- Carbonylative cross-coupling reaction of ethynylstibane with aryl iodides
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Palladium-catalyzed carbonylative cross-coupling reaction of ethynylstibane (Ph-=-SbPh2) and aryl iodides (Ar-I) is described. The reaction of the stibanes and the halides under 1 atm of carbon monoxide in N,N-dimethylacetamide using a combination of 5 mol% Pd(OAc)2 and 4 equivalents (20 mol%) of PPh3 brought about carbonylative cross-coupling reaction to afford arylethynylketones [ArC(O)-=-Ph] in good yields along with a small amount of directly coupled products, aryl acetylens (Ar-=-Ph). Formation of the side product was completely suppressed by conducting the reaction under high CO pressure (20 atm) conditions. The present method provides a variety of carbonylated products in good yield even with electron-deficient aryl iodides which usually give inferior results due to their tendency to undergo decarbonylation in the cross-coupling reaction of ethynylstibanes and acyl halides.
- Kakusawa, Naoki,Kurita, Jyoji
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- Palladium-catalyzed coupling of benzoyl halides with aryltrifluorosilanes leading to diaryl ketones
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Acyl-aryl Hiyama coupling of acyl halides with arylsilanes has been achieved by employing a palladium/phosphine catalyst system. A variety of acyl chlorides and fluorides can be applied for coupling with arylsilicon reagents, and unsymmetrical benzophenone derivatives can be prepared using this protocol.
- Ogiwara, Yohei,Maegawa, Yuki,Sakino, Daisuke,Sakai, Norio
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- Highly efficient etherification and oxidation of aromatic alcohols using supported and unsupported phosphorus pentoxide as a heterogeneous reagent
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A highly efficient procedure for etherification and oxidation of aromatic alcohol is described using unsupported and supported P2O5 on alumina and/or silica gel. The silica gel and alumina proved to be the most suitable support among the supports examined in our experiments. It was illustrated that the etherification and oxidative performance in reactions depend largely upon variables including reaction temperature, the nature of the P2O5 used (supported or unsupported P2O 5), and whether solvent-free conditions are applied. It was shown that P2O5 not only can convert the aromatic alcohols into corresponding ethers and/or aldehyde and ketone but also can convert aromatic ethers into aldehyde or ketone via oxidative cleavage. Finally, quantum mechanical calculations were performed to rationalized these events, and it was indicated that aldehyde and ketone are more favorable products on the basis of the heat of formation (Hf).
- Khazaei, Ardeshir,Rad, Mohammad Navid Soltani,Borazjani, Maryam Kiani,Saednia, Shahnaz,Borazjani, Mohammad Kiani,Golbaghi, Maryam,Behrouz, Somayeh
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- Synthesis, structure, and characterization of picolyl- and benzyl-linked biphenyl palladium N-heterocyclic carbene complexes and their catalytic activity in acylative cross-coupling reactions
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N-heterocyclic carbene ligands with picolyl (L1H2Br2, L3H2Br2) and benzyl (L2H2Br2, L4H2Br2) linked biphenyl backbone were synthesized and characterized. Their palladium(II) complexes [PdL1]Br2 (1), [PdL2Br2] (2), [PdL3]Br2 (3), and [PdL4Br2] (4) were synthesized by direct method using Pd(OAc)2. All complexes (1–4) were characterized by CHN analysis, electrospray ionization-MS, nuclear magnetic resonance, and single-crystal X-ray diffraction. Molecular structures confirm the distorted square planar geometry around the Pd(II) center. All of them showed good catalytic activity in acylative Suzuki cross coupling of phenyl boronic acid with benzoyl chloride to afford benzophenone in good yields.
- Muniyappan, Nalluchamy,Sabiah, Shahulhameed
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- Room-temperature palladium-catalyzed and copper(I)-mediated coupling reactions of acid chlorides with boronic acids under neutral conditions
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The palladium-catalyzed cross-coupling reactions of acid chlorides with arylboronic acids in the presence of copper(I) thiophene-2-carboxylate (CuTC) as an activator under strictly non-basic and mild reaction conditions afford the unsymmetrical ketones in moderate to excellent yields. A wide range of substrates bearing an electron-donating or an electron-withdrawing substituent on the aromatic ring is compatible. Georg Thieme Verlag Stuttgart.
- Nishihara, Yasushi,Inoue, Yoshiaki,Fujisawa, Mamoru,Takagi, Kentaro
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- Phosphane-free palladium-catalyzed carbonylative suzuki coupling reaction of aryl and heteroaryl iodides
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The carbonylative cross-coupling reaction of an arylboronic acid with an aryl iodide and a heteroaryl iodide to give unsymmetrical biaryl ketones was carried out by using Pd(tmhd)2/Pd (OAc)2 as a phosphane-free catalyst. Various aryl and heteroaryl iodides with different arylboronic acid derivatives provided, good, to excellent yields of the desired products under optimized reaction conditions. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009.
- Tambade, Pawan J.,Patil, Yogesh P.,Panda, Anil G.,Bhanage, Bhalchandra M.
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- Silica-supported phosphine palladium(0) complex catalyzed phenylation of acid chlorides and aryl iodides by sodium tetraphenylborate
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In the presence of a catalytic amount of silica - supported phosphine palladium(0) complex, sodium tetraphenylborate (NaBPh4) reacts with acid chlorides under mild conditions to give the corresponding phenyl ketones in 57-80% yields; it also reacts with aryl iodides to afford the corresponding biaryls in 75-84% yields.
- Cai, Ming-Zhong,Song, Cai-Sheng,Huang, Xian
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- A convenient method for preparing aromatic ketones from acyl chlorides and arylboronic acids via Suzuki-Miyaura type coupling reaction
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Aromatic ketones are synthesized efficiently via palladium-catalyzed cross-coupling reaction of boronic acids with acyl chlorides in the presence of K3PO4 hydrate in toluene. This allows the use of aliphatic acyl chlorides as the starting material. Hydrated water plays a significant role as an H2O source to activate the catalytic system.
- Urawa, Yoshio,Ogura, Katsuyuki
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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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- Nucleophilic acylation of arylfluorides catalyzed by imidazolidenyl carbene
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Imidazolidenyl carbene catalyzes nucleophilic acylation reaction of arylfluorides with electron withdrawing groups to give benzophenone derivatives.
- Suzuki, Yumiko,Toyota, Tomonori,Imada, Fumie,Sato, Masayuki,Miyashita, Akira
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- Successful application of indirect electrooxidation for the transformation of biaryl methanols to the corresponding biaryl ketones
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Various biaryl methanols were electrooxidized into the corresponding biaryl ketones in good yields and under very mild reaction conditions. Because of the relatively high oxidation potential, bulky structure, and somewhat poor solubility, biaryl methanols do not readily undergo direct electrooxidative transformations as a synthetic step toward the corresponding biaryl ketones. Herein, we report the successful indirect electrooxidation of secondary biaryl methanols featuring the use of a slight excess amount of KI (1.2 equivalents, relative to the substrate) in MeOH. Copyright
- Okimoto, Mitsuhiro,Yoshida, Takashi,Hoshi, Masayuki,Chiba, Tomohito,Maeo, Kei
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- Palladium-catalyzed synthesis of diaryl ketones from aldehydes and (hetero)aryl halides via C-H bond activation
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We developed a palladium-catalyzed C-H transformation that enabled the synthesis of ketones from aldehydes and (hetero)aryl halides. The use of picolinamide ligands was key to achieving the transformation. Heteroaryl ketones, as well as diaryl ketones, were synthesized in good to excellent yields, even in gram-scale, using this reaction. Results of density functional theory (DFT) calculations support the C-H bond activation pathway.
- Wakaki, Takayuki,Togo, Takaya,Yoshidome, Daisuke,Kuninobu, Yoichiro,Kanai, Motomu
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- Reaction of pentaarylantimony with acid halide, aldehyde and ketone
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Pentaarylantimony (pentaphenylantimony, penta-p-tolylantimony and penta-p-chlorophenylantimony) was found to be a mild arylation reagent. The arylation was chemoselective toward aromatic acid halides to give the corresponding aromatic ketones. No direct addition to ketone and acid anhydride occurred. Arylation reactions of aldehyde or ketone were promoted by the addition of Lewis acid. The nucleophilicities of aromatic antimony compounds depend on the number of antimony-aromatic carbon bonds.
- Fujiwara, Masahiro,Tanaka, Mutsuo,Baba, Akio,Ando, Hisanori,Souma, Yoshie
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- KCC-1/GMSI/VB12 as a new nano catalyst for the carbonylative Suzuki-Miyaura crosscoupling reaction
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In this study, vitamin B12 (VB12) modified with a (3-glycidyloxypropyl)trimethoxysilane (GMSI) moiety grafted onto KCC-1 (KCC-1/GMSI/VB12) was prepared for the first time. Its capability was evaluated for the carbonylative Suzuki-Miyaura crosscoupling reaction between carbon monoxide, 4-iodoanisole and phenylboronic acid, affording the desired products in high yield. Applying 1 mg of catalyst and 1 mmol of K2CO3 as base in 10 mL anisole and heating under reflux for 1 h are the best conditions for the reaction. The catalysts were very active in catalytic recycling experiments over ten catalytic cycles.
- Sadeghzadeh, Seyed Mohsen,Zhiani, Rahele,Emrani, Shokufe
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- Pd/C: An efficient, heterogeneous and reusable catalyst for phosphane-free carbonylative suzuki coupling reactions of aryl and heteroaryl iodides
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The carbonylative Suzuki coupling reaction of aryl boronic acid with different aryl and heteroaryl iodides was carried out to synthesize various unsymmetrical biaryl ketones by using Pd/C as an efficient, heterogeneous and reusable catalyst. The catalyst exhibits remarkable activity, and its reusability was tested up to four consecutive cycles. The reaction is applicable for various aryl and heteroaryl iodides having different steric and electronic properties. It provides good to excellent yield of the desired products. The developed protocol is advantageous with regard to the ease in handling the catalyst and the simple work-up procedure; it is also an environmentally benign process with effective catalyst recyclability. A facile protocol has been developed for the carbonylative Suzuki coupling reaction of aryl and heteroaryl iodides with Pd/C as effective, heterogeneous, reusable catalyst. The system is applicable for a wide variety of aryl and heteroaryl iodides. Copyright
- Khedkar, Mayur V.,Tambade, Pawan J.,Qureshi, Ziyauddin S.,Bhanage, Bhalchandra M.
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- DMC mediated one pot synthesis of biaryl ketones from aryl carboxylic and boronic acids
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Synthesis of biaryl ketones has been realized from aryl carboxylic acids in the presence of DMC, facilitated by palladium catalyst under thermal condition. This methodology gives the introduction of carbonyl functionality in one pot from corresponding ary
- Pathak, Arunendra,Rajput, Chatrasal S.,Bora, Pushkar S.,Sharma, Somesh
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- Palladium-catalyzed carbonylative cross-coupling reaction of triarylantimony dicarboxylates with arylboronic acids: Synthesis of biaryl ketones
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A novel palladium-catalyzed three-component carbonylative coupling reaction by use of triarylantimony diacetate, arylboronic acid and carbon monoxide (1 atm) could be attained under mild reaction conditions without any base as an additive. The reaction can be applied to a wide range of triarylantimony diacetates and boronic acids to afford the corresponding unsymmetrical biaryl ketones in good yields.
- Qin, Weiwei,Yasuike, Shuji,Kakusawa, Naoki,Kurita, Jyoji
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- Mechanistic studies of oxidation of diphenylmethanols by sodium N-chlorobenzenesulphonamide catalysed by ruthenium(III)
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The kinetics of oxidation of six para-substituted diphenylmethanols (Y-DPM, where Y=H, Cl, Br, NO2, CH3 and OCH3) by sodium N-chlorobenzenesulphonamide [chloramine-B (CAB)] in the presence of HCI and catalysed by RuCl3 in 30% (v/v) methanol medium was studied at 35 °C. The experimental rate law is rate=k′[CAB]0[DPM]0x[RuCl 3]y[H+]z, where x, y and z are fractions. Addition of reaction product, benzenesulphonamide (BSA), retards the reaction. An increase in the dielectic constant of the medium decreases the rate. Rate studies in D2O medium showed that the solvent isotope effect k′ (H2O)/k′ (D2O)=0·53. Proton inventory studies were carried out using H2O-D2O mixtures. The rates correlate satisfactorily with the Hammett σ relationship and the plot is biphasic. The reaction constant ρ is -2·8 for electron-releasing groups and -0·31 for electron-withdrawing groups at 35 °C. The activation parameters ΔH?, ΔS?, ΔG? and logA were calculated. ΔH? and ΔS? are linearly related and an isokinetic relationship is observed with β=343 K, indicating enthalpy as a controlling factor,
- Rangappa,Ramachandra,Mahadevappa
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- Rhodium-catalyzed synthesis of aryl ketones from carboxylic acid anhydrides and potassium aryltrifluoroborates in the presence of CuI
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A new rhodium-catalyzed cross-coupling of carboxylic acid anhydrides and potassium aryltrifluoroborates was described. In this system CuI played a very important role. Various functionalities were compatible in the reaction, and the desired products were obtained in good to excellent yields. A mechanism of this reaction using a Rh(I) model catalyst have also been proposed.
- Liu, Xia,Yi, Ze,Yi, Maocong,Wang, Jianhui,Liu, Guiyan
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- ELECTRONIC EFFECTS IN THE SEMICONDUCTOR - PHOTOCATALYZED OXIDATIVE CLEAVAGE OF OLEFINS
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A linear Hammett plot (p+=-0.56) is obtained from relative rates of TiO2 powder sensitized oxidative cleavage of para-substituted 1,1-diphenylethylenes, better correlation having been observed with ?+ parameters than with ?.
- Fox, Marye Anne,Chen, Chia-Chung
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- Iron-catalyzed carbonylation of aryl halides with arylborons using stoichiometric chloroform as the carbon monoxide source
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A general iron-catalyzed carbonylative Suzuki-Miyaura coupling of aryl halides with arylborons is reported, using stoichiometric CHCl3 as the CO source. The high efficiency, economy, selectivity, and operational simplicity of this transformation make this method a valuable tool in organic synthesis. Importantly, the presented strategy allows effective 13C labeling simply by using the commercially available 13C-labeled CHCl3. On the basis of the initial mechanistic exploration, an aryl radical intermediate is proposed in the present carbonylation process.
- Zhao, Hongyuan,Du, Hongyan,Yuan, Xiaorong,Wang, Tianjiao,Han, Wei
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- Palladium nanoparticles immobilized onto supported ionic liquid-like phases (SILLPs) for the carbonylative Suzuki coupling reaction
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Crosslinked polymeric materials based on poly(ionic liquid)s, also named supported ionic liquid-like phases (SILLPs) were prepared by copolymerization of dication imidazole ionic liquids with divinylbenzene (DVB). Using the SILLPs-related polymeric materials as supports, palladium (Pd) metal nanoparticles were immobilized and stabilized, which can efficiently catalyze the carbonylative Suzuki coupling reaction of aryl iodides with aryl boronic acids, affording the corresponding products in good to excellent yields. The Pd nanoparticles immobilized onto SILLPs were characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TG), and X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR). The size and dispersion of the Pd nanoparticles supported on polymers are influenced possibly by varying the contents of the ionic liquid units and the introduction of amine groups. Furthermore, hot filtration and mercury poisoning tests indicated that the palladium species leached into the solvent during the reaction and returned to the polymers after the reaction was completed. In addition, the catalyst was easily recovered from the reaction mixture by filtration and reused over five consecutive cycles without a significant decrease in its activity. This journal is
- Jiao, Nianming,Li, Zelong,Wang, Yan,Liu, Jianhua,Xia, Chungu
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- Efficient N-heterocyclic carbene palladium(II) catalysts for carbonylative Suzuki-Miyaura coupling reactions leading to aryl ketones and diketones
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New N, N′-substituted imidazolium salts (L1 and L2) and their corresponding diiodopyridinepalladium(II) complexes (C1 and C2) were successfully synthesized and characterized. Reactions of palladium iodide with the newly synthesized N, N′-substituted imidazolium iodides in pyridine afforded the corresponding new palladium-N-heterocyclic carbene pyridine complexes in high yields. The new palladium(II) complex C1 was characterized by single crystal X-ray diffraction analysis. The Pd(II) ion is bonded to the nitrogen atom of the pyridine, the carbon atom of the NHC carbene ligand and two trans iodides resulting in distorted square planar geometry. The two Pd-NHC-Py complexes C1 and C2 displayed higher catalytic activity in the carbonylative Suzuki-Miyaura coupling reactions with much lower catalyst loading as compared to the catalytic systems reported in the literature.
- Ibrahim, Mansur,Malik, Imran,Mansour, Waseem,Sharif, Muhammad,Fettouhi, Mohammed,El Ali, Bassam
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- Efficient, recyclable and phosphine-free carbonylative Suzuki coupling reaction using immobilized palladium ion-containing ionic liquid: Synthesis of aryl ketones and heteroaryl ketones
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The carbonylative Suzuki coupling reaction of aryl and heteroaryl iodides was studied by using immobilized palladium ion-containing ionic liquid (ImmPd-IL). The protocol was optimized with respect to various reaction parameters, applied to a wide variety of substituted aryl/heteroaryl iodides and various aryl/heteroaryl boronic acids with different steric and electronic properties, and afforded the corresponding products in good to excellent yield. This is an efficient, heterogeneous catalyst which avoids the use of phosphine ligands, and its reusability was tested in up to four consecutive cycles. The recycled catalyst was characterized by using XPS analysis.
- Khedkar, Mayur V.,Sasaki, Takehiko,Bhanage, Bhalchandra M.
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- Cu (II) Schiff base complex grafted guar gum: Catalyst for benzophenone derivatives synthesis
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In this study Guar gum based Cu(II) Schiff's base complex (GG-Cu) has been synthesized and characterized by FT-IR, PXRD, UV–vis, TGA, XPS, FESEM, TEM, EDAX, solid-state NMR, Elemental mapping, CHNS and AAS analysis. This moiety has been found to be an efficient heterogeneous catalyst for selective oxidation reactions. Fifteen model reactions have been carried to establish the catalytic behavior of GG-Cu, and five of these yield novel products. The ease of separation of catalyst from the reaction mixture simply by filtration is an added advantage; furthermore the catalyst can be reused up to five times without significant loss of catalytic activity. The overall concept of developing newer, efficient and environmental benign catalysts with ease of separation and recycling ability has been successfully demonstrated. All of the isolated products were fully characterized on the basis of their physical and spectral data.
- Krishna,Kumari, Shweta,Sharma, Sunil K.,Yadav, Deepak
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- Carbonylative Suzuki Coupling Reaction Catalyzed by a Hydrospirophosphorane Palladium Complex
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A Pd complex with the H-spirophosphorane ligand, PdCl2{P(OCMe2CMe2O)OC6H4NH2} (Cat. 1), was used as the catalyst in the carbonylative Suzuki coupling of substituted iodobenzenes with arylboronic acids and with sodium tetraphenylborate. Substituted diarylketones were obtained in good to excellent yields and a selectivity over 95 % under 1 atm of CO with 1.5 mol % of the catalyst. The promoting role of the H-spirophosphorane ligand in the catalytic process was evidenced. We used X-ray photoelectron spectroscopy, TEM, and 31P NMR spectroscopy to reveal that during the reaction Cat. 1 undergoes transformation into Pd complexes that bear the spirophosphorane ligand or other P ligands formed by its dealkylation and to Pd nanoparticles. All these Pd species contribute to the high productivity of the system.
- Wójcik, Przemys?aw,Sygellou, Labrini,Gniewek, Andrzej,Skar?yńska, Anna,Trzeciak, Anna
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- Novel palladium nanoparticles supported on β-cyclodextrin@graphene oxide as magnetically recyclable catalyst for Suzuki–Miyaura cross-coupling reaction with two different approaches in bio-based solvents
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A novel nanocatalyst was designed and prepared. Initially, the surface of magnetic graphene oxide (M-GO) was modified using thionyl chloride, tris(hydroxymethyl)aminomethane and acryloyl chloride as linkers which provide reactive C═C bonds for the polymerization of vinylic monomers. Separately, β-cyclodextrin (β-CD) was treated with acryloyl chloride to provide a modified β-CD. Then, in the presence methylenebisacrylamide as a cross-linker, monomers of modified β-CD and acrylamide were polymerized on the surface of the pre-prepared M-GO. Finally, palladium acetate and sodium borohydride were added to this composite to afford supported palladium nanoparticles. This fabricated nanocomposite was fully characterized using various techniques. The efficiency of this easily separable and reusable heterogeneous catalyst was successfully examined in Suzuki–Miyaura cross-coupling reactions of aryl halides and boronic acid as well as in modified Suzuki–Miyaura cross-coupling reactions of N-acylsuccinimides and boronic acid in green media. The results showed that the nanocatalyst was efficient in coupling reactions for direct formation of the corresponding biphenyl as well as benzophenone derivatives in green media based on bio-based solvents. In addition, the nanocatalyst was easily separable, using an external magnet, and could be reused several times without significant loss of activity under the optimum reaction conditions.
- Heidari, Bahareh,Heravi, Majid M.,Nabid, Mohammad Reza,Sedghi, Roya,Hooshmand, Seyyed Emad
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- General and greener route to ketones by palladium-catalyzed direct conversion of carboxylic acids with organoboronic acids
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Cross-coupling reaction of carboxylic acids with organoboron compounds catalyzed by palladium complexes in the presence of an activator such as dimethyl dicarbonate under mild conditions gives ketones in excellent yields except for certain substrates.
- Kakino, Ryuki,Narahashi, Hirohisa,Shimizu, Isao,Yamamoto, Akio
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- Microwave-promoted cross-coupling of acid chlorides with arylboronic acids: a convenient method for preparing aromatic ketones
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Simple catalytic systems for cross-coupling reactions of acyl chlorides with arylboronic acids under microwave conditions were tested. Microwave irradiation facilitated the reaction course. Mild reaction conditions afford the symmetrical and unsymmetrical aryl ketones in reasonable to high yields within a short time. A wide range of substrates bearing an electron-donating or an electron-withdrawing substituent on aryl ring of acid chloride as well as on boronic acid were examined and high yields of ketones were produced.
- Polá?ková, Viera,Toma, ?tefan,Augustínová, Iveta
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- Carbonylative Suzuki coupling reactions of aryl iodides with arylboronic acids over Pd/SiC
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High surface area SiC has been used to prepare a Pd/SiC catalyst using the liquid reduction method, and the resulting catalyst was used for the carbonylative Suzuki coupling reaction of aryl iodides with arylboronic acids. The catalyst was also characterized by X-ray diffraction, inductively coupled plasma-mass spectroscopy and high-resolution transmission electron microscopy. The results of these analyses showed that homogeneous Pd nanoparticles with a mean diameter of 2.8 nm were uniformly dispersed on the SiC surface. Optimization of the reaction conditions for the carbonylative Suzuki coupling reaction, including the solvent, base, pressure, temperature and reaction time, revealed that the model reaction of iodobenzene (1.0 mmol) with phenylboronic acid (1.5 mmol) could reach 90% conversion with a selectivity of 99% towards the diphenyl ketone using 3 wt% Pd/SiC under 1.0 MPa of CO pressure at 100 °C for 8 h with K2CO3 (3.0 mmol) as the base and anisole as the solvent. The Pd/SiC catalyst exhibited broad substrate scope towards the carbonylative Suzuki coupling reaction of aryl iodides with arylboronic acids bearing a variety of different substituents. Furthermore, the Pd/SiC catalyst exhibited good recyclability properties and could be recovered and reused up to five times with the conversion of iodobenzene decreasing only slightly from 90% to 76%. The decrease in the catalytic activity after five rounds was attributed to the loss of active Pd during the organic reaction.
- Cui, Yanli,Guo, Xiaoning,Wang, Yingyong,Guo, Xiangyun
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- Ruthenium(III)-catalyzed mechanistic studies of oxidation of benzhydrols by sodium N-chloro-p-toluenesulfonamide in HCl medium
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The reaction rate of the ruthenium(III)-catalyzed oxidation of benzyhydrol and its derivatives by sodium N-chloro-p-toluenesulfonamide or chloramine-T (CAT) in the presence of hydrochloric acid in 30% (v/v) MeOH medium was determined at 35 °C. The reaction rate showed a first-order dependence on [CAT]o and a fractional-order each on [YBH]o [Ru(III)], and [H+]. The reaction rate also has a negative fractional-order behavior in the reduction product of CAT and p-toluenesulfonamide.
- Ramachandra,Mahadevappa,Rangappa,Gowda
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- Palladium-Catalyzed suzuki?Miyaura cross-Coupling of amides via site-Selective n?C bond cleavage by cooperative catalysis
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Palladium-catalyzed Suzuki?Miyaura cross-coupling of primary benzamides enabled by a merger of site-selective N,N-di-Boc-activation and cooperative catalysis via N?C bond cleavage for the synthesis of biaryl ketones is reported. We present the synergistic combination of Lewis base and palladium catalysis as a concept to activate inert amide N?C bonds. The mild reaction conditions provide a direct route to structurally diverse ketones. The reaction tolerates a wide range of electrophilic functional groups. Considering the fundamental importance of primary amides as pharmaceutical and synthetic intermediates, the strategy has a potential for developing a diverse array of valuable amide N?C bond functionalization reactions by the synergistic merger of Lewis base and organometallic catalysis.
- Meng, Guangrong,Shi, Shicheng,Szostak, Michal
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- KETONE SYNTHESIS VIA PALLADIUM-CATALYZED CARBONYLATION OF ORGANOALUMINIUM COMPOUNDS
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Arylaluminium compounds react with aryl iodides and carbon monoxide in the presence of palladium complex to produce unsymmetrical ketones.
- Bumagin, N. A.,Ponomaryov, A. B.,Beletskaya, I. P.
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- Carbonylative Suzuki-Miyaura Coupling Reactions of Aryl Iodides with Readily Available Polymer-Immobilized Palladium Nanoparticles
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Polysilane/alumina-supported palladium nanoparticle catalyzed carbonylative Suzuki-Miyaura coupling reactions under ligand-free conditions have been developed to synthesize diaryl ketones. High yields and selectivities were achieved even with low catalyst loading under atmospheric pressure of CO gas. A variety of aryl iodides and arylboronic acids could be utilized to afford the diaryl ketones in excellent yields. Moreover, the ligand-free immobilized palladium nanoparticles could be recovered by simple filtration and the catalytic activity could be maintained for several runs.
- Yasukawa, Tomohiro,Zhu, Zhiyuan,Yamashita, Yasuhiro,Kobayashi, Shu
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- Palladium(II)-catalyzed addition of arylboronic acid to nitriles
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The addition of arylboronic acid to nitriles catalyzed by palladium(II) species in the presence of bipyridine as the ligand was developed. The use of bipyridine is crucial for changing the properties of arylpalladium species from more electrophilic to more nucleophilic making the reaction possible.
- Zhao, Baowei,Lu, Xiyan
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- Synthesis of biaryl ketones and biaryl diketones via carbonylative Suzuki-Miyaura coupling reactions catalyzed by bridged bis(N-heterocyclic carbene)palladium(II) catalysts
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This disclosure relates to bridged bis(N-heterocyclic carbene)palladium(II) complexes, methods of preparing the complexes, and methods of using the complexes in Suzuki-Miyaura coupling reactions.
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Page/Page column 20; 22-26
(2021/12/23)
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- C(acyl)-C(sp2) and C(sp2)-C(sp2) Suzuki-Miyaura cross-coupling reactions using nitrile-functionalized NHC palladium complexes
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Application of N-heterocyclic carbene (NHC) palladium complexes has been successful for the modulation of C-C coupling reactions. For this purpose, a series of azolium salts (1a-f) including benzothiazolium, benzimidazolium, and imidazolium, bearing a CN-substituted benzyl moiety, and their (NHC)2PdBr2 (2a-c) and PEPPSI-type palladium (3b-f) complexes have been systematically prepared to catalyse acylative Suzuki-Miyaura coupling reaction of acyl chlorides with arylboronic acids to form benzophenone derivatives in the presence of potassium carbonate as a base and to catalyse the traditional Suzuki-Miyaura coupling reaction of bromobenzene with arylboronic acids to form biaryls. All the synthesized compounds were fully characterized by Fourier Transform Infrared (FTIR), and 1H and 13C NMR spectroscopies. X-ray diffraction studies on single crystals of 3c, 3e and 3f prove the square planar geometry. Scanning Electron Microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), metal mapping analyses and thermal gravimetric analysis (TGA) were performed to get further insights into the mechanism of the Suzuki-Miyaura cross coupling reactions. Mechanistic studies have revealed that the stability and coordination of the complexes by the CN group are achieved by the removal of pyridine from the complex in catalytic cycles. The presence of the CN group in the (NHC)Pd complexes significantly increased the catalytic activities for both reactions.
- ?akir, Sinem,Karabiyik, Hande,Kavukcu, Serdar Batikan,Rethinam, Senthil,Türkmen, Hayati
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p. 37684 - 37699
(2021/12/09)
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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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p. 4583 - 4594
(2021/08/06)
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- Photo-induced oxidative cleavage of C-C double bonds for the synthesis of biaryl methanoneviaCeCl3catalysis
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A Ce-catalyzed strategy is developed to produce biaryl methanonesviaphotooxidative cleavage of C-C double bonds at room temperature. This reaction is performed under air and demonstrates high activity as well as functional group tolerance. A synergistic Ce/ROH catalytic mechanism is also proposed based on the experimental observations. This protocol should be the first successful Ce-catalyzed photooxidation reaction of olefins with air as the oxidant, which would provide inspiration for the development of novel Ce-catalyzed photochemical synthesis processes.
- Xie, Pan,Xue, Cheng,Du, Dongdong,Shi, SanShan
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supporting information
p. 6781 - 6785
(2021/08/20)
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- Gold complexes of bis-indazole-derived N-Heterocyclic carbene: Synthesis, structural characterizations, and catalysis
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A novel series of bis Indy-NHC gold complexes have been developed and investigated via a mild Ag-carbene transfer route. The obtained complexes were characterized by NMR spectroscopy and X-ray diffraction analysis. The catalytic property of these gold complexes was further evaluated in the oxidation of benzylic. The gold complex E1 showed a high catalytic activity in the oxidation of various benzylic substrates, resulting in the corresponding carbonyl compounds with excellent yields using TBHP as oxidant.
- Zhang, Hua,Xu, Ting,Li, Dongdong,Cheng, Tao,Chen, Jing,Zhou, Yang
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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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- Suzuki coupling of aroyl-MIDA boronate esters – A preliminary report on scope and limitations
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Recent methodological reports for synthesizing acyl-MIDA boronate esters compel an investigation of their potential use as substrates in a standard Suzuki-Miyaura cross-coupling reaction. Here we report the production of benzophenones by C[sbnd]C cross coupling between a benzoyl-MIDA boronate ester and a multitude of aryl bromide substrates in adequate yields following optimization under ambient conditions outside of a glove box. Under these standard conditions, none of several acyl-MIDA boronate esters (in an alkyl series) serves as a competent coupling partner. The substrate scope is also limited by the finding that the corresponding trifluoroborates of both acyl- and aroyltrifluroborates are not suitable substrates. For reasons of availability and synthetic difficulty in procuring other aroyl-MIDA boronates, this preliminary study examines the reactivity of benzoyl-MIDA boronate with several aryl bromide substrates.
- Lai, Samson,Lin, Wen Xuan,Perrin, David M.,Takaesu, Noah
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- Pd-Catalysed carbonylative Suzuki-Miyaura cross-couplings using Fe(CO)5under mild conditions: generation of a highly active, recyclable and scalable ‘Pd-Fe’ nanocatalyst
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The dual function and role of iron(0) pentacarbonyl [Fe(CO)5] has been identified in gaseous CO-free carbonylative Suzuki-Miyaura cross-couplings, in which Fe(CO)5supplied COin situ, leading to the propagation of catalytically active Pd-Fe nanoparticles. Compared with typical carbonylative reaction conditions, CO gas (at high pressures), specialised exogenous ligands and inert reaction conditions were avoided. Our developed reaction conditions are mild, do not require specialised CO high pressure equipment, and exhibit wide functional group tolerance, giving a library of biaryl ketones in good yields.
- Zhu, Zhuangli,Wang, Zhenhua,Jian, Yajun,Sun, Huaming,Zhang, Guofang,Lynam, Jason M.,McElroy, C. Robert,Burden, Thomas J.,Inight, Rebecca L.,Fairlamb, Ian J. S.,Zhang, Weiqiang,Gao, Ziwei
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supporting information
p. 920 - 926
(2021/02/09)
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- 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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- Palladium supported on MRGO@CoAl-LDH catalyzed reductive carbonylation of nitroarenes and carbonylative Suzuki coupling reactions using formic acid as liquid CO and H2 source
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In the present study, a heterogeneous palladium catalyst system, Pd nanoparticles supported on MRGO@CoAl-LDH, was synthesized and employed in reductive carbonylation of nitroarenes and carbonylative Suzuki coupling reactions using formic acid as CO and H2 source. The as-obtained heterogeneous catalyst was characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDAX), thermal gravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The nanocatalyst was reused for 5 cycles with a negligible reduction in the yield of products. All reactions were carried out with high yields and under suitable and safe conditions. Also, we have successfully applied formic acid as a good and safe alternative to CO and H2 gases.
- Jadidi Nejad, Masoumeh,Heydari, Akbar
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- Visible light-driven direct synthesis of ketones from aldehydes via C[sbnd]H bond activation using NiCu nanoparticles adorned on carbon nano onions
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An efficient, straightforward and high yield synthetic approach is described for the direct synthesis of diaryl ketones via the C[sbnd]H bond activation of aldehydes using NiCu nanoparticles adorned on carbon nano onions as an efficient heterogeneous catalyst under the irradiation of a mercury-vapor lamp (400 w) via simple workup. This C[sbnd]H bond activation reaction appears simple and convenient with a wide substrate scope in view of its excellent synthesis prowess as illustrated in the preparation of new-approved anti-Alzheimer and anti-HIV medicinal compounds under greener and mild reaction conditions; catalyst could be recycled and reused five times without any loss of catalytic activity.
- Heydari, Akbar,Khorsandi, Zahra,Metkazini, S. Fatemeh Mohammadi,Varma, Rajender S.
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- Highly selective electrocatalytic oxidation of benzyl C-H using water as safe and sustainable oxygen source
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The selective oxidation of C-H bond is critical for feedstock manufacturing in chemical industry. Current strategies typically involve the use of oxygen or peroxide as the oxidation reagent under high temperature, which sets severe challenges in production sustainability and industrial safety. Herein, we demonstrate an environmental-friendly and safe electrocatalytic strategy for the selective oxidation of benzyl group to ketones at ambient conditions, while using water as the sole oxygen source. Water addition reduces the onset potential of anodic C-H oxidation, and produces 1-tetralone with satisfying conversion and excellent ketone to alcohol ratio. Layered MnO2 catalysts (with rich oxygen vacancies) further adjust the water affinity and facilitate the oxidation, leading to a significantly improved faradaic efficiency. This journal is
- Ding, Mengning,Li, Xiaoshan,Sun, Yuxia,Xie, Jin,Xu, Wentao,Yang, Miao
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supporting information
p. 7543 - 7551
(2020/11/18)
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- Palladium-Catalyzed Amide N-C Hiyama Cross-Coupling: Synthesis of Ketones
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N-Acylglutarimides and arylsiloxanes reacted in the presence of Pd(OAc)2/PCy3, Et3N·3HF, and LiOAc to provide the corresponding arylketones in good yields. Aryl-, vinyl-, and alkyl-substituted N-acylglutarimides showed good activity in the coupling reactions of arylsiloxanes. The reaction had a broad substrate scope and showed good functional group tolerance. N-Benzoylsuccinimide and N-protected N-phenylbenzamides showed good activities in coupling reactions with phenylsiloxane. The employment of CuF2 as an activor afforded the decarbonylative products at 160 °C.
- Idris, Muhammad Aliyu,Lee, Sunwoo
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supporting information
p. 9190 - 9195
(2020/11/18)
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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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- Ionic liquid-mediated benzoyl transfer-coupling in the Suzuki and Sonogashira reactions and aryl transfer-coupling by decarbonylative Heck reaction, using N-Benzoyl-saccharin (NBSac) as reagent
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The efficacy of N-benzoyl-saccharin (NBSac) as reagent for selective benzoyl transfer-coupling in the Suzuki reaction in BMIM-IL/[PAIM][NTf2] as solvent/base, and in the Sonogashira reaction employing guanidinium-IL (GIL) as solvent, are demonstrated. Decarbonylative aryl transfer-coupling occurs in the Heck reaction employing GIL as solvent. The reactions are catalyzed by Pd(OAc)2 or NiCl2(dppp), are performed under mild conditions in good yields, and have the potential for recycling/reuse of the IL solvent. Collectively, these methods provide facile access to diverse libraries of diarylketones, keto-ethynes and diaryl-ethenes.
- Malunavar, Shruti S.,Sutar, Suraj M.,Prabhala, Pavankumar,Kalkhambkar, Rajesh G.,Laali, Kenneth K.
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supporting information
(2020/05/18)
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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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- Carbonylative Suzuki coupling reactions catalyzed by ONO pincer–type Pd(II) complexes using chloroform as a carbon monoxide surrogate
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Benzoylhydrazone Schiff base–ligated three new ONO pincer–type palladium(II) complexes, [(PdL1(PPh3)] (1), [(PdL2(PPh3)] (2), and [(PdL3(PPh3)] (3), were synthesized by the reaction of the respective ligand, N-(2-hydroxybenzylidene)benzohydrazide (HL1), N-(2-hydroxy-3-methoxybenzylidene)benzohydrazide (HL2), or N-(5-bromo-2-hydroxybenzylidene) benzohydrazide (HL3), with Pd(OAc)2 and PPh3 in methanol and isolated as air-stable reddish-orange crystalline solids in high yields (78%–83%). All three complexes were fully characterized by elemental analysis, Fourier-transform infrared spectroscopy, UV–Visible, 1H nuclear magnetic resonance (NMR), 13C{1H} NMR, and 31P{1H} NMR spectroscopic studies. The molecular structure of all three complexes was established unambiguously by single-crystal X-ray diffraction studies which revealed a distorted square planar geometry of all three complexes. The ONO pincer–type ligands occupied three coordination sites at the palladium, while the fourth site is occupied by the monodentate triphenylphosphine ligand. The catalytic potential of all three complexes was explored in the carbonylative Suzuki coupling of aryl bromides and iodides with arylboronic acids to yield biaryl ketones, using CHCl3 as the source of carbonyl. The reported protocol is convenient and safe as it obviates the use of carbon monoxide (CO) balloons or pressured CO reactors which are otherwise needed for the carbonylation reactions. The methodology has been successfully applied to the synthesis of two antineoplastic drugs, namely, phenstatin and naphthylphenstatin, in good yields (81% and 85%, respectively). Under the optimized reaction conditions, complex 2 exhibited the best catalytic activity in the carbonylative Suzuki couplings. The reported catalysts have wide reaction scope with good functional group tolerance. All catalysts could be retrieved from the reaction after completion and recycled up to three times with insignificant loss in the catalytic activity.
- Layek, Samaresh,Agrahari, Bhumika,Ganguly, Rakesh,Das, Parthasarathi,Pathak, Devendra D.
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- Recyclable polyetheretherketone fiber-supported N-heterocyclic carbene catalysts for nucleophilic acylation of fluorobenzenes
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We report for the first time a novel support of polyetheretherketone fiber for the synthesis of recyclable N-heterocyclic carbene (NHC) catalysts. The fiber catalysts were verified in nucleophilic acylation of fluorobenzenes with superior catalytic activities, and successfully recycled by a tiny pair of tweezers over 21 cycles with minimal loss of performance.
- Shi, Xian-Lei,Sun, Benyu,Hu, Qianqian,Liu, Kun,Li, Pengyu,Wang, Juanjuan
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supporting information
p. 11390 - 11393
(2020/10/12)
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- Novel and efficient bridged bis(N-heterocyclic carbene)palladium(II) catalysts for selective carbonylative Suzuki–Miyaura coupling reactions to biaryl ketones and biaryl diketones
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Bridged N,N′-substituted bisbenzimidazolium bromide salts (L1, L2, and L3) were synthesized and fully characterized. Reactions of palladium acetate with L1, L2, and L3 afforded corresponding new bridged bis(N-heterocyclic carbene)palladium(II) complexes (C1, C2, and C3) in high yields. The X-ray structure of complex C1 showed that the Pd(II) ion is bonded to the two carbon atoms of the bis(N-heterocyclic carbene) and two bromido ligands are in the cis position, resulting in a distorted square planar geometry. The three Pd(NHC)2Br2 complexes C1, C2, and C3 were evaluated in carbonylative Suzuki–Miyaura coupling reactions of aryl boronic acids with aryl halides and displayed high catalytic activity with low catalyst loading. The coupling reactions of aryl bromides were selective towards the carbonylation product at higher carbon monoxide pressure.
- El Ali, Bassam,Fettouhi, Mohammed,Mansour, Waseem
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- A sodium trifluoromethanesulfinate-mediated photocatalytic strategy for aerobic oxidation of alcohols
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A sodium trifluoromethanesulfinate-mediated photocatalytic strategy for the aerobic oxidation of alcohols has been developed for the first time, and the photoredox aerobic oxidation of secondary and primary alcohols provided the corresponding ketones and carboxylic acids, respectively, in high to excellent yields.
- Zhu, Xianjin,Liu, Can,Liu, Yong,Yang, Haijun,Fu, Hua
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p. 12443 - 12446
(2020/10/30)
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- Solvent-free, microwave assisted oxidation of alcohols with 4-hydroxypyridinium chlorochromate functionalized silica gel
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4-Hydroxypyridinium chlorochromate functionalized silica gel was found to be an efficient and reusable oxidant for the very fast oxidation of primary and secondary alcohols to the corresponding carbonyl compounds under solventfree conditions and microwave irradiation in excellent yields.
- AHMADI, Sayed Ali,GHALEHBANDI, Shermineh Sadat,GHAZANFARI, Dadkhoda,SHEIKHHOSSEINI, Enayatollah
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p. 283 - 289
(2020/10/06)
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- Ruthenium-Catalyzed Dehydrogenation of Alcohols with Carbodiimide via a Hydrogen Transfer Mechanism
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Ruthenium-catalyzed oxidative dehydrogenation of alcohols using carbodiimide as an efficient hydrogen acceptor has been developed. The protocol exhibits wide substrate scope with good to excellent yields. The results of the kinetic analysis indicated that the reaction mechanism includes the hydrogen transfer process and that the addition of carbodiimide is essential for the reaction system, and the resulting amidine also could react as a hydrogen acceptor.
- Sueki, Shunsuke,Matsuyama, Mizuki,Watanabe, Azumi,Kanemaki, Arata,Katakawa, Kazuaki,Anada, Masahiro
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p. 4878 - 4885
(2020/06/02)
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- Scalable Aerobic Oxidation of Alcohols Using Catalytic DDQ/HNO3
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A selective, practical, and scalable aerobic oxidation of alcohols is described that uses catalytic amounts of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and HNO3, with molecular oxygen serving as the terminal oxidant. The method was successfully applied to the oxidation of a wide range of benzylic, propargylic, and allylic alcohols, including two natural products, namely, carveol and podophyllotoxin. The conditions are also applicable to the selective oxidative deprotection of p-methoxybenzyl ethers.
- Arseniyadis, Stellios,Clavier, Louis,Copin, Chloé,Fournier, Jean,Giffard, Jean-Fran?ois,Jean, Alexandre,Katsina, Tania,Macedo Portela Da Silva, Nayane,Tamion, Rodolphe
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supporting information
p. 856 - 860
(2020/07/14)
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- NITRATION
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The present invention relates to a process for preparing a nitrated compound, comprising the step of reacting a compound (A) comprising at least one substituted or unsubstituted aromatic or heteroaromatic ring, wherein said heteroaromatic ring comprises at least one heteroatom selected from the group consisting of oxygen, sulfur, phosphor, selenium and nitrogen, with a compound of formula (I) wherein Y is selected from the group consisting of hydrogen and nitro.
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Page/Page column 36; 38; 43; 52-53; 68; 69
(2020/05/28)
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- Method for catalytically dehydrogenating and oxidizing aryl secondary alcohol into ketone
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The invention discloses a method for catalytically dehydrogenating and oxidizing aryl secondary alcohol into ketone. The method comprises the following steps: dissolving the aryl secondary alcohol inan organic solvent, and reacting at 40-120 DEG C in the presence of an acid catalyst and a cocatalyst to obtain substituted aryl ketone, wherein the acid is aryl sulfonic acid (ArSO3H), alkyl sulfonicacid (RSO3H) or boron trifluoride diethyl ether, and the cocatalyst is tertiary halogenated hydrocarbon or benzyl halogenated hydrocarbon. According to the method, a metal catalyst and an oxidizing agent are not used, the adopted catalyst is cheap and non-toxic and can tolerate water and air, the reaction condition is mild, and the method is simple to operate and high in atom economy, and can beused for large scale production.
- -
-
Paragraph 0028; 0033-0036
(2019/12/02)
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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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- 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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p. 1473 - 1481
(2019/06/11)
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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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- Connecting a carbonyl and a π-conjugated group through a: P-phenylene linker by (5+1) benzene ring formation
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A benzene ring was formed to connect a carbonyl group of various methyl ketones with a π-conjugated group through a p-phenylene linker. Methyl ketones and streptocyanines were used as the C1 and C5 sources, respectively, in the (5+1) annulation, which could form donor-π-acceptor molecules.
- Morofuji, Tatsuya,Kinoshita, Hanae,Kano, Naokazu
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supporting information
p. 8575 - 8578
(2019/07/25)
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- Transition-metal-free carbonylation of aryl halides with arylboronic acids by utilizing stoichiometric CHCl3 as the carbon monoxide-precursor
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Under transition-metal-free conditions, carbonylative Suzuki couplings of aryl halides with arylboronic acid using stoichiometric CHCl3 as the carbonyl source has been developed. The simple, efficient, and environmentally benign method was successfully applied to the synthesis of Fenofibric acid, naphthyl phenstatin, and carbon-13 labeled biaryl ketone.
- Xu, Fangning,Li, Dan,Han, Wei
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p. 2911 - 2915
(2019/06/18)
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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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- 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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- Carbonylative Suzuki coupling and alkoxycarbonylation of aryl halides using palladium supported on phosphorus-doped porous organic polymer as an active and robust catalyst
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Developing highly active catalysts with the combined advantages of molecular and solid catalysis is considered as the “Holy Grail” in the area of catalysis research. Herein, a phosphorus-doped porous polymer-immobilized palladium was successfully developed as an efficient, robust, and recyclable catalyst for the carbonylative Suzuki coupling and alkoxycarbonylation reactions of aryl halides. Rather than just as an immobilizing molecular catalyst, palladium supported on phosphorus-doped porous organic polymer exhibits even better catalytic performances than that of its analogue homogeneous catalysts in both carbonylation reactions. Moreover, the catalyst can be easily separated and reused for at least 5 times without significant loss in reactivity. Importantly, the catalyst was highly stable under carbonylation reaction conditions, and no palladium nanoparticle was observed even after the 5th reuse.
- Wan, Yali,Song, Fangxiang,Ye, Tao,Li, Guangxing,Liu, Dingfu,Lei, Yizhu
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- A Deoximation Method for Deprotection of Ketones and Aldhydes Using a Graphene-Oxide-Based Co-catalysts System
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The deoximation of a wide range of ketoximes and aldoximes to their corresponding carbonyl compounds with high yields has been achieved using graphene oxide (GO) and sodium nitrite (NaNO2) as highly efficient catalysts and air as the green oxidant under mild conditions. The mechanism of deprotection and recycling use of catalyst were revealed in deep experiment. The carboxylic acid groups on the GO were essential for high catalytic activity. (Figure presented.).
- Tong, Qiaolin,Liu, Yang,Gao, Xuezhi,Fan, Zhanfang,Liu, Tianfu,Li, Bo,Su, Dangsheng,Wang, Qinghe,Cheng, Maosheng
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supporting information
p. 3137 - 3145
(2019/05/01)
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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 0046-0049
(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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- Polystyrene-supported Pd(II)–N-heterocyclic carbene complex as a heterogeneous and recyclable precatalyst for cross-coupling of acyl chlorides with arylboronic acids
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Palladium-catalysed cross-coupling reaction of aroyl chlorides with arylboronic acids was achieved in the presence of polystyrene-supported palladium(II)–N-heterocyclic carbene complex, using K2CO3 in acetone–water, providing diaryl ketones in high yields. Furthermore, the heterogeneous catalyst could be reused up to four times without significant loss of activity.
- Movassagh, Barahman,Hajizadeh, Fatemeh,Mohammadi, Elmira
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- Synthesis, Coordination, and Catalytic Use of 1′-(Diphenylphosphino)ferrocene-1-sulfonate Anion
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Sulfonation of (diphenylphosphinothioyl)ferrocene (1) with chlorosulfonic acid in acetic anhydride affords the crude sulfonic acid Ph2P(S)fcSO3H (2; fc = ferrocene-1,1′-diyl), which can be efficiently purified and isolated after conversion to Ph2P(S)fcSO3(HNEt3) (3). Methyl triflate/P(NMe2)3 can be used to convert compound 3 to the stable sulfonate salt Ph2PfcSO3(HNEt3) (4) and Ph2P(Me)fcSO3 (5) as a minor, zwitterionic byproduct. Alternatively, compound 4 can be prepared by lithiation of 1′-(diphenylphosphino)-1-bromoferrocene (6; Ph2PfcBr) and trapping of the lithiated intermediate with SO3·NMe3. Reactions of [(LNC)PdX]2 and [(LSC)PdX]2, where X = Cl, AcO, LNC = 2-[(dimethylamino-κN)methyl]phenyl-κC1, and LSC = 2-[(methylthio-κS)methyl]phenyl-κC1, with 4 uniformly produced the bis-chelate complexes [(LNC)Pd(Ph2PfcSO3-κ2O,P)] (7) and [(LSC)Pd(Ph2PfcSO3-κ2O,P)] (8), respectively. The reaction of [PdCl2(MeCN)2] with 4 afforded the bis(phosphine) complex trans-(Et3NH)2[PdCl2(Ph2PfcSO3-κP)2] (9). Complexes 7-9 were used as defined catalyst precursors for the Suzuki-Miyaura cross-coupling of boronic acids with acyl chlorides to give ketones. Reactions of aromatic substrates in the presence of Na3PO4 and 9, the base and Pd source that showed the best performance, in a toluene/water biphasic system provided the coupling products in good yields; however, aliphatic substrates typically resulted in poor conversions. Extensive tests of the reaction scope revealed that the transposition of the substituents between the reaction partners can have a substantial effect on the yield of the coupling product in otherwise complementary reactions, which highlights the importance of the judicious choice of starting materials for this particular reaction.
- Zábransky, Martin,Císa?ová, Ivana,?těpni?ka, Petr
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p. 1615 - 1626
(2018/06/11)
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- Synthesis and palladium(II) metal chemistry of thiazoline/imidazoline derived ligands: An efficient catalyst for cross-coupling reactions of arylboronic acids with acid chlorides and aryl halides
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The synthesis, reactivity, spectroscopic characterization and catalytic activities of a series of Pd(II) complexes bearing the chelating ligands 2-(4,5-dihydrothiazol-2-yl)aniline (2) and 2-(4,5-dihydro-1H-imidazol-2-yl)aniline (3) are reported. The reactions of 2 with [Pd(COD)Cl2] in 1:1 and 1:2 (ligand into metal and metal into ligand) molar ratios afforded the mononuclear complexes, PdCl2{κ2?N,S ? 2?(4,5-dihydrothiazol-2-yl)aniline} (4), Pd{κ2?N,N’?2?(4,5-dihydrothiazol-2-yl)aniline}2 (5) and Pd{κ12?N,N’?κ22?N,S ? 2?(4,5-dihydrothiazol-2-yl)aniline}2 (6), respectively, in good yields. The neutral mononuclear palladium complexes PdCl2{κ2?N,N’?(4,5-dihydro-1H-imidazol-2-yl)aniline} (7) and Pd{κ2?N,N’?2?(4,5-dihydro-1H-imidazol-2-yl)aniline}2 (8) were synthesized using [Pd(COD)Cl2] with appropriate molar ratios. The palladium complexes 4–8 were evaluated for their catalytic activities in base assisted cross coupling reactions between acid chlorides and aryl halide with boronic acids. The complex 4 was found to be an efficient catalyst for producing unsymmetrical ketones (TOF = 19.8 min?1) while complex 7 was effective for making biaryls (TOF = 19.8 min?1).
- Sudharsan, Murugesan,Suresh
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p. 598 - 608
(2018/09/18)
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- Revealing the Structure and Reactivity of the Active Species in the FeCl2-TBHP System: Case Study on Alkene Oxidation
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A mechanism involving a quintet ferryl [FeIV=O] species has been disclosed for the oxidation of alkene under the FeCl2-TBHP system. Both theoretical and experimental results suggested that the quintet ferryl species [FeIV=O] was produced by the reaction of FeCl2 with TBHP. A Mulliken atomic spin density distribution on [FeIV=O] showed that the O site has strong radical character and could easily react with alkene to form a carbon radical intermediate. This radical could be further oxidized by TBHP to lead to the C=C bond cleavage of alkene.
- Huang, Zhiliang,Qi, Xiaotian,Lee, Jyh-Fu,Lei, Aiwen
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supporting information
p. 1635 - 1640
(2018/06/11)
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- Palladium-Catalyzed Ligand-Free Decarboxylative Coupling of α- Oxocarboxylic Acid with Aryl Diazonium Tetrafluoroborate: An Access to Unsymmetrical Diaryl Ketones
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Diaryl ketones are of much importance in organic synthesis as versatile intermediates and in industry for their useful properties. A mild and efficient palladium-catalyzed traditional ligand-free decarboxylative coupling of aryl α-keto carboxylic acid with aryl diazonium fluoroborate has been developed. A series of unsymmetrical diaryl ketones has been synthesized in moderate to good yields using this procedure. A radical pathway involving the acyl radical has been suggested.
- Panja, Subir,Maity, Pintu,Ranu, Brindaban C.
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p. 12609 - 12618
(2018/10/20)
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- Palladium-Catalyzed Carbonylative Coupling Reactions of N,N-Bis(methanesulfonyl)amides through C–N Bond Cleavage
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Palladium-catalyzed carbonylative coupling reactions of various N,N-bis(methanesulfonyl)amides with arylboronic acids through C–N bond cleavage were carried out. The reactions proceeded under mild conditions in a short period of time without any additives to afford a wide range of unsymmetrical aryl ketones in excellent yields. This is the first example of a carbonylative coupling reaction using N,N-bis(methanesulfonyl)amide as a coupling substrate.
- Lim, Minkyung,Kim, Hyeji,Ban, Jaeyoung,Son, Junghan,Lee, Jae Kyun,Min, Sun-Joon,Lee, Sang Uck,Rhee, Hakjune
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p. 5717 - 5724
(2018/09/29)
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- Acyl and Decarbonylative Suzuki Coupling of N-Acetyl Amides: Electronic Tuning of Twisted, Acyclic Amides in Catalytic Carbon-Nitrogen Bond Cleavage
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We report the Pd-catalyzed acyl and the Ni-catalyzed biaryl Suzuki-Miyaura cross-coupling of N-acetyl-amides with arylboronic acids by selective N-C(O) cleavage. Activation of the amide bond by N-acylation provides electronically destabilized, acyclic, nonplanar amide, which readily undergoes cross-coupling with a wide range of boronic acids to produce biaryl ketones or biaryls in a highly efficient manner. Most crucially, the presented results introduce N-acetyl-amides as reactive acyclic amides in the emerging manifold of transition-metal-catalyzed amide cross-coupling. The scope and origin of high selectivity are discussed. Mechanistic studies point to remodeling of amidic resonance and amide bond twist as selectivity determining features in a unified strategy for cross-coupling of acyclic amides. Structural studies, mechanistic investigations as well as beneficial effects of the N-acyl substitution on cross-coupling of amides are reported.
- Liu, Chengwei,Li, Guangchen,Shi, Shicheng,Meng, Guangrong,Lalancette, Roger,Szostak, Roman,Szostak, Michal
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p. 9131 - 9139
(2018/09/21)
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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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- α-Chlorobenzylation of Nitroarenes via Vicarious Nucleophilic Substitution with Benzylidene Dichloride: Umpolung of the Friedel-Crafts Reaction
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Readily available α,α-dichlorotoluenes enter a vicarious nucleophilic substitution (VNS) reaction with electron-deficient arenes to give α-chlorobenzylated nitrobenzenes, as well as six- and five-membered heterocycles. Oxidation of the initially formed α-chlorobenzylic carbanions instead of protonation results in formation of diaryl ketones, providing a means for overall nucleophilic C-H benzoylation of electron-deficient aromatic rings. Alternatively, benzoylated nitroarenes can be obtained via the reaction of isolated α-chlorodiarylmethanes with sodium azide.
- Brze?kiewicz, Jakub,Loska, Rafa?,Makosza, Mieczys?aw
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p. 8499 - 8508
(2018/06/25)
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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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