- A Convenient Palladium-Catalyzed Carbonylative Suzuki Coupling of Aryl Halides with Formic Acid as the Carbon Monoxide Source
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A practical palladium-catalyzed carbonylative Suzuki coupling of aryl halides under carbon monoxide gas-free conditions has been developed. Here, formic acid was utilized as the carbon monoxide source for the first time with acetic anhydride as the additive. A variety of diarylketones were produced in moderate to excellent yields from the corresponding aryl halides and arylboronic acids.
- Qi, Xinxin,Jiang, Li-Bing,Li, Hao-Peng,Wu, Xiao-Feng
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- Phosphine-free cross-coupling reaction of arylboronic acids with carboxylic anhydrides or acyl chlorides in aqueous media
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The palladium acetate-catalyzed coupling reaction of aryl boronic acid with carboxylic anhydride or acyl chloride was carried out smoothly in water in the presence of poly(ethylene glycol) (PEG) or 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) to give high yields of ketones without the use of phosphine ligands. The Pd(OAc)2-H 2O-[bmim][PF6] catalytic system can be recovered and reused eight times with high efficiency for both carboxylic anhydride and acyl chloride.
- Xin, Bingwei,Zhang, Yuhong,Cheng, Kai
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- Convenient Stille carbonylative cross-couplings using molybdenum hexacarbonyl
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Palladium catalysis was used in Stille-type carbonylative cross-couplings employing Mo(CO)6 as the carbon monoxide source. Robust and convenient transformations were carried out in closed vessels at 100 °C, providing a set of diaryl ketones in good yields. Aryl triflates and bromides were used as coupling partners with aryl stannanes. Inclusion of the Mo(CO)6 destabilizing agent DBU made this protocol operationally simple and suppressed side-product formation.
- Lindh, Jonas,Fardost, Ashkan,Almeida, Maria,Nilsson, Peter
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- Synthesis and structural characterization of Pd(II) thiosemicarbazonato complex: Catalytic evaluation in synthesis of diaryl ketones from aryl aldehydes and arylboronic acids
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A simple route to synthesize triphenylphosphinopalladium(II) thiosemicarbazonato complex has been described. Elemental analysis, spectral (IR, NMR) and single crystal X-ray diffraction techniques were employed for the complete characterization of the complex. The latter was found to be effective catalyst for carbon–carbon cross-coupling reaction of aryl- and heteroarylboronic acids with aromatic and heteroaromatic aldehydes to form the corresponding diaryl ketones. The influence of reaction parameters such as solvent, base, reaction temperature and catalyst loading was also investigated.
- Prabhu, Rupesh Narayana,Ramesh, Rengan
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- Substituent modulation of mild fluorination of aromatic molecules with caesium fluoroxysulphate
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Functionalization of mono- and di-substituted benzene derivative with CsSO4F has been modulated by substituents on the benzene ring. α-Hydroxyalkylbenzenes, with a deactivated ring, were oxidized to phenones, while fluorodealkylation was achieved in high yield when electron-donating groups were present in a para position. Electron-withdrawing substituents favoured chain fluorofunctionalization in alkylbenzenes, while ring fluorination was found exclusively in acylamino-derivatized alkylbenzenes; fluoro-addition products were formed in the case of p-alkoxy-substituted alkylbenzene derivatives.
- Stavber, Stojan,Planinsek, Zdenka,Kosir, Iztok,Zupan, Marko
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- Direct preparation of arylmanganese bromides using active manganese
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Arylmanganese compounds were easily prepared via the direct oxidative addition of Rieke manganese to aryl bromides under mild conditions. The resulting organomanganese reagents undergo coupling reaction with acid chlorides to give the corresponding ketones in moderate yields.
- Kim, Seung-Hoi,Rieke, Reuben D.
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- Pd(II)-Catalyzed decarboxylative cross-coupling of potassium aryltrifluoroborates with α-oxocarboxylic acids at room temperature
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A novel Pd-catalyzed decarboxylative cross-coupling of potassium aryltrifluoroborates with R-oxocarboxylic acids is performed at room temperature. This reaction provides an efficient access to aryl ketones under mild conditions.
- Li, Mingzong,Wang, Cong,Ge, Haibo
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- Isinglass–palladium as collagen peptide–metal complex: a highly efficient heterogeneous biocatalyst for Suzuki cross-coupling reaction in water
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The class of bio-nanocatalysts (BNCs) is an evolving innovation that synergistically assimilates advanced nanotechnology with biotechnology. BNCs promote green processes due to their low consumption of chemicals and the absence of toxic by-products. Isinglass (IG), from the Dutch huizenblaas (sturgeon bladder), containing approximately 98% protein collagen, is used to support the immobilization of palladium (Pd) nanoparticles. This process leads to Pd/IG composite, a new class of heterogeneous collagen peptides–metal BNCs that exhibit high catalytic activity and reusability for ligand-free Suzuki coupling reaction in water. Additionally, these BNCs are obviously active in the cross-coupling reaction between acid chloride and arylboronic acid, producing a high yield of the desired ketones. The synthesized BNCs are well-characterized by Fourier transform infrared spectroscopy, field emission scanning electron microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma, and transmission electron microscopy.
- Dolatkhah, Zahra,Javanshir, Shahrzad,Bazgir, Ayoob
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- Pd-catalyzed synthesis of functionalized arylketones from boronic acids and carboxylic acids activated in situ with dimethyl dicarbonate
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Highly efficient catalyst systems were developed that allow the palladium-catalyzed cross-coupling of arylboronic acids with carboxylic acids activated in situ with dimethyl dicarbonate at room temperature. As byproducts, only methanol, CO2, an
- Goo?en, Lukas J.,Winkel, Lars,D?hring, Arno,Ghosh, Keya,Paetzold, Jens
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- Synthesis of aryl ketones by cross-coupling reaction of arylboronic acids with carboxylic anhydrides in aqueous phase
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A highly efficient aqueous system of PdCl2-catalyzed cross-coupling reaction of arylboronic acid with carboxylic anhydride (Suzuki-type reaction) without the use of phosphine ligands was developed. The reactions went smoothly in acetone/H2O phase to give good yields of aryl ketones in short reaction times (1-3 h) at room temperature in air and were unaffected by the presence of electron-releasing and electron-withdrawing substituents in both the arylboronic acids and carboxylic anhydrides. Copyright Taylor & Francis Group, LLC.
- Xin, Bing-Wei
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- Carbonylative Hiyama coupling of aryl halides with arylsilanes under balloon pressure of CO
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An efficient protocol has been developed for the carbonylative Hiyama coupling of aryl halides using the cesium fluoride as a promoter by palladium-catalyzed in NMP. This protocol was applied to a wide variety of functionalized and hindered aryl iodides and bromides with arylsilanes, to afford the desired biaryl ketones in good to excellent yields.
- Chang, Sheng,Jin, Ying,Zhang, Xiu Rong,Sun, Yong Bing
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- Biaryl Ketones by Suzuki–Miyaura Cross-Coupling of Organotrifluoroborates and Acyl Chlorides
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A procedure for the synthesis of biaryl ketones by a palladium-catalyzed Suzuki–Miyaura cross-coupling reaction between phenyltrifluoroborates and benzoyl chlorides is described. Organotrifluoroborates are unique to other cross-coupling reagents as they have a high functional-group tolerance and are moisture-stable. Moderate to excellent yields were obtained for all substrates tested.
- Forbes, Alaina M.,Meier, G. Patrick,Jones-Mensah, Ebenezer,Magolan, Jakob
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- Copper-catalyzed aerobic synthesis of bisaryl ketones from alkynes via the cleavage of C-C triple bonds
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A novel copper-catalyzed aerobic synthesis of bisaryl ketones from 1,2-diarylalkynes via the cleavage of C-C triple bonds is reported. This reaction is a new transformation of 1,2-diarylalkynes into bisaryl ketones.
- Gu, Lijun,Zhang, Hongtao
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- Multiwalled Carbon Nanotubes Supported Pd(II)-Salen Complex: An Effective, Phosphorous-Free, and Reusable Heterogeneous Precatalyst for the Synthesis of Diaryl Ketones
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The Suzuki–Miyaura cross-coupling reaction of aroyl chlorides and arylboronic acids has been carried out efficiently in the presence of Pd(II)-salen@MWCNTs as an air-moisture stable precatalyst. The influence of various parameters, such as solvent, temperature, and base on the reaction system, was studied. Furthermore, the catalyst can be easily recovered quantitatively by a simple filtration and reused for three consecutive runs without significant loss of its activity.
- Mohammadi, Elmira,Hajilou, Zahra,Movassagh, Barahman
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- Palladacycle-catalyzed cross-coupling reactions of arylboronic acids with carboxylic anhydrides or acyl chlorides
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The triphenylphosphine-cyclopalladated ferrocenylimine (Cat. 2) exhibited highly catalytic activity for the both of arylboronic acids with carboxylic anhydrides and acyl chlorides with low catalyst loading (0.5 mol %). The reactions were unaffected by the presence of electron-releasing and electron-withdrawing substituents in both the arylboronic acids and carboxylic derivatives. Up to 98% yield was obtained for 32 examples. However, they were limited for arylboronic acid with strong electron-withdrawing groups. It is noting that catalyst 2 can be reused for eight times without losing its catalytic activity.
- Yu, Ajuan,Shen, Lei,Cui, Xiuling,Peng, Dongpo,Wu, Yangjie
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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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- Novelmeta-benzothiazole and benzimidazole functionalised POCOP-Ni(ii) pincer complexes as efficient catalysts in the production of diarylketones
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The synthesis of four novel non-symmetric Ni(ii)-POCOP pincer complexesmeta-functionalized with either benzothiazole or benzimidazole at the central aryl ring is described. All complexes were fully characterised in solution by various analytical techniques and the molecular structures in the solid state of complexes1b,2aand2bwere unequivocally determined by single crystal X-ray diffraction analysis. In addition, the Ni(ii)-POCOP pincer complexes were efficiently used as catalysts in the synthesis of diarylketones by cross-coupling reactions of functionalized benzaldehydes and boronic acid derivatives under relatively mild conditions. An important aspect of this transformation is the dependence on the steric properties of the donor groups (OPR2) of the pincer ligands, the more active compounds having the phosphinitos bearing isopropyl groups (1aand2a) than those containingtert-butyl substituents (1band2b).
- Castillo-García, Antonio A.,González-Sebastián, Lucero,Lomas-Romero, Leticia,Hernandez-Ortega, Simon,Toscano, Ruben A.,Morales-Morales, David
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- Palladium-catalyzed Suzuki-Miyaura coupling of amides by carbon-nitrogen cleavage: General strategy for amide N-C bond activation
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The first palladium-catalyzed Suzuki-Miyaura cross-coupling of amides with boronic acids for the synthesis of ketones by sterically-controlled N-C bond activation is reported. The transformation is characterized by operational simplicity using bench-stable, commercial reagents and catalysts, and a broad substrate scope, including substrates with electron-donating and withdrawing groups on both coupling partners, steric-hindrance, heterocycles, halides, esters and ketones. The scope and limitations are presented in the synthesis of >60 functionalized ketones. Mechanistic studies provide insight into the catalytic cycle of the cross-coupling, including the first experimental evidence for Pd insertion into the amide N-C bond. The synthetic utility is showcased by a gram-scale cross-coupling and cross-coupling at room temperature. Most importantly, this process provides a blueprint for the development of a plethora of metal catalyzed reactions of typically inert amide bonds via acyl-metal intermediates. A unified strategy for amide bond activation to enable metal insertion into N-C amide bond is outlined (Scheme 1).
- Meng, Guangrong,Szostak, Michal
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- Photoinduced Radical Cleavage of Iodobenzophenones
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The triplet state cleavage of m-iodo-(mibp) and p-iodobenzophenone (pIBP) to benzoylphenyl and iodine radicals has been studied by both steady state and laser flash techniques.Phosphorescence spectra in methanol/ ethanol glasses at 77 K indicate triplet energies of 68.4 and 67.8 kcal/mol for mIBP and pIBP, respectively.In most organic solvents products are benzophenone and iodinated solvents; these are formed by hydrogen abstraction from solvent by the initially formed benzoylphenyl radicals.Quantum yields for product formation decrease with increasing solvent viscosity, ranging from 0.45 in acetonitrile to 0.28 in cyclopentane and 0.05 in cyclooctane; they appear to reflect significant in-cage recoupling of the initial radical pairs.Quenching of the reaction by naphthalene indicates 25 degC triplet lifetimes of 25 and 0.2 ns for mIBP and pIBP, respectively, which were confirmed by flash kinetics.Laser excitation produced transient signals assigned to the iodine atom-toluene complex (in toluene) and, for mIBP, the triplet ketone.Decay of the latter revealed activation parameters ΔH = 4.0 +/- 0.2 kcal/mol and log A = 10.6 +/- 0.2 for mIBP in both methanol and toluene.The strong phosphorescence of both ketones at 77 K indicates that ΔH for pIBP must be >= 3kcal/mol, such that log A is ca. 12, much higher than for mIBP.The different rates and A values reflect different ?* spin densities at the meta and para positions in the lowest n,?* triplets, which react either by mixing with dissociative ?,?* states or by thermally converting into a dissociative ?,?* or ?1,?* state.The dependence of ?* spin density and the low A values strongly suggest an inefficient state interconversion at a surface crossing between n,?* and ?,?* states, because of their different symmetries.It is suggested that the low A values, which might indicate negative Δs values, are better understood as low transmission coefficients.
- Wagner, Peter J.,Waite, Carol I.
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- Triphenylphosphinopalladium(II) complexes with ONO-donor ligands: syntheses, structures and catalytic applications in C?C cross-coupling reactions
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Reactions of 1-((2-hydroxy-5-R-phenylimino)methyl)naphthalen-2-ols (H2Ln, n?=?1–3 for R?=?H, Me, Cl, respectively) with [Pd(PPh3)2Cl2] and Et3N in toluene under reflux produced three new mononuclear square-planar palladium(II) complexes with the general formula [Pd(Ln)(PPh3)] (1, R?=?H; 2, R?=?Me; 3, R?=?Cl). All the complexes were characterized using elemental analysis, solution conductivity and various spectroscopic (infrared, UV–visible and NMR) measurements. Molecular structures of 1, 2, 3 were confirmed using single-crystal X-ray diffraction analysis. In each complex, the fused 5,6-membered chelate rings forming phenolate-O, azomethine-N and naphtholate-O donor (Ln)2? and the PPh3 form a square-planar ONOP coordination environment around the metal centre. Infrared and NMR spectroscopic features of 1, 2, 3 are consistent with their molecular structures. Electronic spectra of the three complexes display several strong primarily ligand-centred absorption bands in the range 322–476?nm. All the complexes were found to be effective catalysts for carbon–carbon cross-coupling reactions of arylboronic acids with aromatic and heteroaromatic aldehydes to form the corresponding diaryl ketones. Copyright
- Prabhu, Rupesh Narayana,Babu, G. Narendra,Pal, Samudranil
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- Palladium on magnetic Irish moss: A new nano-biocatalyst for suzuki type cross-coupling reactions
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A novel heterogeneous magnetic palladium nano-biocatalyst was designed by utilizing Irish moss, a family of sulfated polysaccharides extracted from algae, as a natural biopolymer. This magnetic Irish moss decorated with palladium (Pd–Fe3O4@IM) to form a biomagnetic catalytic system was synthesized and well characterized by FT–IR analysis, X-ray powder diffraction, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, atomic absorption spectroscopy and transmission electron microscopy. The catalyst was stable to air and moisture and displayed high catalytic activity in ligand-free Suzuki–Miyaura cross-coupling reactions conducted under green chemistry reaction conditions. The aromatic ketones are produced by the cross-coupling reaction between acid chlorides and aryl boronic acid derivatives in high yields.
- Dolatkhah, Zahra,Javanshir, Shahrzad,Bazgir, Ayoub,Hemmati, Behnaz
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- Tetraethylammonium iodide catalyzed synthesis of diaryl ketones via the merger of cleavage of C-C double bonds and recombination of aromatic groups
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An efficient method for synthesizing diaryl ketones via merging of oxidative cleavage of C-C double bonds and recombination of aromatic groups is developed with Et4NI (2.5 mol%) as the catalyst and NaIO4 as the oxidant. The control experiments provide valuable mechanistic insights into the formation of diaryl ketones, and suggest that NaIO4 serves as an epoxidation and nucleophilic deformylation reagent.
- Zeng, Xianghua,Xu, Daqian,Miao, Chengxia,Xia, Chungu,Sun, Wei
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- A new convenient procedure to prepare organomanganese reagents from organic halides and activated manganese
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A new method to obtain activated manganese metal, especially attractive for large scale preparative organic chemistry, is described. The key point is the use of 2-phenylpyridine as electron carrier to reduce manganese chloride by lithium. The active manganese thus obtained was used to prepare various organomanganese reagents from organic halides. The reactivity of these reagents has been studied (acylation, 1,2- or 1,4-addition, alkylation and alkenylation).
- Cahiez, Gerard,Martin, Arnaud,Delacroix, Thomas
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- Carbonylative coupling of aryl tosylates/triflates with arylboronic acids under CO atmosphere
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The carbonylative Suzuki-Miyaura reaction between aryl tosylates/triflates with arylboronic acid is herein reported, using base-free conditions and a balloon pressure of carbon monoxide. Under these conditions, unsymmetrical biaryl ketones were obtained in modest to excellent yields. This method was adapted to the synthesis of oxybenzone and ketoprofen in good yields under mild conditions.
- Hao, Cheng Yi,Wang, Dan,Li, Ya Wei,Dong, Lin Lin,Jin, Ying,Zhang, Xiu Rong,Zhu, He Yun,Chang, Sheng
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- Ultrasound-assisted synthesis of benzophenones by Stille cross-coupling reactions. Optimization via experimental design
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A series of diaryl ketones have been synthesized in moderate to excellent yields through the selective cross-coupling reaction of benzoyl chlorides with arylstannanes using a sonochemical variation of the Stille coupling. Ultrasound significantly enhances this useful organometallic transformation affording the desired products in higher yields and shorter reaction times than conventional reactions. The scope of the protocol has been explored with a selection of arylstannanes and different aroyl chlorides as reaction partners. Remarkably, no by-products resulting from homo-coupling could be detected. The ultrasound-promoted cross-coupling reaction was optimized through experimental design.
- Luong, Martín,Domini, Claudia E.,Silbestri, Gustavo F.,Chopa, Alicia B.
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- Ni-Catalyzed Reductive Cross-Coupling of Amides with Aryl Iodide Electrophiles via C-N Bond Activation
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A Ni-catalyzed reductive cross-coupling reaction between two electrophiles, amides and aryl iodides, has been developed. This work is the first example using amide as an electrophile to couple with another electrophile, instead of using highly basic and pyrophoric nucleophiles. Furthermore, the Ni catalyst chemoselectively inserting the C-N bond of amide triggered the reductive cross-coupling reaction, which solves the problem that the Ni catalyst preferentially inserts the more reactive C-I bond to form a self-coupling product.
- Ni, Shengyang,Zhang, Wenzhong,Mei, Haibo,Han, Jianlin,Pan, Yi
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- Fe-S Catalyst Generated in Situ from Fe(III)- And S3?--Promoted Aerobic Oxidation of Terminal Alkenes
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An iron-sulfur complex formed by the simple mixture of FeCl3 with S3?- generated in situ from K2S is developed and applied to selective aerobic oxidation of terminal alkenes. The reaction was carried out under an atmosphere of O2 (balloon) and could proceed on a gram scale, expanding the application of S3?- in organic synthesis. This study also encourages us to explore the application of an Fe-S catalyst in organic reactions.
- Ai, Jing-Jing,Huang, Cheng-Mi,Li, Jian,Liu, Bei-Bei,Rao, Weidong,Wang, Fei,Wang, Shun-Yi
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- Chloroindate(III) ionic liquids: Recyclable media for Friedel-Crafts acylation reactions
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Chloroindate(III) ionic liquids are versatile reaction media for Friedel-Crafts acylation reactions; the system is catalytic and totally recyclable, using an aqueous workup, with no leaching of the indium into the product phase. The Royal Society of Chemistry 2005.
- Earle, Martyn J.,Hakala, Ullastiina,Hardacre, Christopher,Karkkainen, Johanna,McAuley, Barry J.,Rooney, David W.,Seddon, Kenneth R.,Thompson, Julian M.,Waehaelae, Kristina
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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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- Microwave promoted Suzuki reactions between aroyl chlorides and boronic acids catalyzed by heterogeneous and homogeneous phosphine-free palladium catalysts
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Suzuki cross-coupling reactions between arylboronic acids and aroyl chlorides with phosphine-free palladium catalysis under microwave irradiation were performed to obtainment of aromatic ketones in good yields within short times. Heterogeneous and homogeneous catalysts were studied as well as their influence in the reaction selectivity relative to homocoupling of the boronic acids.
- De Luna Martins, Daniela,Aguiar, Lúcia C.S.,Antunes, Octavio A.C.
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- Efficient synthetic route to bisaryl ketones via copper-catalyzed C-C triple bonds cleavage
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An efficient copper-catalyzed aerobic synthesis of bisaryl ketones from 1,2-diarylalkynes via C-C triple bonds cleavage has been demonstrated. The aniline compounds were found to be crucial in our conditions and a plausible mechanism was put forward. This reaction constitutes a new transformation from 1,2-diarylalkynes into bisaryl ketones with a practical, neutral, and mild synthetic approach.
- Li, Xiangguang,Huang, Wenzhong,Liang, Deqiang,Yuan, Lin,Ma, Yinhai,Gu, Lijun
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- An efficient and recyclable thermoregulated phosphine-palladium catalyst for the carbonylative Suzuki coupling of aryl halides with arylboronic acids in water
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An efficient protocol has been developed for the carbonylative Suzuki coupling of aryl halides using the thermoregulated phosphine-palladium as a reusable catalyst in pure water. This protocol was applied to a wide variety of hindered and functionalized aryl iodides and bromides with arylboronic acids, to afford the desired biaryl ketones in good to high yields. The palladium catalyst was easily recovered in the aqueous phase and reused up to eight cycles without a significant decrease in its activity.
- Hao, Yuanping,Jiang, Jingyang,Wang, Yanhua,Jin, Zilin
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- Synthesis and application of SBA-Pr-Py@Pd in Suzuki-type cross-coupling reaction
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SBA-Pr-Py was synthesized by functionalization of SBA-15 with 4-pyridine carbaldehyde, and then it was grafted by palladium ions to give SBA-Pr-Py@Pd nanocatalyst, which was used in cross-coupling reaction. In this process, aryl boronic acid is treated with various acyl halides using SBA-Pr-Py@Pd catalyst to provide aryl ketones under mild conditions. Graphical abstract: [Figure not available: see fulltext.].
- Mohammadi Ziarani, Ghodsi,Ebrahimi, Zahra,Mohajer, Fatemeh,Badiei, Alireza
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- Supported Palladium-Catalyzed Carbonylative Synthesis of Diaryl Ketones from Aryl Bromides and Arylboronic Acids
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A palladium supported on graphitic carbon nitride (Pd/g-C3N4) catalyzed carbonylative reaction of aryl bromides and arylboronic acids by has been developed for the construction of diaryl ketones. Using benzene-1,3,5-triyl triformate (TFBen) as the CO source, the reaction proceeded well to give various diaryl ketones in moderate to good yields.
- Xu, Tiefeng,Wang, Qi,Yang, Zeyi,Yi, Lili,Wang, Jian-Shu,Lu, Wangyang,Ying, Jun,Wu, Xiao-Feng
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- Ag(i)/persulfate-catalyzed decarboxylative coupling of α-oxocarboxylates with organotrifluoroborates in water under room temperature
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The decarboxylative coupling reaction of α-oxocarboxylates and organotrifluoroborates was carried out smoothly in the presence of catalytic AgNO3 using K2S2O8 as oxidant to generate diarylketone products in high
- Chang, Sheng,Wang, Jian Feng,Dong, Lin Lin,Wang, Dan,Feng, Bo,Shi, Yuan Tai
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- Copper/palladium-cocatalyzed aerobic synthesis of bisaryl ketones from Olefins via C-C double bonds cleavage
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A novel palladium/copper-catalyzed aerobic synthesis of bisaryl ketones from 1,2-diarylalkenes via C-C double bonds cleavage has been described. This reaction constitutes a new transformation from 1,2-diarylalkenes into bisaryl ketones, providing a unifying, simple and environmentally friendly complement to the available methods.
- Gu, Lijun,Liu, Jiyan,Zhang, Hongtao
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- Ligand-free Pd/Cu-catalyzed decarboxylative coupling of aryl iodides with α-oxocarboxylates
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This paper describes a palladium/copper-catalyzed decarboxylative coupling of aryl iodides with α-oxocarboxylates. The cross-coupling reaction gives high chemical yields of aryl ketones and has wide functional group tolerance, making the transformation an attractive alternative to the traditional cross-coupling approaches for aryl ketones. Copyright
- Ji, Yongfeng,Yang, Xiaomin,Mao, Weixi
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- Nickel-catalyzed diaryl ketone synthesis by N-C cleavage: Direct negishi cross-coupling of primary amides by site-selective N,N-Di-boc activation
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A general Negishi acylation of primary amides enabled by a combination of site-selective N,N-di-Boc activation and nickel catalysis is reported for the first time. The reaction is promoted by a bench-stable, inexpensive Ni catalyst. The reaction shows excellent functional group compatibility, affording functionalized diaryl ketones by selective N-C cleavage. Most notably, this protocol represents the first amide cross-coupling by direct metal insertion of simple and readily available primary amides. The overall strategy by N,N-di-Boc activation/metal insertion is suitable for a broad range of coupling protocols via acylmetals. Mechanistic experiments suggest high reactivity of N,N-di-Boc activated 1° amides in direct amide C-N cross-couplings.
- Shi, Shicheng,Szostak, Michal
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- Carbonylative Suzuki cross-coupling reaction catalyzed by bimetallic Pd-Pt nanodendrites under ambient CO pressure
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Pd-catalyzed reactions between aryl boronic acids and aryl halides have undergone rapid development since the pioneering work of Suzuki and co-workers in 1979. In this paper, we described a high-efficient and cost-effective bimetallic Pd-Pt nanodendrites catalyst based on a ligand-free strategy to synthesize diaryl ketones via CO direct insertion to boronic acids and aryl halides. A variety of aryl boronic acids and aryl halides were investigated, which showed great functional group tolerance and versatile aryl ketone products in high yield.
- Wang, Zheng-Jun,Wang, Xue-Yan,Wang, Xia,Liang, Zhi-Wu,Xu, Xinhua
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- Mechanochemical Solvent-Free Suzuki–Miyaura Cross-Coupling of Amides via Highly Chemoselective N?C Cleavage
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Although cross-coupling reactions of amides by selective N?C cleavage are one of the most powerful and burgeoning areas in organic synthesis due to the ubiquity of amide bonds, the development of mechanochemical, solid-state methods remains a major challe
- Ma, Yangmin,Shao, Lei,Szostak, Michal,Wang, Ruihong,Zhang, Jin,Zhang, Pei
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supporting information
(2022/01/04)
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- AIBN initiated functionalization of the benzylic sp3 C[sbnd]H and C[sbnd]C bonds in the presence of dioxygen
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A sp3 C[sbnd]H bond functionalization and C[sbnd]C bond cleavage were realized by AIBN/O2 catalyst system, providing a series of benzophenones under mild reaction conditions. The mechanistic study shows that a peroxide intermediate is involved in this transformation, and in the case of diphenylmethanes, the sp3 C[sbnd]C bond is cleaved through the peroxide rearrangement, which might provides a new way to cleave relatively strong C[sbnd]C bond and be applied to more general C[sbnd]C bond activation.
- Hu, Yingying,Shao, Yu,Zhang, Shuwei,Yuan, Yuan,Sun, Zheng,Yuan, Yu,Jia, Xiaodong
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supporting information
(2021/02/01)
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- Photo-induced oxidative cleavage of C-C double bonds of olefins in water
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The carbonyl compounds, synthesized by the oxidative cleavage of their corresponding olefins, are of great significance in organic synthesis, especially aryl ketones. We have developed a gentle and effective protocol, using acid red 94 as the organic metal-free photocatalyst, O2 as the oxidant, and water as the solvent. Under visible light irradiation, aryl ketone derivatives were obtained in moderate to excellent yields, showing good economic and environmental advantages.
- Zhang, Yilan,Yue, Xiaoguang,Liang, Chenfeng,Zhao, Jianming,Yu, Wenbo,Zhang, Pengfei
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supporting information
(2021/08/27)
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- Copper-Catalyzed Oxidative Fragmentation of Alkynes with NFSI Provides Aryl Ketones
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A copper-catalyzed oxidative cleavage reaction of alkynes using NFSI and TBHP was described. Various terminal and internal alkyne substrates were employed to render quick access to aryl ketone products in moderate to good yields. NFSI not only functioned as N-centered radical precursors but also engaged in the aryl group migration. Mechanistic studies also suggested the important role of water in the title reactions.
- Chen, Hanfei,Cheng, Hao,Huang, Yifan,Jin, Chaochao,Song, Weihan,Tan, Chen,Tan, Jiajing,Tang, Lin,Yang, Fang,Zhang, Shuaifei
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supporting information
(2020/11/03)
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- A Bifunctional Iron Nanocomposite Catalyst for Efficient Oxidation of Alkenes to Ketones and 1,2-Diketones
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We herein report the fabrication of a bifunctional iron nanocomposite catalyst, in which two catalytically active sites of Fe-Nx and Fe phosphate, as oxidation and Lewis acid sites, were simultaneously integrated into a hierarchical N,P-dual doped porous carbon. As a bifunctional catalyst, it exhibited high efficiency for direct oxidative cleavage of alkenes into ketones or their oxidation into 1,2-diketones with a broad substrate scope and high functional group tolerance using TBHP as the oxidant in water under mild reaction conditions. Furthermore, it could be easily recovered for successive recycling without appreciable loss of activity. Mechanistic studies disclose that the direct oxidation of alkenes proceeds via the formation of an epoxide as intermediate followed by either acid-catalyzed Meinwald rearrangement to give ketones with one carbon shorter or nucleophilic ring-opening to generate 1,2-diketones in a cascade manner. This study not only opens up a fancy pathway in the rational design of Fe-N-C catalysts but also offers a simple and efficient method for accessing industrially important ketones and 1,2-diketones from alkenes in a cost-effective and environmentally benign fashion.
- Ma, Zhiming,Ren, Peng,Song, Tao,Xiao, Jianliang,Yang, Yong,Yuan, Youzhu
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p. 4617 - 4629
(2020/05/19)
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- Cercosporin-bioinspired selective photooxidation reactions under mild conditions
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The development of an efficient system for selective oxidation of organic compounds to generate more valuable compounds with molecular oxygen is a significant challenge in industrial chemistry. Bioinspired by the ability of naturally occurring perylenequinonoid pigments (PQPs) to generate reactive oxygen species (ROS) upon photoirradiation, here we report that cercosporin, one of the perylenequinonoid pigments, can function as a cost-effective and environmentally friendly photocatalyst for a wide range of selective oxidations, including benzylic C-H bonds to carbonyls, amines to aldehydes, and sulfides to sulfoxides. All of the representative reactions proceeded smoothly with high efficiency under mild conditions. Owing to the use of inexpensive metal-free visible light-driven photocatalyst produced from microbial fermentation with cheap glucose as the starting material and the ease of handling, we expect that this developed method will be particularly attractive for many more applications in synthetic transformation.
- Li, Jia,Bao, Wenhao,Tang, Zhaocheng,Guo, Baodang,Zhang, Shiwei,Liu, Haili,Huang, Shuping,Zhang, Yan,Rao, Yijian
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supporting information
p. 6073 - 6081
(2019/11/20)
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- Combined Photoredox/Enzymatic C?H Benzylic Hydroxylations
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Chemical transformations that install heteroatoms into C?H bonds are of significant interest because they streamline the construction of value-added small molecules. Direct C?H oxyfunctionalization, or the one step conversion of a C?H bond to a C?O bond, could be a highly enabling transformation due to the prevalence of the resulting enantioenriched alcohols in pharmaceuticals and natural products,. Here we report a single-flask photoredox/enzymatic process for direct C?H hydroxylation that proceeds with broad reactivity, chemoselectivity and enantioselectivity. This unified strategy advances general photoredox and enzymatic catalysis synergy and enables chemoenzymatic processes for powerful and selective oxidative transformations.
- Betori, Rick C.,May, Catherine M.,Scheidt, Karl A.
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supporting information
p. 16490 - 16494
(2019/11/03)
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- Heterogeneous Suzuki-Miyaura coupling of heteroaryl ester: Via chemoselective C(acyl)-O bond activation
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A site-selective supported palladium nanoparticle catalyzed Suzuki-Miyaura cross-coupling reaction with heteroaryl esters and arylboronic acids as coupling partners was developed. This methodology provides a heterogeneous catalytic route for aryl ketone formation via C(acyl)-O bond activation of esters by successful suppression of the undesired decarbonylation phenomenon. The catalyst can be reused and shows high activity after eight cycles. The XPS analysis of the catalyst before and after the reaction suggested that the reaction might be performed via a Pd0/PdII catalytic cycle that began with Pd0.
- Ma, Hongpeng,Bai, Chaolumen,Bao, Yong-Sheng
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p. 17266 - 17272
(2019/06/24)
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- Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions
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Conversion of a wide range of N-Boc amides to aryl ketones was achieved with Grignard reagents via chemoselective C(O)-N bond cleavage. The reactions proceeded under catalyst-free conditions with different aryl, alkyl, and alkynyl Grignard reagents. α-Ketoamide was successfully converted to aryl diketones, while α,β-unsaturated amide underwent 1,4-addition followed by C(O)-N bond cleavage to provide diaryl propiophenones. N-Boc amides displayed higher reactivity than Weinreb amides with Grignard reagents. A broad substrate scope, excellent yields, and quick conversion are important features of this methodology.
- Sureshbabu, Popuri,Azeez, Sadaf,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
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p. 11823 - 11838
(2019/10/02)
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- Continuous flow synthesis of diaryl ketones by coupling of aryl Grignard reagents with acyl chlorides under mild conditions in the ecofriendly solvent 2-methyltetrahydrofuran
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An efficient continuous flow sequential synthesis of diaryl ketones was achieved by coupling of aryl Grignard reagents with acyl chlorides in the bio-derived “green” solvent 2-methyltetrahydrofuran (2-MeTHF) under mild reaction conditions (ambient temperature, 1 hour), allowing a safe and on-demand generation of 2-(3-benzoylphenyl)propionitrile with a productivity of 3.16 g hour?1
- Zhang, Chuan-Tao,Zhu, Rui,Wang, Zheng,Ma, Bing,Zajac, Adrian,Smiglak, Marcin,Xia, Chun-Nian,Castle, Steven L.,Wang, Wen-Long
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p. 2199 - 2204
(2019/01/26)
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- A convenient and practical heterogeneous palladium-catalyzed carbonylative Suzuki coupling of aryl iodides with formic acid as carbon monoxide source
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A practical heterogeneous palladium-catalyzed carbonylative Suzuki coupling of aryl iodides with arylboronic acids under carbon monoxide gas-free conditions has been developed using a bidentate phosphino-functionalized magnetic nanoparticle-immobilized palladium(II) complex as catalyst. Formic acid was utilized as the carbon monoxide source with dicyclohexylcarbodiimide as the activator, and a wide variety of biaryl ketones were generated in moderate to high yields. The new heterogeneous palladium catalyst can be prepared via a simple procedure and can easily be separated from a reaction mixture by simply applying an external magnet and recycled up to 10 times without any loss of activity.
- You, Shengyong,Yan, Chenyu,Zhang, Rongli,Cai, Mingzhong
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- Method for preparing aromatic ketone in aqueous phase
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The invention discloses a method for preparing aromatic ketone in an aqueous phase, comprising the following steps: enabling aryl formyl potassium formate and aryl potassium fluoborate to generate decarboxylation acylation reaction in water under the actions of a silver catalyst and an oxidizing agent, and performing treatment after reaction is ended to obtain the disclosed aromatic ketone. According to the preparation method, the silver catalyst replaces a noble metal catalyst, water is taken as a solvent, an aromatic ketone product is obtained with relatively high yield, the adopted catalystis low in cost and easy to obtain, reaction conditions are mild, and meanwhile, the product is good in university, and therefore, the method has good application potential.
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Paragraph 0042-0045
(2018/04/26)
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- Preparation method of aromatic ketone
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The invention discloses a preparation method of aromatic ketone. Under the effects of a palladium catalyst and a nitrogen-containing ligand, nitrile compounds and arylsulfonylhydrazide take desulfurization addition reaction in an organic solvent; after the reaction is completed, post treatment is performed to obtain aromatic ketone. The reaction is applicable to aromatic nitrile compounds, and isalso applicable to aliphatic nitrile compounds; the reaction realizes the wide substrate applicability and functional group tolerance; the potential application value is realized in the aspect of aryl-carbonyl building.
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Paragraph 0041; 0042; 0043; 0045
(2018/09/11)
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- Method of utilizing continuous flow microreactor to synthesize benzophenone derivative
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The invention belongs to the technical field of organic synthesis, and particularly relates to a method of utilizing a continuous flow microreactor to synthesize a benzophenone derivative. The methodincludes: using aryl Grignard reagent and acyl chloride as raw materials; at normal temperature, continuously synthesizing the benzophenone derivative in the microreactor; recycling a reaction solvent2-methyl tetrahydrofuran. Problems of environmental pollution and reaction operation safety caused by the fact that conventional Fridel-Crafts reaction is excessively dependent on reagents like aluminum trichloride, ferric trichloride and zinc dichloride are avoided, the defect that novel catalytic processes are expensive in catalytic reagent and harsh in operation condition is made up, and continuous synthesis of a medical intermediate ketoprofen nitrile is realized efficiently. The method has the advantages of high operation convenience, high reaction safety, high yield, high efficiency andreaction solvent reusability and is environment-friendly and efficient.
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Paragraph 0041-0044; 0046
(2018/09/11)
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- MeZnOMe-mediated reaction of aldehydes with Grignard reagents: A glance into nucleophilic addition/Oppenauer oxidation pathway
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A novel organozincate of RMgX ?MeZnOMe ?LiCl type, formed in situ via transmetalation of Grignard reagent RMgBr ?LiCl with MeZnOMe, is shown to be an excellent organometallic species in the nucleophilic addition/Oppenauer oxidation of aldehydes to generate aromatic ketones in high yield. This transformation allows quick access to structurally diverse aryl, heteroaryl, benzyl and alkyl ketones with broad substrate scope and excellent functional group tolerance.
- Fu, Ying,Ma, Xian-Zhen,Shi, Chun-Zhao,Shen, Tong,Du, Zhengyin
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- Kumada Arylation of Secondary Amides Enabled by Chromium Catalysis for Unsymmetric Ketone Synthesis under Mild Conditions
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The synthesis of aromatic ketones by chromium-catalyzed Kumada arylation of secondary amides with organomagnesium reagents is described. This reaction was enabled by using low-cost chromium(III) salt as a precatalyst, combined with trimethylsilyl chloride
- Chen, Changpeng,Liu, Pei,Luo, Meiming,Zeng, Xiaoming
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p. 5864 - 5868
(2018/05/29)
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- Pd(II)-Catalyzed Denitrogenative and Desulfinative Addition of Arylsulfonyl Hydrazides with Nitriles
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A Pd(II)-catalyzed denitrogenative and desulfinative addition of arylsulfonyl hydrazides with nitriles has been successfully achieved under mild conditions. This transformation is a new method for the addition reaction to nitriles with arylsulfonyl hydrazides as arylating agent, thus providing an alternative synthesis of aryl ketones. The reported addition reaction is tolerant to many common functional groups, and works well in the presence of electron-donating and electron-withdrawing substituents. Notably, the reported denitrogenative and desulfinative addition was also appropriate for alkyl nitriles, making this newly developed transformation attractive.
- Meng, Mengting,Yang, Liangfeng,Cheng, Kai,Qi, Chenze
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p. 3275 - 3284
(2018/03/25)
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- Manganese complex-catalyzed oxidation and oxidative kinetic resolution of secondary alcohols by hydrogen peroxide
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The highly efficient catalytic oxidation and oxidative kinetic resolution (OKR) of secondary alcohols has been achieved using a synthetic manganese catalyst with low loading and hydrogen peroxide as an environmentally benign oxidant in the presence of a small amount of sulfuric acid as an additive. The product yields were high (up to 93%) for alcohol oxidation and the enantioselectivity was excellent (>90% ee) for the OKR of secondary alcohols. Mechanistic studies revealed that alcohol oxidation occurs via hydrogen atom (H-atom) abstraction from an α-CH bond of the alcohol substrate and a two-electron process by an electrophilic Mn-oxo species. Density functional theory calculations revealed the difference in reaction energy barriers for H-atom abstraction from the α-CH bonds of R- and S-enantiomers by a chiral high-valent manganese-oxo complex, supporting the experimental result from the OKR of secondary alcohols.
- Miao, Chengxia,Li, Xiao-Xi,Lee, Yong-Min,Xia, Chungu,Wang, Yong,Nam, Wonwoo,Sun, Wei
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p. 7476 - 7482
(2017/10/30)
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- Method for preparing diaryl ketone from aryl sulfonate
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The invention discloses a method for preparing diaryl ketone from aryl sulfonate. The method includes following steps: in the presence of a catalyst and carbon monoxide, allowing aryl sulfonate and aryl boronic acid to react in an organic solvent; after reaction is finished, performing aftertreatment to obtain diaryl ketone. Aryl sufonate is adopted as an electrophilic reagent for Suzuki cross carbonylation coupling reaction, diaryl ketone is directly synthesized through carbon monoxide, aryl sulfonate and aryl boronic acid, reaction conditions are milk, functional groups are high in tolerance, a substrate is cheap and easy to get, and diaryl ketone can be prepared with high yield.
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Paragraph 0055; 0056
(2017/01/12)
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- Two-step one-pot synthesis method for meta-substituted diphenyl ketone compound
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The invention discloses a two-step one-pot synthesis method for a meta-substituted diphenyl ketone compound. According to the method, transition metal palladium is used as a catalyst, anhydrous sodium acetate is used as an additive, aromatic acid and a benzoylformic compound are subjected to an ortho-position C-H functionalization reaction based on carboxyl groups, then by means of the synergistic effect of CuO and the additive anhydrous sodium acetate, a decarboxylation coupling reaction is directly carried out without separating products, and the meta-substituted diphenyl ketone compound is synthesized through the two-step one-pot method. The two-step one-pot synthesis method has the advantages that the raw materials are simple and easy to obtain, reaction operations are simple, the method is environmentally friendly, and the product yield is high.
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Paragraph 0013; 0014; 0015; 0016; 0017; 0047-0051
(2016/10/09)
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- Ortho C-H acylation of aryl iodides by palladium/norbornene catalysis
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Reported herein is a palladium/norbornene-catalyzed ortho-arene acylation of aryl iodides by a Catellani-type C-H functionalization. This transformation is enabled by isopropyl carbonate anhydrides, which serve as both an acyl cation equivalent and a hydride source. Double (re)agent: A palladium/norbornene-catalyzed ortho-acylation of aryl iodides was developed, and is enabled by isopropyl carbonate anhydrides, which function as both an acyl cation equivalent and a hydride source. This reaction exhibits excellent functional-group compatibility and broad substrate scope. Heterocycle moieties can be tolerated on both the aryl and acyl partners. FG=functional group.
- Dong, Zhe,Wang, Jianchun,Ren, Zhi,Dong, Guangbin
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p. 12664 - 12668
(2015/10/28)
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- Direct electrosynthesis of ketones from benzylic methylenes by electrooxidative C-H activation
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Electrify your chemistry! Direct electrosynthesis of ketones from benzylic methylenes in an undivided cell was realized in moderate to good yields (see scheme). In this electrosynthesis, electrons instead of conventional oxidants and catalysts are employed to make the reaction environmentally benign. Moreover, the reaction intermediate radical was detected by ESR spectroscopy and the reaction mechanism was clarified.
- Meng, Li,Su, Jihu,Zha, Zhenggen,Zhang, Li,Zhang, Zhenlei,Wang, Zhiyong
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supporting information
p. 5542 - 5545
(2013/05/23)
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- Efficient and scalable synthesis of ketones via nucleophilic Grignard addition to nitriles using continuous flow chemistry
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In the present Letter we report the development of efficient continuous flow chemistry conditions for the scalable preparation of ketones. This transformation is achieved via nucleophilic addition of Grignard reagents to the corresponding nitriles and imine hydrolysis by means of in-series plug flow reactors.
- Mateos, Carlos,Rincón, Juan A.,Villanueva, José
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supporting information
p. 2226 - 2230
(2013/05/08)
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- Pd-tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) complex catalyzed acylodeboronation of arylboronic acids with benzoyl chloride or acetic anhydride
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The palladium-tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) complex, in the form of [NaL]+[PdCl3]-, exhibited high catalytic efficiency for the acylodeboronation reaction of arylboronic acids with benzoyl chloride or acetic anhydride, producing the corresponding ketones in good to excellent yields under mild reaction conditions. Various arylboronic acids, benzoyl chlorides and acetic anhydrides were tolerated in this method. Moreover, a typical method for synthesis of acetyl aryl ketones was obtained.
- Zhang, Jinli,Han, Zixing,Li, Junmiao,Wu, Yangjie
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p. 251 - 271
(2013/10/21)
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