- Development of Trifluoromethanesulfonic Acid-Immobilized Nitrogen-Doped Carbon-Incarcerated Niobia Nanoparticle Catalysts for Friedel-Crafts Acylation
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Heterogeneous trifluoromethanesulfonic acid-immobilized nitrogen-doped carbon-incarcerated niobia nanoparticle catalysts (NCI-Nb-TfOH) that show excellent catalytic performance with low niobium loading (1 mol %) in Friedel-Crafts acylation have been developed. These catalysts exhibit higher activity and higher tolerance to catalytic poisons compared with the previously reported TfOH-treated NCI-Ti catalysts, leading to a broader substrate scope. The catalysts were characterized via spectroscopic and microscopic studies.
- Yang, Xi,Yasukawa, Tomohiro,Yamashita, Yasuhiro,Kobayashi, Shū
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p. 15800 - 15806
(2021/10/25)
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- Generation and reaction of alkyl radicals in open reaction vessels
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An operationally simple process to transform alkyl iodides into reactive alkyl radicals is described. Aryl diazonium salts react with Hantzsch esters and molecular oxygen to give aryl radicals, which participate in halogen atom transfers to give alkyl radicals. These intermediates react with a variety of acceptors. The reaction cascade occurs at room temperature, in open reaction vessels, with short reaction times. This journal is
- McErlean, Christopher S. P.,Tatunashvili, Elene
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supporting information
p. 7818 - 7821
(2020/11/02)
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- Ketide compounds, method for manufacturing, and use for treating diabetes thereof
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The present invention relates to ketide compounds, as well as ketide compounds. The present invention relates to a method for preparing a ketide compound, and a use thereof, in which various anti-diabetic TMPA derivative designs can be induced, and is effective in comparison with existing multi-stage synthesis. In addition, the ketide compounds according to the present invention have strong AMPMPK activity and are expected to be useful as a therapeutic agent for diabetes. (by machine translation)
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Paragraph 0078; 0178-0181; 0235-0237
(2019/08/27)
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- Acylation of anisole with carboxylic acids catalyzed by tungsten oxide supported on titanium dioxide
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Friedel-Crafts (F-C) acylation of anisole with octanoic acid was carried out on tungsten oxide (WO3) supported on various types of oxide supports. We have found that the highest activity was obtained when TiO2 was used as the support. WO3/TiO2 was found to be active in the acylation of anisole with carboxylic acids of varying alkyl chain lengths (C6–C10). It was possible to recycle the WO3/TiO2 catalyst for up to 5 times without deactivation. The turnover frequency (TOF) of the catalyst was closely correlated with the electronegativity of the cation of the support used for WO3. When a strong basic oxide such as CeO2 was used as a support, the acid strength of WO3 was diminished, while the strong acidity of WO3 was retained on a weak basic support like TiO2. This explains why the acid strength and consequently, the activity, were found to be the highest for the WO3/TiO2 catalyst. The trend of the catalytic performance was consistent with the order of acid strength of WO3 on different supports measured by temperature-programmed desorption of NH3.
- Okumura, Kazu,Iida, Masaki,Yamashita, Hajime
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- Pd-catalyzed Oxidative Cross-coupling of Alkyl Chromium(0) Fischer Carbene Complexes with Organoboronic Acids
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Alkyl chromium(0) carbene complexes have been explored as the cross-coupling partners in the palladium-catalyzed reaction with aryl or alkenyl boronic acids. This coupling reaction displays the versatile reactivities of alkyl chromium(0) carbenes under palladium catalysis. Mechanistically, this transformation is proposed to involve deprotonation of the alkyl chromium carbene substrate to generate a vinyl chromium anion intermediate that undergoes transmetalation to organopalladium species and reductive elimination.
- Wang, Kang,Yang, Jinghui,Yao, Xingqi,Wang, Jianbo
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supporting information
p. 3165 - 3168
(2018/10/15)
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- Catalytic Ring-Opening of Cyclic Alcohols Enabled by PCET Activation of Strong O-H Bonds
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We report a new photocatalytic protocol for the redox-neutral isomerization of cyclic alcohols to linear ketones via C-C bond scission. Mechanistic studies demonstrate that key alkoxy radical intermediates in this reaction are generated via the direct homolytic activation of alcohol O-H bonds in an unusual intramolecular PCET process, wherein the electron travels to a proximal radical cation in concert with proton transfer to a weak Br?nsted base. Effective bond strength considerations are shown to accurately forecast the feasibility of alkoxy radical generation with a given oxidant/base pair.
- Yayla, Hatice G.,Wang, Huaiju,Tarantino, Kyle T.,Orbe, Hudson S.,Knowles, Robert R.
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p. 10794 - 10797
(2016/09/09)
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- Synthesis of Ketones through Microwave Irradiation Promoted Metal-Free Alkylation of Aldehydes by Activation of C(sp3)-H Bond
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In this paper, a novel methodology for the synthesis of ketones via microwave irradiation promoted direct alkylation of aldehydes by activation of the inert C(sp3)-H bond has been developed. Notably, the reactions were accomplished under metal-free conditions and used commercially available aldehydes and cycloalkanes as substrates without prefunctionalization. By using this novel method, an alternative synthetic approach toward the key intermediates for the preparation of the pharmaceutically valuable oxaspiroketone derivatives was successfully established.
- Zhang, Xinying,Wang, Zhangxin,Fan, Xuesen,Wang, Jianji
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p. 10660 - 10667
(2015/11/18)
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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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- One-pot β-alkylation of secondary alcohols with primary alcohols catalyzed by ruthenacycles
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A ruthenacycle-catalyzed one-pot β-alkylation of secondary alcohols with primary alcohols is described. A survey of four C-N chelate ruthenacycles synthesized via the cyclometallation reaction of phenylmethanamine, N-methylphenylmethanamine, N,N-dimethylphenylmethanamine, and naphthalen-1-ylmethanamine with [(η6-C6H 6)RuCl2]2 was undertaken. All four complexes were found to be active with the phenylmethanamine-based ruthenacycle showing the best combination of reactivity and product selectivity among the four. An expanded scope of substrates was also studied with the inclusion of unsaturated primary alcohols. The reactivity trend observed gave insights into the role of hydrogen bonding in the catalytic mechanism involving transfer hydrogenation between the substrates and the transition metal catalyst.
- Chang, Xu,Chuan, Low Wei,Yongxin, Li,Pullarkat, Sumod A.
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experimental part
p. 1450 - 1455
(2012/04/10)
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- Friedel-crafts acylation of arenes with carboxylic acids using polystyrene-supported aluminum triflate
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Cross-linked polystyrene-supported aluminum triflate (Ps-Al(OTf) 3) has been shown to be a mild, efficient, and chemoselective heterogeneous Lewis acid catalyst for the acylation of aromatic compounds. The catalyst can be easily prepared from cheap starting materials, is stable (as a bench top catalyst) and is reusable.
- Boroujeni, Kaveh Parvanak,Parvanak, Kamran
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experimental part
p. 155 - 163
(2012/01/02)
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- Direct acylation of aryl chlorides with aldehydes by palladium-pyrrolidine Co-catalysis
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A palladium catalyst system has been developed that allows for the direct acylation of aryl chlorides with aldehydes. The choice of ligand, as well as the presence of pyrrolidine and molecular sieves is shown to be critical to the catalysis, which appears to proceed via an enamine intermediate. The reaction was successful for a wide range of aryl chlorides and tolerant of functionality on the aldehyde component, giving easy access to alkyl aryl ketones in modest to good yields.
- Colbon, Paul,Ruan, Jiwu,Purdie, Mark,Xiao, Jianliang
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supporting information; experimental part
p. 3670 - 3673
(2010/10/20)
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- Palladium(0) nanoparticle-catalyzed sp2 C-H activation: A convenient route to alkyl-aryl ketones by direct acylation of aryl bromides and iodides with aldehydes
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Palladium(0) nanoparticles efficiently catalyze aliphatic aldehyde C-H functionalization by aryl halides to produce alkyl-aryl ketones in good yields. A wide range of substituted aryl and hetero-aryl bromides/iodides and open-chain aldehydes of varied chain length participated in this reaction.
- Adak, Laksmikanta,Bhadra, Sukalyan,Ranu, Brindaban C.
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experimental part
p. 3811 - 3814
(2010/08/19)
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- Friedel-Crafts acylation of arenes with carboxylic acids using silica gel supported AlCl3
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Aromatic compounds react smoothly with carboxylic acids in the presence of silica gel supported aluminium trichloride to afford the corresponding ketones with high regioselectivity in high to excellent yields. The catalyst is stable (as a bench top catalyst) and can be easily recovered and reused without appreciable change in its efficiency. tuebitak.
- Parvanak Boroujeni, Kaveh
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experimental part
p. 621 - 630
(2010/11/04)
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- Direct acylation of aryl bromides with aldehydes by palladium catalysis
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A new protocol for the direct acylation of aryl bromides with aldehydes is established. It appears to involve palladium-amine cooperative catalysis, affording synthetically important alkyl aryl ketones in moderate to excellent yields in a straightforward manner, and broadening the scope of metal-catalyzed coupling reactions. Copyright
- Ruan, Jiwu,Saidi, Ourida,Iggo, Jonathan A.,Xiao, Jianliang
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supporting information; experimental part
p. 10510 - 10511
(2009/02/05)
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- Novel, potent THC/anandamide (hybrid) analogs
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The structure-activity relationship (SAR) of the end pentyl chain in anandamide (AEA) has been established to be very similar to that of Δ9-tetrahydrocannabinol (Δ9-THC). In order to broaden our understanding of the structural similarities between AEA and THC, hybrid structures 1-3 were designed. In these hybrids the aromatic ring of THC-DMH was linked to the AEA moiety through an ether linkage with the oxygen of the phenol of THC. Hybrid 1 (O-2220) was found to have very high binding affinity to CB1 receptors (Ki = 8.5 nM), and it is interesting to note that the orientation of the side chain with respect to the oxygen in the phenol is the same as in THCs. To further explore the SAR in this series the terminal carbon of the side chain was modified by adding different substituents. Several such analogs were synthesized and tested for their CB1 and CB2 binding affinities and in vivo activity (tetrad tests). The details of the synthesis and the biological activity of these compounds are described.
- Bourne, Caryl,Roy, Sucharita,Wiley, Jenny L.,Martin, Billy R.,Thomas, Brian F.,Mahadevan, Anu,Razdan, Raj K.
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p. 7850 - 7864
(2008/04/12)
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- Friedel-Crafts acylation reaction using carboxylic acids as acylating agents
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Dehydrative Friedel-Crafts acylation reaction of aromatic compounds with carboxylic acids as acylating agents was investigated in the presence of Lewis acid- or Br?nsted acid-catalyst. Various metal triflates and bis(trifluoromethanesulfonyl)amides showed catalytic activity at high temperature, among which Eu(NTf2)3 proved to be the most effective and efficiently catalyzed the acylation reaction of alkyl- and alkoxybenzenes with aliphatic and aromatic carboxylic acids at 250 °C. Bi(NTf2)3 was more effective than Eu(NTf2)3 at lower temperature, but proved to be hydrolyzed in the presence of a small amount of water to give HNTf2 and [Bi6O4(OH)4(H2O)6](NTf2)6. The structure of the latter compound was confirmed by a single crystal X-ray analysis. Among five Br?nsted acids, HOTf, HNTf2, HCTf3, TsOH, and Nafion SAC-13, HNTf2 has proved to be the most efficient catalyst and more effective than Eu(NTf2)3 for the acylation of p-xylene with heptanoic acid at 220 °C or lower temperature. HNTf2 catalyzed the acylation of anisole with carboxylic acids in high yields in refluxing toluene with azeotropic removal of water.
- Kawamura, Masato,Cui, Dong-Mei,Shimada, Shigeru
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p. 9201 - 9209
(2007/10/03)
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- Recyclable self-assembly-supported catalyst for chelation-assisted hydroacylation of an olefin with a primary alcohol
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A novel recyclable catalyst for chelation-assisted hydroacylation of an olefin with a primary alcohol was developed by utilizing a hydrogen-bonding self-assembly motif consisting of a barbiturate bearing 2-aminopyridin-4-yl group and 5-hexyl-2,4,6-triaminopyrimidine. This was further applied to a mixed catalyst system to recycle both organic and organometallic catalysts.
- Kim, Do-Won,Lim, Sung-Gon,Jun, Chul-Ho
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p. 2937 - 2940
(2007/10/03)
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- Preparation of ketones from nitriles and phosphoranes
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The preparation of a ketone from a phosphorane and a nitrile is described. The workup conditions are mild, and the yields are high. The unreacted starting materials can easily be recovered.
- Taber, Douglass F.,Cai, Lisi
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p. 4887 - 4888
(2007/10/03)
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- Selective iron-catalyzed cross-coupling reactions of Grignard reagents with enol triflates, acid chlorides, and dichloroarenes
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Cheap, readily available, air stable, nontoxic, and environmentally benign iron salts such as Fe(acac)3 are excellent precatalysts for the cross-coupling of Grignard reagents with alkenyl triflates and acid chlorides. Moreover, it is shown that dichloroarene and -heteroarene derivatives as the substrates can be selectively monoalkylated by this method. All cross-coupling reactions proceed very rapidly under notably mild conditions and turned out to be compatible with a variety of functional groups in both reaction partners. A detailed analysis of the preparative results suggests that iron-catalyzed C-C bond formations can occur via different pathways. Thus, it is likely that reactions of methylmagnesium halides involve iron-ate complexes as the active components, whereas reactions of Grignard reagents with two or more carbon atoms are effected by highly reduced iron-clusters of the formal composition [Fe(MgX)2]n generated in situ. Control experiments using the ate-complex [Me4Fe]Li2 corroborate this interpretation.
- Scheiper, Bodo,Bonnekessel, Melanie,Krause, Helga,Fuerstner, Alois
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p. 3943 - 3949
(2007/10/03)
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- A New Solvent System for Recycling Catalysts for Chelation-Assisted Hydroacylation of Olefins with Primary Alcohols
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A new method to separate and reuse the catalyst system consisting of a rhodium complex and 2-aminopyridines for chelation-assisted hydroacylation was achieved using phenol and 4,4′-dipyridyl as the reaction medium, and 4-diphenylphosphinobenzoic acid as a ligand. Copyright
- Chang, Duck-Ho,Lee, Dae-Yon,Hong, Boo-Sun,Choi, Jun-Hack,Jun, Chul-Ho
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p. 424 - 425
(2007/10/03)
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- Lewis acid-catalyzed Friedel-Crafts acylation reaction using carboxylic acids as acylating agents
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Rare-earth metal Lewis acids, in particular Eu(NTf2) 3, were found to be efficient catalysts for Friedel-Crafts acylation reaction using aliphatic as well as aromatic carboxylic acids as acylating agents at high temperature.
- Kawamura, Masato,Cui, Dong-Mei,Hayashi, Teruyuki,Shimada, Shigeru
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p. 7715 - 7717
(2007/10/03)
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- Direct conversion of benzyl alcohol to ketone by polymer-supported Rh catalyst
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Benzyl alcohol reacted with 1-alkene to give the corresponding ketone by in situ generated polystyrene-based rhodium catalyst. The catalytic activity of this polymer-supported rhodium catalyst has not been reduced after reusing it four times.
- Jun, Chul-Ho,Hong, Hye-Suk,Huh, Chan-Woo
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p. 8897 - 8900
(2007/10/03)
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- Process for producing acylaromatic compounds
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Acylaromatic compounds STR1 (Q: aromatic compound residue; R: straight, branched or cyclic aliphatic group, aromatic group or araliphatic group) are prepared in high yield by a reaction, in the presence of a boron trifluoride complex catalyst, of an aromatic compound with STR2 (X: H, Cl, Br; Y: Cl, Br) or with RCOOH in the presence of (XYCHCO)2 O.
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- DIMETHYLALUMINIUM METHANESELENOLATE - A USEFUL REAGENT FOR THE PREPARATION OF SELENOESTERS. A NEW FRIEDEL-CRAFTS ACYLATION PROCEDURE PROMOTED BY Cu(I)
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The preparation of a new aluminium reagent, dimethylaluminium methaneselenolate (Me2AlSeMe) is described.The reactivity of this aluminium reagent toward a variety of organic substrates has been studied.Me2AlSeMe will convert O-alkyl esters to selenoesters in high yield.These selenoesters function as extremely reactive acyl transfer agents and are converted to acids, esters, and amides on reaction with water, alcohols or amines in the presence of a selenophilic metal cation.The selenoesters will, moreover, acylate reactive arenes and heterocyclic compounds when cuprous triflate is employed as the selenophilic metal cation.This latter transformation constitutes a new transition metal promoted variant of the Friedel-Crafts acylation reaction.
- Kozikowski, Alan P.,Ames, Anthony
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p. 4821 - 4834
(2007/10/02)
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