- One-pot synthesis of a highly disperse core-shell CuO-alginate nanocomposite and the investigation of its antibacterial and catalytic properties
-
In this study, sodium alginate was extracted from Sargassum algae, collected from coastal waters of Bushehr, Persian Gulf, Iran and used as a stabilizing and wrapping agent for CuO nanoparticles. The synthesized nanocomposite was characterized by some spectroscopic and microscopic techniques, such as IR, XRD, Uv-vis, BET, BJH, zeta potential, SEM, TEM, HR-TEM, and XPS. The antibacterial effects of the CuO-alginate nanocomposite against some bacteria, isolated from a burn wound, were evaluated. The results showed that this nanocomposite had better antibacterial effects than its components onPseudomonas aeruginosaATCC 27853,Staphylococcus aureusATCC 12600,Streptococcus pyogenesATCC 19615, andStaphylococcus epidermidisATCC 49461. Among these,Staphylococcus aureusATCC 12600 was the most sensitive one to this nanocomposite, with the lowest minimum inhibitory concentration (2.08 mg mL?1) observed. Moreover, the synthesized nanocomposite showed good catalytic activity in the oxidative coupling of carboxylic acids withN,N-dialkylformamides toward the synthesis of amides.
- Habibi, Hassan,Mansourinejhad, Sanam,Saberi, Dariush,Shadi, Ahmad
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p. 199 - 211
(2021/12/30)
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- Pd-Catalyzed Oxidative Aminocarbonylation of Arylboronic Acids with Unreactive Tertiary Amines via C-N Bond Activation
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An efficient synthesis of tertiary amides from aryl boronic acids and inert tertiary amines through the oxidative carbonylation via C(sp3)-N bond activation is presented. This protocol significantly restricts the homocoupling biarylketone product. It involves the use of a homogeneous PdCl2/CuI catalyst and a heterogeneous Pd/C based catalyst, which promotes C(sp3)-N bond activation of tertiary amines with aryl boronic acids. This process represents a ligand-free, base-free, and recyclable catalyst along with an ideal oxidant like molecular oxygen.
- Kolekar, Yuvraj A.,Bhanage, Bhalchandra M.
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p. 14028 - 14035
(2021/05/29)
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- Pd-Catalyst Containing a Hemilabile P,C-Hybrid Ligand in Amino Dicarbonylation of Aryl Halides for Synthesis of α-Ketoamides
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The amino dicarbonylation of aryl halides affording α-ketoamides with Pd catalysts is highly dependent on the stereoelectronic properties of the involved ligands. Ionic diphosphine ligand L4 can serve as precursor of a hemilabile P,C (phosphine, carbene)-hybrid ligand to form a stable Pd(II)-complex, Pd-L4. In contrast, analogues L1-L3 with a similar 1-(thiophen-3-yl)-benzimidazolyl skeleton behave as typical (mono/di)phosphines. The catalytic system resulting from the complexation of PdCl2(MeCN)2 and L4 exhibits good catalytic performance in terms of aryl iodides conversion (81-95%) and α-ketoamide selectivity (80-91%), as well as the available recyclability in the RTIL of [Bpy]BF4. The in situ FT-IR analysis reveals that the PdCl2(MeCN)2-L4 catalytic system favors the amino dicarbonylation toward α-ketoamides according to the proposed mechanism of cycle I, which involves two independent CO-insertion steps.
- Yang, Shu-Qing,Yao, Yin-Qing,Chen, Xiao-Chao,Lu, Yong,Zhao, Xiao-Li,Liu, Ye
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p. 1032 - 1041
(2021/05/07)
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- Amide Bond Formation via the Rearrangement of Nitrile Imines Derived from N-2-Nitrophenyl Hydrazonyl Bromides
-
We report how the rearrangement of highly reactive nitrile imines derived from N-2-nitrophenyl hydrazonyl bromides can be harnessed for the facile construction of amide bonds. This amidation reaction was found to be widely applicable to the synthesis of primary, secondary, and tertiary amides and was used as the key step in the synthesis of the lipid-lowering agent bezafibrate. The orthogonality and functional group tolerance of this approach was exemplified by the N-acylation of unprotected amino acids.
- Boyle, Mhairi,Elwood, Jessica M. L.,Henry, Martyn C.,Jamieson, Craig,Livingstone, Keith,Lopez-Fernandez, J. Daniel
-
supporting information
(2022/01/20)
-
- CuO-decorated magnetite-reduced graphene oxide: a robust and promising heterogeneous catalyst for the oxidative amidation of methylarenes in waterviabenzylic sp3C-H activation
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A magnetite-reduced graphene oxide-supported CuO nanocomposite (rGO/Fe3O4-CuO) was preparedviaa facile chemical method and characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), UV-vis spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), Brunauer-Emmett-Teller (BET) analysis, vibrating-sample magnetometry (VSM), and thermogravimetric (TG) analysis. The catalytic activity of the rGO/Fe3O4-CuO nanocomposite was probed in the direct oxidative amidation reaction of methylarenes with free amines. Various aromatic and aliphatic amides were prepared efficiently at room temperature from cheap raw chemicals usingtert-butyl hydroperoxide (TBHP) as a “green” oxidant and low-toxicity TBAI in water. This method combines the oxidation of methylarenes and amide bond formation into a single operation. Moreover, the synthesized nanocomposites can be separated from the reaction mixtures using an external magnet and reused in six consecutive runs without a noticeable decrease in the catalytic activity.
- Ebrahimi, Edris,Khalafi-Nezhad, Ali,Khalili, Dariush,Rousta, Marzieh
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p. 20007 - 20020
(2021/11/12)
-
- Visible light-mediated synthesis of amides from carboxylic acids and amine-boranes
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Here, a photocatalytic deoxygenative amidation protocol using readily available amine-boranes and carboxylic acids is described. This approach features mild conditions, moderate-to-good yields, easy scale-up, and up to 62 examples of functionalized amides with diverse substituents. The synthetic robustness of this method was also demonstrated by its application in the late-stage functionalization of several pharmaceutical molecules.
- Chen, Xuenian,Kang, Jia-Xin,Ma, Yan-Na,Miao, Yu-Qi
-
supporting information
p. 3595 - 3599
(2021/06/06)
-
- HMF and furfural: Promising platform molecules in rhodium-catalyzed carbonylation reactions for the synthesis of furfuryl esters and tertiary amides
-
A biomass involved rhodium-catalyzed carbonylative synthesis of furfuryl esters and tertiary amides has been developed. 5-Hydroxymethylfurfural (HMF) was used as both substrate and CO surrogate for the first time in a carbonylation reaction, and both alkyl and aryl iodides were tolerated well to afford the desired furfuryl esters in moderate to good yields. In addition, furfural was also utilized as a CO source for the synthesis of tertiary amides. A variety of tertiary amides were obtained in moderate to excellent yields with good functional groups compatibility. Notably, tertiary amines were used as the amine source through a C[sbnd]N bond cleavage pathway in the absence of additional oxidant.
- Qi, Xinxin,Zhou, Rong,Ai, Han-Jun,Wu, Xiao-Feng
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p. 215 - 221
(2019/11/25)
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- Palladium-Catalyzed N-Acylation of Tertiary Amines by Carboxylic Acids: A Method for the Synthesis of Amides
-
A palladium-catalyzed N-acylation of tertiary amines by carboxylic acids was achieved through C-N cleavage. This reaction showed a wide substrate scope. Both aromatic and aliphatic acids served well as the acylating reagents and coupled with tertiary amines to produce the corresponding amides in good to excellent yields. With the strategy, bioactive carboxylic acids were also efficiently modified, highlighting the synthetic value of the process in organic synthesis.
- Li, Zhaohui,Liu, Long,Xu, Kaiqiang,Huang, Tianzeng,Li, Xinyi,Song, Bin,Chen, Tieqiao
-
supporting information
p. 5517 - 5521
(2020/07/14)
-
- Versatile Heterogeneous Palladium Catalysts for Diverse Carbonylation Reactions under Atmospheric Carbon Monoxide Pressure
-
Herein, we report a versatile carbonylation protocol using heterogeneous Pd0 nanoparticles supported on the metal–organic frameworks (MOFs) MIL-88B-NH2 (Fe/Cr). The synthesis of a vast array of carbonyls, which includes amides, esters, carboxylic acids, and α-ketoamides, was achieved through mono- and dicarbonylation reactions. The selectivity could be controlled simply by tuning the reaction conditions. Superior activity and selectivity were recorded in some cases compared to that achieved with commercial Pd/C. However, the utility of an elaborate catalyst support is questionable and important reactivity and recyclability issues are discussed.
- Vico Solano, Marta,González Miera, Greco,Pascanu, Vlad,Inge, A. Ken,Martín-Matute, Belén
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p. 1089 - 1095
(2018/02/06)
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- Group 13 metal carbochalcogenoato complexes: Synthesis, X-ray structure analysis, and reactions
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A series of alkali metal tetrakis(carbochalcogenoato)-gallates and -indates M[M′(EOCR)4](solv.) (M?=?alkali metal; M′?=?Ga, In; E?=?S, Se) and tris(carbodithioato)aluminum, -gallates and -indates M′ (SSCR)3 (M′?=?Al, Ga, In) were prepared by the reactions of alkali metal carbochalcogenate with metal trihalogenides (M′X3; M′?=?Al, Ga, In; X?=?Cl, Br) and by those of piperidinium carbodithioates or carbodithioic and carboselenoic acids with M′X3, respectively. An X-ray molecular structure analysis revealed that they have an acetone molecule as a crystal solvent. The reactions of the potassium complexes K[M′ (EOCR)4](H2O) (E?=?S, Se) with methanol and primary and secondary amines gave the corresponding methyl ester and amides in good yields, while the reactions with iodomethane and iodine gave S- and Se-methyl chalcogenoesters RCOEMe (E?=?S, Se) in good yields. Similar reactions of the tris(carbodithioato)gallates and -indates led to the corresponding O-methyl thioesters, thioamides, and S-methyl dithioesters in moderate to good yields. Oxidation of the tetrakis- and tris-derivatives with iodine afforded the corresponding diacyl dichalcogenides (RCOE)2 (E?=?S, Se) and di(carbothioyl) disulfides in quantitative yields. These reactions appeared to occur on the carbonyl or selenium atom of the tetrakis compounds and on the sulfide sulfur or thiocarbonyl carbon atom of the tris-compounds, respectively. A possible mechanism for these I2-oxidation reactions is discussed.
- Nakata, Norio,Kato, Shinzi,Niyomura, Osamu,Ebihara, Masahiro
-
-
- Restricted amide rotation with steric hindrance induced multiple conformations
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The C–N bond character is dependent directly upon the resonance-contributor structure population driven by the delocalized nitrogen lone-pair of electrons. In the case of N, N-dibenzyl-ortho-toluamide (o-DBET), the molecule adopts subpopulations of confor
- Krishnan,Vazquez, Salvador,Maitra, Kalyani,Maitra, Santanu
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p. 148 - 151
(2017/10/23)
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- Sunlight assisted direct amide formation: Via a charge-transfer complex
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We report on the use of charge-transfer complexes between amines and carbon tetrachloride, as a novel way to activate the amine for photochemical reactions. This principle is demonstrated in a mild, transition metal free, visible light assisted, dealkylative amide formation from feedstock carboxylic acids and amines. The low absorption coefficient of the complex allows deep light penetration and thus scale up to a gram scale.
- Cohen, Irit,Mishra, Abhaya K.,Parvari, Galit,Edrei, Rachel,Dantus, Mauricio,Eichen, Yoav,Szpilman, Alex M.
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supporting information
p. 10128 - 10131
(2017/09/23)
-
- Practical Synthesis of Amides via Copper/ABNO-Catalyzed Aerobic Oxidative Coupling of Alcohols and Amines
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A modular Cu/ABNO catalyst system has been identified that enables efficient aerobic oxidative coupling of alcohols and amines to amides. All four permutations of benzylic/aliphatic alcohols and primary/secondary amines are viable in this reaction, enabling broad access to secondary and tertiary amides. The reactions exhibit excellent functional group compatibility and are complete within 30 min-3 h at rt. All components of the catalyst system are commercially available.
- Zultanski, Susan L.,Zhao, Jingyi,Stahl, Shannon S.
-
supporting information
p. 6416 - 6419
(2016/06/09)
-
- Pd/C-catalyzed aminocarbonylation of aryl iodides via oxidative C-N bond activation of tertiary amines to tertiary amides
-
This work reports oxidative N-dealkylation/carbonylation of tertiary amines to tertiary amides by using molecular oxygen as a sole oxidant using a Pd/C catalyst. This protocol is free from ligands, additives, bases, and cocatalysts. Different tertiary amines as well as aryl iodides have been examined for this transformation, providing desired products in good to excellent yield.
- Mane, Rajendra S.,Bhanage, Bhalchandra M.
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p. 1223 - 1228
(2016/02/18)
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- Palladium supported on triphenylphosphine-functionalized porous organic polymer: An efficient heterogeneous catalyst for aminocarbonylation
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An efficient route for the catalytic synthesis of aryl amides via the aminocarbonylation of aryl iodides with amines is described using palladium supported on triphenylphosphine-functionalized porous organic polymer (Pd@KAPs(Ph-PPh3)) as the catalyst. Under low carbon monoxide pressure, the catalyst exhibited remarkable activity, and only 0.5 mol% palladium loading was required to achieve moderate to excellent yields (70-97 %) of aryl amides. The catalyst can be easily separated by a simple filtration process and recycled up to seven times with only minor loss of activity. The salient features of this protocol are the simplicity in handling of catalyst, low CO pressure, good functional group tolerance, high catalytic activity, negligible palladium leaching and effective catalyst recyclability.
- Lei, Yizhu,Zhang, Xuefeng,Gu, Yanlong,Hu, Jianglin,Li, Guangxing,Shi, Kaiyi
-
-
- Room-Temperature Decarboxylative Couplings of α-Oxocarboxylates with Aryl Halides by Merging Photoredox with Palladium Catalysis
-
Enabled by merging iridium photoredox catalysis and palladium catalysis, α-oxocarboxylate salts can be decarboxylatively coupled with aryl halides to generate aromatic ketones and amides at room temperature. DFT calculations suggest that this reaction proceeds through a Pd0-PdII-PdIII pathway, in which the PdIII intermediate is responsible for reoxidizing IrII to complete the IrIII-IrIII-IrII photoredox cycle. Like a mergin': Enabled by merging iridium photoredox catalysis and palladium catalysis, palladium-catalyzed decarboxylative coupling of α-oxocarboxylates with aryl halides can proceed at room temperature. DFT calculations suggest that a Pd0-PdII-PdIII catalytic cycle is merged with an IrIII-IrIII-IrII photoredox cycle, in which PdIII is responsible for oxidizing IrII to complete the photoredox cycle.
- Cheng, Wan-Min,Shang, Rui,Yu, Hai-Zhu,Fu, Yao
-
supporting information
p. 13191 - 13195
(2015/09/15)
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- Copper-catalyzed aerobic oxidative inert C-C and C-N bond cleavage: A new strategy for the synthesis of tertiary amides
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A copper-catalyzed aerobic oxidative amidation reaction of inert C-C bonds with tertiary amines has been developed for the synthesis of tertiary amides, which are significant units in many natural products, pharmaceuticals, and fine chemicals. This method combines C-C bond activation, C-N bond cleavage, and C-H bond oxygenation in a one-pot protocol, using molecular oxygen as the sole oxidant without any additional ligands.
- Chen, Xiuling,Chen, Tieqiao,Li, Qiang,Zhou, Yongbo,Han, Li-Biao,Yin, Shuang-Feng
-
supporting information
p. 12234 - 12238
(2015/03/31)
-
- NHC-Pd complex-catalyzed double carbonylation of aryl iodides with secondary amines to α-keto amides
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A series of palladium-NHC compounds were prepared and their catalytic activity in the double carbonylation of aryl iodides to synthesize α-keto amides were examined. Palladium complexes bearing mixed NHC-phosphine exhibited high efficiency for the double carbonylation reaction. The effects of different solvents, base, temperature, carbon monoxide (CO), pressure, various amine and aryl iodides were investigated. Both electron-rich and electron-deficient aryl iodides afforded the corresponding substituted α-keto amides in moderate to good yields. A possible mechanism was also proposed. Copyright
- Zheng, Shuzhan,Wang, Yan,Zhang, Chunyan,Liu, Jianhua,Xia, Chungu
-
-
- Palladium-1,10-phenanthroline complex encaged in y zeolite: An efficient and highly recyclable heterogeneous catalyst for aminocarbonylation
-
A promising route for catalytic synthesis of amides by aminocarbonylation of aryl iodides with amines is described using a palladium-1,10-phenanthroline complex encaged in Y zeolite. Complete conversions for aryl iodides and good to excellent yields (71-97%) of various amides were obtained at low Pd loadings of 0.6 mol%. The turnover frequency (TOF) could be up to 139 h-1. A satisfactory yield was obtained even after the catalyst was reused 16 times and the total turnover number (TON) for the 16 cycles was up to 2250. As evidenced by atomic absorption spectrophotometry, UV-vis spectroscopy and X-ray photoelectron spectroscopy, the palladium complex could well nestle down in the supercages of the zeolite without leaching during the recycling process. The significantly enhanced recyclability could be attributed to the double-protection strategy provided by the ligand and the zeolite structure for Pd0 species generated in situ within supercages preventing the migration and leaching of palladium. The supported catalyst has the advantages of easy handing, good to excellent yields, and outstanding recycling capacity for aminocarbonylation reactions of aryl iodides.
- Mei, Hui,Hu, Jianglin,Xiao, Se,Lei, Yizhu,Li, Guangxing
-
-
- Asymmetric synthesis of functionalized dihydronaphthoquinones containing quaternary carbon centers via a metal-free catalytic intramolecular acylcyanation of activated alkenes
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A novel metal-free catalytic annulation was developed through a Lewis base-catalyzed asymmetric allylic alkylation and the ensuing unprecedented asymmetric intramolecular acylcyanation of alkenes. This protocol provides a unique and facile access to prepare enantioenriched densely functionalized dihydronaphthoquinones accompanied by enantiomerically pure 3,3-disubstituted phthalides bearing quaternary carbon centers.
- Zhuang, Zhe,Hu, Zhi-Peng,Liao, Wei-Wei
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p. 3380 - 3383
(2014/07/08)
-
- Branch-selective, Iridium-catalyzed hydroarylation of monosubstituted alkenes via a cooperative destabilization strategy
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Highly branch-selective, carbonyl-directed hydroarylations of monosubstituted alkenes are described. The chemistry relies upon a cationic Ir(I) catalyst modified with an electron deficient, wide bite angle bisphosphine ligand. This work provides a regioisomeric alternative to the Murai hydroarylation protocol.
- Crisenza, Giacomo E. M.,McCreanor, Niall G.,Bower, John F.
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supporting information
p. 10258 - 10261
(2014/08/05)
-
- The direct amidation of α-diketones with amines via TBHP-promoted oxidative cleavage of C(sp2)-C(sp2) bonds
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A novel and efficient direct amidation of α-diketones with amines via TBHP-promoted oxidative cleavage of C(sp2)-C(sp2) bonds has been developed. The strategy provides an alternative approach to amides under metal-free conditions.
- Zhao, Qiong,Li, Hongji,Wang, Lei
-
supporting information
p. 6772 - 6779
(2013/10/01)
-
- Quantification of the effect of conformational restriction on supramolecular effective molarities
-
The association constants for a family of 96 closely related zinc porphyrin-pyridine ligand complexes have been measured in two different solvents, toluene and 1,1,2,2-tetrachloroethane (TCE). The zinc porphyrin receptors are equipped with phenol side arms, which can form intramolecular H-bonds with ester or amide side arms on the pyridine ligands. These association constants were used to construct 64 chemical double mutant cycles, which measure the free energy contributions of intramolecular H-bonding interactions to the overall stability of the complexes. Measurement of association constants for the corresponding intermolecular H-bonding interactions allowed determination of the effective molarities (EM) for the intramolecular interactions. Comparison of ligands that feature amide H-bond acceptors and ester H-bonds at identical sites on the ligand framework show that the values of EM are practically identical. Similarly, the values of EM are practically identical in toluene and in TCE. However, comparison of two ligand series that differ by one degree of torsional freedom shows that the values of EM for the flexible ligands are an order of magnitude lower than for the corresponding rigid ligands. This observation holds for a range of different supramolecular architectures with different degrees of receptor-ligand complementarity and suggests that in general the cost of freezing a rotor in supramolecular complexes is of the order of 5 kJ/mol.
- Adams, Harry,Chekmeneva, Elena,Hunter, Christopher A.,Misuraca, Maria Cristina,Navarro, Cristina,Turega, Simon M.
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p. 1853 - 1863
(2013/04/10)
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- Tandem oxidative amidation of benzyl alcohols with amine hydrochloride salts catalysed by iron nitrate
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A tandem process for the oxidative amidation of benzyl alcohols with amine hydrochloride salts has been developed using inexpensive Fe(NO3) 3 as the catalyst, air and aqueous t-butyl hydroperoxide as oxidants. A wide range of benzamides have been synthesized under mild conditions. This greener amide formation method provides an economical and practical assess to benzamides from readily available and inexpensive starting materials.
- Ghosh, Subhash Chandra,Ngiam, Joyce S.Y.,Seayad, Abdul M.,Tuan, Dang Thanh,Johannes, Charles W.,Chen, Anqi
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p. 4922 - 4925
(2013/09/02)
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- Copper-catalyzed oxidative coupling of carboxylic acids with N,N-dialkylformamides: An approach to the synthesis of amides
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A new synthetic approach for amide bond formation through the oxidative coupling of N,N-dialkylformamides with carboxylic acids was achieved by using a copper catalyst. Furthermore, this method was applied in the coupling of chiral amino acids in which the stereochemistry was retained in the resulting amide products. A new synthetic approach to amide bond formation through the oxidative coupling of N,N-dialkylformamides with carboxylic acids was achieved by using a copper catalyst and aqueous tert-butyl hydroperoxide (TBHP) as a sacrificial oxidant. Furthermore, this method was applied in the coupling of chiral amino acids in which the stereochemistry was retained in the resulting amide products. Copyright
- Kumar, P. Santhosh,Kumar, G. Sathish,Kumar, R. Arun,Reddy, N. Veera,Rajender Reddy
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supporting information
p. 1218 - 1222
(2013/04/10)
-
- Silicadiphenyl phosphinite (SDPP)/Pd(0) nanocatalyst for efficient aminocarbonylation of aryl halides with POCl3 and DMF
-
Silicadiphenyl phosphinite (SDPP) as a new phosphorylated silica and catalytic amounts of Pd(II) generates nano SDPP/Pd(0) catalyst for the efficient aminocarbonylation of aryl halides in the presence of POCl3 and N,N-dimethylformamide (DMF). Amides are obtained in high yields from aryl iodides and also activated aryl bromides, chlorides.
- Iranpoor, Nasser,Firouzabadi, Habib,Motevalli, Somayeh
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experimental part
p. 69 - 74
(2012/03/09)
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- Pd(ii)-catalyzed decarboxylative cross-coupling of oxamic acids with potassium phenyltrifluoroborates under mild conditions
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A novel Pd-catalyzed decarboxylative cross-coupling of oxamic acids with potassium phenyltrifluoroborates has been realized under mild reaction conditions. This method provides an efficient access to N-mono- or N,N-disubstituted benzamides and benzoates.
- Li, Mingzong,Wang, Cong,Fang, Ping,Ge, Haibo
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supporting information; experimental part
p. 6587 - 6589
(2011/06/25)
-
- Efficient palladium-catalysed carbonylative and Suzuki-Miyaura cross-coupling reactions with bis(di-tert-butylphosphino)-o-xylene
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The use of the ligand bis(di-tert-butylphosphino)-o-xylene (dtbpx) in palladium-catalysed carbonylative and Suzuki-Miyaura cross-coupling reactions is described. Aryl and vinyl halides readily entered into the carbonylative catalytic cycle affording carboxylic acids, amides as well as primary, secondary and tertiary esters, respectively, in good yields. Aryl iodides, bromides and chlorides gave high yields of biphenyl products upon reaction with both activated and unactivated boronic acids.
- McNulty, James,Nair, Jerald J.,Sliwinski, Marcin,Robertson, Al J.
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scheme or table
p. 2342 - 2346
(2009/08/17)
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- A synthesis of sulfonamide analogs of platensimycin employing a palladium-mediated carbonylation strategy
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The monodentate ligand 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phenyl-6-phospha-adamantane (PA-Ph) is shown to be highly effective in palladium-catalyzed carbonylative cross-coupling. Aryl and vinyl halides were efficiently converted to carboxylic acids, amides and to primary, secondary, and tertiary esters, respectively. Application of the Pd(OAc)2/PA-Ph (1:1) catalyst system proved critical in the methoxycarbonylation of a functionalized nitroresorcinol halide, allowing convenient access to novel platensimycin sulfonamide analogs.
- McNulty, James,Nair, Jerald J.,Capretta, Alfredo
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scheme or table
p. 4087 - 4091
(2009/12/01)
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- Ketopyrroles useful as ligands in organic iridium compositions
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The present invention provides novel ketopyrroles having structure XXIV wherein R2 is independently at each occurrence a deuterium atom, a halogen, a nitro group, an amino group, a C3-C40 aromatic radical, a C1-C50 aliphatic radical, or a C3-C40 cyclcoaliphatic radical; “a” is an integer from 0 to 3; and X1 and X2 are independently at each occurrence a bromine atom, a hydroxy group, or the group OR10, and wherein the group R10 is independently at each occurrence a deuterium atom, a halogen, a nitro group, an amino group, a C3-C40 aromatic radical, a C1-C50 aliphatic radical, or a C3-C40 cyclcoaliphatic radical. Ketopyrroles XXIV are useful ligands for the preparation of Type (1) and Type (2) organic iridium compositions. In one aspect, the present invention provides deuterated analogs of XXIV. Organic iridium compositions are useful in the preparation optoelectronic devices, such as OLED devices and photovoltaic devices exhibiting enhanced performance characteristics.
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Page/Page column 35-36
(2008/06/13)
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- Efficient carbonylation reactions in phosphonium salt ionic liquids: Anionic effects
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(Formula Presented) Application of phosphonium salt ionic liquids in the carbonylation of aryl and vinyl halides is presented. Anionic effects were uncovered with the bromide ionic liquid emerging as the superior media. Acid bromide intermediates were detected in control experiments providing an extended view on the overall catalytic cycle involved. Solvent-free product isolation and recycling of the ionic liquid containing active Pd-catalyst are also demonstrated.
- McNulty, James,Nair, Jerald J.,Robertson, Al
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p. 4575 - 4578
(2008/03/12)
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- Low pressure Pd-catalyzed carbonylation in an ionic liquid using a multiphase microflow system
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A low pressure microflow system was developed for palladium-catalyzed multiphase carbonylation reactions in an ionic liquid. The microflow system resulted in superior selectivity and higher yields in carbonylative Sonogashira coupling and amidation reactions of aryl iodides compared to the conventional batch system. The Royal Society of Chemistry 2006.
- Rahman, Md. Taifur,Fukuyama, Takahide,Kamata, Naoya,Sato, Masaaki,Ryu, Ilhyong
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p. 2236 - 2238
(2007/10/03)
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- N-heterocyclic inhibitors of TNF-α expression
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N-heterocyclic compounds that block cytokine production via inhibition of p38 kinase are disclosed. In one embodiment, compounds of the present invention are represented by Formula I: Methods of production, pharmaceutical compositions and methods of treating conditions associated with inappropriate p38 kinase activity or TNF-α expression utilizing compounds of the present invention are also disclosed.
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-
-
- One pot direct synthesis of amides or oxazolines from carboxylic acids using Deoxo-Fluor reagent
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A mild and highly efficient one pot-one step condensation and/or condensation-cyclization of various acids to amides and/or oxazolines using Deoxo-Fluor reagents is described. Parallel syntheses of various free fatty acids with 2-amino-2,2-dimethyl-1-propanol resulted with excellent yields.
- Kangani, Cyrous O.,Kelley, David E.
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p. 8917 - 8920
(2007/10/03)
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- Double carbonylation of aryl iodides with diethylamine catalyzed by dinuclear palladium complexes
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Dinuclear palladium complexes bridged by a novel PNNP ligand, N,N ′-bis[(2-diphenylphosphino)phenylformamidinate (dpfam), were found to be very efficient and selective catalysts for the double carbonylation of iodobenzene with diethylamine using K3PO4 as base and 1,4-dioxane as solvent with a TON up to 105 and selectivity of 96%.
- Tsukada, Naofumi,Ohba, Yoichi,Inoue, Yoshio
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p. 436 - 443
(2007/10/03)
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- N-heterocyclic inhibitors of TNF-alpha expression
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N-heterocyclic compounds that block cytokine production via inhibition of p38 kinase are disclosed. In one embodiment, compounds of the present invention are represented by Formula I: Methods of production, pharmaceutical compositions and methods of treating conditions associated with inappropriate p38 kinase activity or TNF-α expression utilizing compounds of the present invention are also disclosed.
- -
-
-
- N- heterocyclic inhibitors of TNF-alpha expression
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N-heterocyclic compounds that block cytokine production via inhibition of p38 kinase are disclosed. In one embodiment, compounds of the present invention are represented by Formula I: Methods of production, pharmaceutical compositions and methods of treating conditions associated with inappropriate p38 kinase activity or TNF-α expression utilizing compounds of the present invention are also disclosed.
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-
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- Pd-benzothiazole carbene catalysed carbonylation of aryl halides in ionic liquids
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The carbonylations of aryl halides with the Pd-carbene catalyst 1 were studied both in molecular solvents and in ionic liquids (ILs). Among the ILs, tetrabutylammonium bromide (TBAB) was found to give better results. Under these conditions the catalyst, when recovered and reused, did not show a significant decrease of activity. The role of TBAB on the catalyst stability is discussed.
- Calò, Vincenzo,Giannoccaro, Potenzo,Nacci, Angelo,Monopoli, Antonio
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p. 152 - 157
(2007/10/03)
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- N-acylbenzotriazoles: Neutral acylating reagents for the preparation of primary, secondary, and tertiary amides
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Readily available N-acylbenzotriazoles 2a-q efficiently acylate aqueous ammonia and primary and secondary amines to give primary, secondary, and tertiary amides in good to excellent yields. The wide applicability of the procedure is illustrated by the preparation of (i) α-hydroxyamides from α-hydroxy acids and of (ii) perfluoroalkylated amides.
- Katritzky,He,Suzuki
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p. 8210 - 8213
(2007/10/03)
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- Fungicides for the control of take-all disease of plants
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A method of controlling Take-All disease of plants by applying a fungicide of the formula STR1 wherein Z1 and Z2 are C and are part of an aromatic ring which is benzothiophene; and A is selected from --C(X)-amine wherein the amine is an unsubstituted, monosubstituted or disubstituted amino radical, --C(O)--SR3, --NH--C(X)R4, and --C(=NR3)--XR7 ; B is --Wm --Q(R2)3 or selected from O-tolyl, 1-naphthyl, 2-naphthyl, and 9-phenanthryl, each optionally substituted with halogen or R4 ; Q is C, Si, Ge, or Sn; W is --C(R3)p H(2-p) --; or when Q is C, W is selected from --C(R3)p H(2-p), --N(R3)m H(1-m)--, --S(O)p--, and --O--; X is 0 or S; n is 0, 1, 2, or 3; m is 0 or 1; p is 0, 1, or 2; each R and R2 is independently defined herein; R3 is C1 -C4 alkyl; R4 is C1 -C4 alkyl, haloalkyl, alkoxy, alkylthio, alkylamino, or dialkylamino; and R7 is C1 -C4 alkyl, haloalkyl, or phenyl, optionally substituted with halo, nitro, or R4 ; or an agronomic salt thereof.
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- THE DIRECT CONVERSION OF CARBOXYLIC ACIDS TO CARBOXAMIDES VIA REACTION WITH UNSOLVATED BIS(DIORGANOAMINO) MAGNESIUM REAGENTS
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It has been found that unsolvated bis(diorganoamino) magnesium compounds react smoothly with carboxylic acids to give the corresponding carboxamides directly in good to excellent yields.
- Sanchez, Ramiro,Vest, Gary,Despres, Lisa
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p. 2909 - 2914
(2007/10/02)
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- Long-acting pyrethrum/pyrethroid based pesticides with silicone stabilizers
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Pesticidal compositions based on nontoxic, naturally unstable insecticides (pyrethrum, synthetic pyrethroids and mixtures thereof) include a liquid alkyl aryl silicone polymer which stabilizes the insecticide to provide an extended effective killing life. The compositions additionally include a synergist to provide an immediate killing action and an antioxidant to protect the insecticide against destruction by oxygen. Ultraviolet protectants and insect repellents may also be included. Applications include control of insect pests to animals and plants and general purpose insect control. Exemplary formulations are given for compositions to be applied as sprays, dips, powdered or dusts, foggers and shampoos.
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- Palladium-Catalysed Double Carbonylation of Aryl Halides To Give α-Keto Amides. Mechanistic Studies
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Various aryl halides are catalytically converted into α-keto amides and amides on treatment with secondary amines and carbon monoxide.Palladium complexes containing tertiary phosphine ligands, particularly diphenylmethylphosphine and 1,4-bis(diphenylphosphino)butane, are most effective among other transition-metal complexes.Detailed examination of factors controlling the reaction rates and selectivity for α-keto amide formation revealed the following characteristics of the reactions. (a) Reactivity of phenyl halide decreases in the order PhI > PhBr >> PhCl. (b) Oxidative addition of phenyl bromide constitutes the rate-determining step in double carbonylation of phenyl bromide, whereas in the reaction of phenyl iodide the rate determinig step is associated with the reaction of a catalitically active palladium species with carbon monoxide. (c) Introduction of an electron-withdrawing substituent into the para position of phenyl halide enhances the reactivity but decreases the selectivity for α-keto amide. (d) Employment of amines of high basicity (pKb Et2NH > piperidine > hexamethyleneimine > Me2NH > pyrrolidine probably reflects the decrease in steric bulkiness of amines. (f) Although primary amines are in general not suitable for the double carbonylation, tert-butylamine can be used because of its inertness to the product α-keto amide.Reactivity of trans-PdPh(I)(PMePh2)2 and trans-Pd(COPh)I(PMePh2)2, supposed intermediates in the catalytic reaction of PhI, toward amines and CO was examined.The relative reactivity of six secondary amines with the benzoylpalladium complex increasing in the order Pr2NH Et2NH piperidine Me2NH hexamethyleneimine pyrrolidine was found to be inversely correlated with decreasing selectivity order for α-keto amide formation in the catalytic systems.On the basis of the experimental results, a mechanism consisting of two catalytic cycles to produce α-keto amides and amides has been proposed.
- Ozawa, Fumiyuki,Soyama, Hidehiko,Yanagihara, Hisayoshi,Aoyama, Issei,Takino, Hiroaki,et al.
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p. 3235 - 3245
(2007/10/02)
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- CATALYTIC DOUBLE CARBONYLATION OF ORGANOHALOGEN COMPOUNDS PROMOTED BY PALLADIUM COMPLEXES
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Various organohalogen compounds can be catalytically converted into α-keto amides on reaction with carbon monoxide and amines.Tertiary phosphine-coordinated palladium compounds are particularly suitable as the double carbonylation catalyst.
- Ozawa, Fumiyuki,Soyama, Hidehiko,Yamamoto, Takakazu,Yamamoto, Akio
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p. 3383 - 3386
(2007/10/02)
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- Reaction of Diazonium Salts with Transition Metals. 6. Preparation of Mixed Acid Anhydrides from Arenediazonium Salts and Sodium Carboxylates under Palladium(0) Catalysis
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The palladium(0)-catalyzed reaction of arenediazonium tetrafluoroborates with carbon monoxide and sodium carboxylates in acetonitrile at 25 deg C gave mixed acid anhydrides, ArCOOCOR (Ar = 3-Me-Ph, 4-Me-Ph, 2-MeO-Ph, 4-Br-Ph, 4-I-Ph, 3-NO2-Ph, 4-NO2-Ph, and Ph; R = H, Me, Et, t-Bu, and Ph) in good yields.Homoaromatic acid anhydrides, (ArCO)2O, were obtained by heating of ArCOOCOMe at 100-120 deg C under vacuum.ArCOOCO-t-Bu can be utilized to obtain the corresponding arenecarboxamides by the reaction with some amines.
- Kikukawa, Kiyoshi,Kono, Kiyoshi,Nagira, Kazuhiko,Wada, Fumio,Matsuda, Tsutomu
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p. 4413 - 4416
(2007/10/02)
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- INVESTIGATIONS ON N,N-DIALKYLBENZAMIDES BY NMR SPECTROSKOPY. PART II. A COMPARISON OF BARRIERS TO ROTATION ABOUT THE AMIDE C-N BOND IN PARA SUBSTITUTED N,N-DIMETHYL- AND N,N-DIETHYLBENZAMIDES
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The barriers to rotation about the amide C-N bond in a series of para-substituted N,N-dimethyl- and N,N-diethylbenzamides have been compared.A method allowing the detection using standard measurement conditions of small differences between barriers to rotation has been proposed.It has been stated that the barriers to rotation in N,N-dimethylbenzamides are ca. 2 kJ/mole higher than those in the corresponding N,N-diethylbenzamides and that the differences ΔMe-Et are at least partially due to those in entropies of activation.It has been observed that ΔMe-Et increases with the increasing electron donating properties of the para substituent .The observed phenomena have been rationalized in terms of steric interactions in the ground state of rotation in the molecules under investigation.
- Gryf-Keller, Adam,Terpinski, Jacek,Zajaczkowska-Terpinska, Ewa
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p. 1465 - 1471
(2007/10/02)
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