of arylzinc compounds 1 using 1 atm of CO and 1,2-dibromoethane as an oxidant was achieved in the presence of Rh-dppf catalyst, affording symmetrical diaryl ketones in good yields. Under similar conditions, Pd or Ni catalysts induced oxidative homocoupling of 1 to yield biaryls instead. The beneficial catalysis by Rh in the carbonylation was presumed to stem from the facility by which the migration of the aryl ligand to CO at the Rh3+ intermediate occurred.
- Kobayashi, Kana,Nishimura, Yugo,Gao, Fuxing,Gotoh, Kazuma,Nishihara, Yasushi,Takagi, Kentaro
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supporting information; experimental part
p. 1949 - 1952
(2011/06/20)
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- Phosphine ligand triggered oxidative decarbonylative homocoupling of aromatic aldehydes: Selectively generating biaryls and diarylketones
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A novel rhodium-catalyzed oxidative decarbonylative homocoupling of aromatic aldehydes to generate biaryls and diarylketones selectively and efficiently, triggered by the choice of different phosphine ligands.
- Yang, Luo,Zeng, Tieqiang,Shuai, Qi,Guo, Xiangyu,Li, Chao-Jun
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supporting information; experimental part
p. 2161 - 2163
(2011/03/22)
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- Oxalyl chloride as carbonyl synthon in Pd-catalyzed carbonylations of triarylbismuth and triarylindium organometallic nucleophiles
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Oxalyl chloride has been demonstrated to function as C1 carbonyl synthon in the carbonylations of triarylbismuth and triarylindium nucleophiles under palladium-catalyzed conditions. All the three aryl groups from both bismuth and indium reagents participated in carbonylative couplings to afford the corresponding functionalized ketones in high yields. This study also disclosed a novel utilization of oxalyl chloride as facile alternative source of CO for carbonylations under palladium catalysis.
- Rao, Maddali L. N.,Venkatesh, Varadhachari,Dasgupta, Priyabrata
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supporting information; experimental part
p. 4975 - 4980
(2011/01/12)
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- Dications of fluorenylidenes. The relationship between redox potentials and antiaromaticity for meta- and para-substituted diphenylmethylidenefluorenes
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Electrochemical oxidation of meta-substituted diphenylmethylidenefluorenes (3a-g) results in the formation of fluorenylidene dications that are shown to be antiaromatic through calculation of the nucleus independent chemical shift (NICS) for the 5- and 6-
- Mills, Nancy S.,Tirla, Cornelia,Benish, Michele A.,Rakowitz, Amber J.,Bebell, Lisa M.,Hurd, Caroline M. M.,Bria, Anna L. M.
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p. 10709 - 10716
(2007/10/03)
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- HYDROXYL COMPOUNDS AND COMPOSITIONS FOR CHOLESTEROL MANAGEMENT AND RELATED USES
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The present invention relates to novel hydroxyl compounds, compositions comprising hydroxyl compounds, and methods useful for treating and preventing a variety of diseases and conditions such as, but not limited to aging, Alzheimer's Disease, cancer, cardiovascular disease, diabetic nephropathy, diabetic retinopathy, a disorder of glucose metabolism, dyslipidemia, dyslipoproteinemia, hypertension, impotence, inflammation, insulin resistance, lipid elimination in bile, obesity, oxysterol elimination in bile, pancreatitis, pancreatitius, Parkinson's disease, a peroxisome proliferator activated receptor-associated disorder, phospholipid elimination in bile, renal disease, septicemia, metabolic syndrome disorders (e.g., Syndrome X), thrombotic disorder. Compounds and methods of the invention can also be used to modulate C reactive protein or enhance bile production in a patient. In certain embodiments, the compounds, compositions, and methods of the invention are useful in combination therapy with other therapeutics, such as hypocholesterolemic and hypoglycemic agents.
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Page 276-277
(2008/06/13)
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- Palladium-catalyzed direct conversion of carboxylic acids into ketones with organoboronic acids promoted by anhydride activators
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A new type of catalytic process to convert carboxylic acids and organoboron compounds into unsymmetrical ketones in one-pot under mild and neutral conditions was presented. The method allowed the use of an α, β-unsatuarted carboxylic acids such as trans-c
- Yamamoto,Kakino,Narahashi,Shimizu
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p. 1333 - 1345
(2007/10/03)
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- Synthesis of substituted phenyl ketones via Pd-catalysed hydrodechlorination of their polychlorinated derivatives
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The following compounds, 2- and 3-methylacetophenones, 2- and 3-methylbenzophenones, and 2,2'-, 2,3'- and 3,3'-dimethylbenzophenones have been synthesized through a Pd-catalysed hydrodechlorination of the corresponding dichlorinated derivatives. The reaction has been carried out under multiphase conditions at 30-50°C, by bubbling H2 at atmospheric pressure into a biphasic system constituted by an organic substrate solution (isooctane solvent) and an aqueous alkaline solution (50% aq KOH), in the presence of Pd/C (5% wt) and Aliquat 336 (tricaprylylmethylammonium chloride). Likewise, fluorinated aceto- and benzophenones (4-fluoro-3-methylacetophenone and 4-fluoro-3-methylbenzo-, 4-fluoro-2',3-dimethylbenzo-, 4-fluoro-3,3'-dimethylbenzophenones) have been prepared starting from the corresponding chlorinated methylfluoro and dimethyfluoro ketones. Under such conditions, the presence of the onium salt allows the reaction to proceed with a high chemoselectivity: chlorine is removed while both the reduction of the carbonyl group and/or fluorine removal are prevented.
- Bomben, Andrea,Marques, Carlos A.,Selva, Maurizio,Tundo, Pietro
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p. 1109 - 1114
(2007/10/03)
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- Carbonylative coupling of iodobenzene to benzophenone with [n-Bu4N][HFe(CO)4]
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The reaction of Bu4N+[HFe(CO)4]- with iodobenzene in a biphasic medium (aqueous NaOH/benzene) under carbon monoxide (1 atm) affords benzophenone in 85% yield. Mechanistic investigations indicate that the reaction first involves an SET from [HFe(CO)4]- to Phi. Evidence for the generation of phenyl radicals and [(PhCO)Fe(CO)4]- species is presented. Separate experiments show that [(PhCO)Fe(CO)4]- does not react with Phi, but does with phenyl radicals, generated from Phi and Smh, leading to benzophenone. Eisevier,.
- Brunet, Jean-Jacques
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- Discovery and optimization of a novel class of orally active nonpeptidic endothelin-A receptor antagonists
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A novel class of endothelin-A receptor ligands was discovered by high-throughput screening. Lead structure optimization led to highly potent antagonists which can be synthesized in a short sequence. The compounds are endothelin-A-selective, are orally available, and show a long duration of action.
- Riechers, Hartmut,Albrecht, Hans-Peter,Amberg, Willi,Baumann, Ernst,Bernard, Harald,B?hm, Hans-Joachim,Klinge, Dagmar,Kling, Andreas,Müller, Stefan,Raschack, Manfred,Unger, Liliane,Walker, Nigel,Wernet, Wolfgang
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p. 2123 - 2128
(2007/10/03)
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- Rhodium(I)- and Palladium(0)-Catalyzed Carbonylation of Triarylbismuthines with Carbon Monoxide via a Possible Oxidative Addition of a Carbon-Bismuth Bond to Rhodium(I) and Palladium(0)
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Triarylbismuthines react with carbon monoxide (CO) at atmospheric pressure in acetonitrile at 25 deg C in the presence of a catalytic amount of a rhodium compound such as 2, RhCl3*3H2O, and 2 to give the corresponding diaryl ketones in high yields.If methanol is used as the solvent, methyl benzoates are also produced.When similar reactions are carried out in methanol in the presence of a catalytic amount of palladium(II) acetate together with potassium carbonate in place of the rhodium compound, methyl benzoates are formed as the sole carbonylation products.The oxidative addition of a carbon-bismuth bond to rhodium(I) and palladium(0) is proposed as the key step of these carbonylation reactions.
- Cho, Chan Sik,Yoshimori, Yasuharu,Uemura, Sakae
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p. 950 - 957
(2007/10/02)
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- Electrochemical Synthesis of Symmetrical Ketones from Acid Chlorides
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The electrochemical reduction of aroyl or arylacetyl chlorides was performed in an undivided cell fitted with a stainless steel anode and a nickel foam cathode.The electrolyses were carried out at constant current in acetonitrile as solvent, leading to the corresponding symmetrical ketones. Key words: symmetrical ketones synthesis, acid chloride electroreduction.
- Folest, Jean-Claude,Pereira-Martins, Edouard,Troupel, Michel,Perichon, Jacques
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p. 7571 - 7574
(2007/10/02)
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- Electrocyclic Aromatic Substitution by Nitrile Ylides to give 3H-2-Benzazepines: Substituent Effects and Mechanism
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Benzonitrile 3,3-diarylallyl nitrile ylides (16), generated by the base-induced dehydrochlorination of imidoyl chlorides, cyclised by 1,7-ring closure to give 3H-2-benzazepines e.g. (19), in contrast to analogous diazo-compounds (1) which prefer 1,5-elect
- Groundwater, Paul W.,Sharp, John T.
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p. 7951 - 7964
(2007/10/02)
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- Bimetallic catalysis: synthesis of benzophenones through carbonylation of aryl iodides catalysed by Fe(CO)5-Co2(CO)8 systems.
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The direct, catalytic carbonylation of aryl iodides to give the corresponding benzophenones is reported for the first time.Under phase transfer conditions (aq.NaOH/C6H6/Bu4NBr) and under 1 atm pressure of carbon monoxide, iron pentacarbonyl alone promotes the conversion of iodobenzene to benzophenone and benzoic acid whereas dicobaltoctacarbonyl alone promotes a slow carbonylation to give solely benzoic acid.A synergetic effect is observed when the reaction is carried out in the presence of catalytic amounts of both carbonyl metals, and benzophenone can be isolated in more than 50percent yield.Under these conditions, o-iodotoluene affords the corresponding 2,2'-dimethylbenzophenone in 47percent isolated yield.
- Brunet, Jean-Jacques,Taillefer, Marc
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p. 193 - 197
(2007/10/02)
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- Reaction of Diazonium Salts with Transition Metals. Part 13. Palladium-catalyzed Carbonylative Coupling of Arenediazonium Salts with Organotin Reagents to give Aromatic Ketones
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Palladium-catalyzed reactions of arenediazonium salts (ArN2X; Ar=Y-Ph, Y=H, 2-, 3-, 4-Me, 2-Ph, 2-, 3-MeO, 2-, 3-, 4-Cl, 4-Br, 4-I, 2-, 3-, and 4-NO2, X=BF4 and PF6) with carbon monoxide and organostannanes (R4Sn, R=Me, Et, and Ph; RSnMe3, R=Ph, 2-, 3-, 4-MeC6H4, and 4-ClC6H4; RSnEt3, R=4-NO2C6H4; RSnBu3, R=Ph) gave aromatic ketones (ArCOR) in good yields (40-95percent) at room temperature.
- Kikukawa, Kiyoshi,Idemoto, Tohru,Katayama, Atsuhiko,Kono, Kiyoshi,Wada, Fumio,Matsuda, Tsutomu
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p. 1511 - 1514
(2007/10/02)
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- 9,24>METACYCLOPHANE-9-ENE, A "TWIN CYCLOPHANE", AND ITS DEHYDROGENATION PRODUCTS - SYNTHESIS, STRUCTURE DETERMINATION AND 1H-NMR-SPECTROSCOPY
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The synthesis of 9,24>metacyclophane-9-ene and of its dehydrogenation products, the new pyrenocyclophanes 8, 10, 11, and 12, is described; their structures are discussed in connection with their (1)H-NMR-spectra.
- Gruetzmacher, Hans-Fr,Husemann, Wolfram
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p. 2431 - 2434
(2007/10/02)
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- A NEW METHOD FOR THE PREPARATION OF SYMMETRICAL AROMATIC KETONES FROM AROMATIC CARBOXYLIC ACID
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Treatment of S-(2-pyridyl) aromatic thioates, readily derived from aromatic carboxylic acids, with bis(1,5-cyclooctadiene)nickel under mild conditions afforded symmetrical aromatic ketones in good yields.
- Goto, Toshio,Onaka, Makoto,Mukaiyama, Teruaki
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-