- Nitrogen Atom Transfer Catalysis by Metallonitrene C?H Insertion: Photocatalytic Amidation of Aldehydes
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C?H amination and amidation by catalytic nitrene transfer are well-established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C?H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd?N) with a diradical nitrogen ligand that is singly bonded to PdII. Despite the subvalent nitrene character, selective C?H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N3SiMe3. Based on these results, a photocatalytic protocol for aldehyde C?H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C?H nitrogen atom transfer offers facile access to primary amides after deprotection.
- Schmidt-R?ntsch, Till,Verplancke, Hendrik,Lienert, Jonas N.,Demeshko, Serhiy,Otte, Matthias,Van Trieste, Gerard P.,Reid, Kaleb A.,Reibenspies, Joseph H.,Powers, David C.,Holthausen, Max C.,Schneider, Sven
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- A “universal” catalyst for aerobic oxidations to synthesize (hetero)aromatic aldehydes, ketones, esters, acids, nitriles, and amides
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Functionalized (hetero)aromatic compounds are indispensable chemicals widely used in basic and applied sciences. Among these, especially aromatic aldehydes, ketones, carboxylic acids, esters, nitriles, and amides represent valuable fine and bulk chemicals, which are used in chemical, pharmaceutical, agrochemical, and material industries. For their synthesis, catalytic aerobic oxidation of alcohols constitutes a green, sustainable, and cost-effective process, which should ideally make use of active and selective 3D metals. Here, we report the preparation of graphitic layers encapsulated in Co-nanoparticles by pyrolysis of cobalt-piperazine-tartaric acid complex on carbon as a most general oxidation catalyst. This unique material allows for the synthesis of simple, functionalized, and structurally diverse (hetero)aromatic aldehydes, ketones, carboxylic acids, esters, nitriles, and amides from alcohols in excellent yields in the presence of air.
- Bartling, Stephan,Beller, Matthias,Chandrashekhar, Vishwas G.,Jagadeesh, Rajenahally V.,Rabeah, Jabor,Rockstroh, Nils,Senthamarai, Thirusangumurugan
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supporting information
p. 508 - 531
(2022/02/11)
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- Aerobic oxidation of primary amines to amides catalyzed by an annulated mesoionic carbene (MIC) stabilized Ru complex
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Catalytic aerobic oxidation of primary amines to the amides, using the precatalyst [Ru(COD)(L1)Br2] (1) bearing an annulated π-conjugated imidazo[1,2-a][1,8]naphthyridine-based mesoionic carbene ligand L1, is disclosed. This catalytic protocol is distinguished by its high activity and selectivity, wide substrate scope and modest reaction conditions. A variety of primary amines, RCH2NH2 (R = aliphatic, aromatic and heteroaromatic), are converted to the corresponding amides using ambient air as an oxidant in the presence of a sub-stoichiometric amount of KOtBu in tBuOH. A set of control experiments, Hammett relationships, kinetic studies and DFT calculations are undertaken to divulge mechanistic details of the amine oxidation using 1. The catalytic reaction involves abstraction of two amine protons and two benzylic hydrogen atoms of the metal-bound primary amine by the oxo and hydroxo ligands, respectively. A β-hydride transfer step for the benzylic C-H bond cleavage is not supported by Hammett studies. The nitrile generated by the catalytic oxidation undergoes hydration to afford the amide as the final product. This journal is
- Yadav, Suman,Reshi, Noor U Din,Pal, Saikat,Bera, Jitendra K.
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p. 7018 - 7028
(2021/11/17)
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- 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
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supporting information
p. 3595 - 3599
(2021/06/06)
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- Application of acylthiourea compound in preparation of medicines for resisting enterovirus
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The invention discloses an application of an acylthiourea compound in preparation of an anti-enterovirus drug, and belongs to the technical field of medicines. The structure of the acylthiourea compound of the present invention is as shown in the general
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Paragraph 0053-0056
(2021/11/03)
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- Ring Opening/Site Selective Cleavage in N-Acyl Glutarimide to Synthesize Primary Amides
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A LiOH-promoted hydrolysis selective C-N cleavage of twisted N-acyl glutarimide for the synthesis of primary amides under mild conditions has been developed. The reaction is triggered by a ring opening of glutarimide followed by C-N cleavage to afford primary amides using 2 equiv of LiOH as the base at room temperature. The efficacy of the reactions was considered and administrated for various aryl and alkyl substituents in good yield with high selectivity. Moreover, gram-scale synthesis of primary amides using a continuous flow method was achieved. It is noted that our new methodology can apply under both batch and flow conditions for synthetic and industrial applications.
- Govindan, Karthick,Lin, Wei-Yu
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supporting information
p. 1600 - 1605
(2021/03/03)
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- Unlocking Amides through Selective C–N Bond Cleavage: Allyl Bromide-Mediated Divergent Synthesis of Nitrogen-Containing Functional Groups
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We report a new set of reactions based on the unlocking of amides through simple treatment with allyl bromide, creating a common platform for accessing a diverse range of nitrogen-containing functional groups such as primary amides, sulfonamides, primary amines, N-acyl compounds (esters, thioesters, amides), and N-sulfonyl esters. The method has potential industrial applicability, as demonstrated through gram-scale syntheses in batch and in a continuous flow system.
- Govindan, Karthick,Chen, Nian-Qi,Chuang, Yu-Wei,Lin, Wei-Yu
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supporting information
p. 9419 - 9424
(2021/11/30)
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- Efficient nitriding reagent and application thereof
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The invention discloses an efficient nitriding reagent and application thereof, wherein the nitriding reagent comprises nitrogen oxide, an active agent, a reducing agent and an organic solvent. By applying the nitriding reagent, nitrogen-containing compounds such as amide, nitrile and the like can be produced, and the method is simple in condition, low in waste discharge amount and simple in reaction equipment.
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-
Paragraph 0269-0271
(2021/03/31)
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- Aerobic oxidation of primary benzylic amines to amides and nitriles catalyzed by ruthenium carbonyl clusters carrying N,O-bidentate ligands
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Four trinuclear ruthenium carbonyl clusters, (6-BrPyCHRO)2Ru3(CO)8 (R = 4-OCH3C6H4, 1a; R = 4-BrC6H4, 1b) and (2-OC6H4-HCN-C6H4R)2Ru3(CO)8 (R = 4-OCH3, 2a; R = 4-Br, 2b), were synthesized from the reactions of Ru3(CO)12 with the corresponding N,O-bidentate ligands (two pyridyl alcohols and two Schiff bases) respectively in a ratio of 1:2. Three new complexes 1b, 2a and 2b have been fully characterized by elemental analysis, FT-IR, NMR and X-ray crystallography. The catalytic activity of these ruthenium complexes for the aerobic oxidation of primary benzylic amines to amides and nitriles in the presence of t-BuOK was investigated, of which the Schiff base complex 2a was found to exhibit the highest activity.
- Dong, Qing,Han, Zhangang,Hao, Zhiqiang,Li, Ying,Lin, Jin,Lu, Guo-Liang,Meng, Lizhen,Yan, Xinlong
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p. 3480 - 3487
(2020/04/02)
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- Synthesis of CF3-containing isoindolinone derivatives through rhodium-catalyzed oxidative coupling of benzamides with 2-trifluoromethylacrylate
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The oxidative coupling of benzamides with methyl 2- trifluoromethylacrylate proceeds smoothly under rhodium(III) catalysis to produce trifluoromethyl-substituted isoindolinone derivatives. The catalyst system [CpERhCl2]2/AgSbF6 is effective for the oxidat
- Yoshimoto, Risa,Morisaka, Hideaki,Usuki, Yoshinosuke,Shibata, Yu,Tanaka, Ken,Satoh, Tetsuya
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supporting information
p. 1481 - 1483
(2020/12/31)
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- Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles
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The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.
- Jiao, Ning,Liu, Jianzhong,Qiu, Xu,Song, Song,Wei, Jialiang,Wen, Xiaojin,Zhang, Cheng,Zhang, Ziyao
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supporting information
p. 281 - 285
(2020/01/28)
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- Supported palladium catalyzed aminocarbonylation of aryl iodides employing bench-stable CO and NH3surrogates
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A simple, efficient and phosphine free protocol for carbonylative synthesis of primary aromatic amides under polystyrene supported palladium (Pd?PS) nanoparticle (NP) catalyzed conditions has been demonstrated. Herein, instead of using two toxic and difficult to handle gases simultaneously, we have employed the solid, economical, bench stable oxalic acid as the CO source and ammonium carbamate as the NH3source in a single pot reaction. For the first time, we have applied two non-gaseous surrogates simultaneously under heterogeneous catalyst (Pd?PS) conditions for the synthesis of primary amides using an easy to handle double-vial (DV) system. The developed strategy showed a good functional group tolerance towards a wide range of aryl iodides and afforded primary aromatic amides in good yields. The Pd?PS catalyst was easy to separate and can be recycled up to four consecutive runs with small loss in catalytic activity. We have successfully extended the scope of the methodology to the synthesis of isoindole-1,3-diones from 1,2-dihalobenzene, 2-halobenzoates and 2-halobenzoic acid following double and single carbonylative cyclization approaches.
- Bains, Rohit,Das, Pralay,Kumar, Ajay,Ram, Shankar,Shaifali,Sheetal
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supporting information
p. 7193 - 7200
(2020/10/02)
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- Transamidation for the Synthesis of Primary Amides at Room Temperature
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Various primary amides have been synthesized using the transamidation of various tertiary amides under metal-free and mild reaction conditions. When (NH4)2CO3 reacts with a tertiary amide bearing an N-electron-withdrawing substituent, such as sulfonyl and diacyl, in DMSO at 25 °C, the desired primary amide product is formed in good yield with good funcctional group tolerance. In addition, N-tosylated lactam derivatives afforded their corresponding N-tosylamido alkyl amide products via a ring opening reaction.
- Chen, Jiajia,Lee, Sunwoo,Xia, Yuanzhi
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supporting information
(2020/05/05)
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- Copper catalyzed reduction of azides with diboron under mild conditions
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We report herein the first Cu catalyzed reduction of azides with B2pin2 (pin = pinacolato) as the reductant under very mild conditions. A series of primary amines and amides were obtained in moderate to excellent yields with high chemoselectivity and good functional group tolerance. This reaction can be performed with a cheap copper salt, a simple NHC ligand and a diboron reagent.
- Chen, Yang,Deng, Shengqi,Gao, Yihua,Liu, Liwen,Liu, Yu,Lu, Da,Wang, Qianwen,Zhang, Xiao
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supporting information
(2020/02/27)
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- Method for preparing acidamide from terminal olefin
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The invention belongs to the technical field of preparation of a fine chemical engineering product and synthesis of a medicine intermediate, and particularly relates to a method for preparing acidamide from terminal olefin. According to the method, the terminal olefin is used as a raw material; firstly, dibromohydantoin is added; stirring is performed; then, iodine and ammonium hydroxide or organic amine is added to obtain the corresponding acidamide. The method provided by the invention can be used for converting aromatic ring substituted terminal olefin; the method is also very effective onthe conversion of aliphatic terminal olefin into the acidamide. Compared with the prior art, the method has the advantages that the raw materials are cheap and can be easily obtained; the cost is low;the conditions are mild; the operation is easy; the toxicity of the used reagents is small; good substrate compatibility is realized; great cost and environmental-friendly advantages and wide application prospects are realized.
- -
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Paragraph 0011; 0012; 0013
(2019/04/04)
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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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- Modular Continuous Flow Synthesis of Imatinib and Analogues
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A modular continuous flow synthesis of imatinib and analogues is reported. Structurally diverse imatinib analogues are rapidly generated using three readily available building blocks via a flow hydration/chemoselective C-N coupling sequence. The newly developed continuous flow hydration and amidation modules each exhibit a broad scope with good to excellent yields. Overall, the method described does not require solvent switches, in-line purifications, or packed-bed apparatuses due to the judicious manipulation of flow setups and solvent mixtures.
- Fu, Wai Chung,Jamison, Timothy F.
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supporting information
p. 6112 - 6116
(2019/08/26)
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- Ti-superoxide catalyzed oxidative amidation of aldehydes with saccharin as nitrogen source: Synthesis of primary amides
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A new heterogeneous catalytic system (Ti-superoxide/saccharin/TBHP) has been developed that efficiently catalyzes oxidative amidation of aldehydes to produce various primary amides. The protocol employs saccharin as amine source and was found to tolerate a wide range of substrates with different functional groups. Moderate to excellent yields, catalyst reusability and operational simplicity are the main highlights. A possible mechanism and the role of the catalyst in oxidative amidation have also been discussed.
- Kamble, Rohit B.,Mane, Kishor D.,Rupanawar, Bapurao D.,Korekar, Pranjal,Sudalai,Suryavanshi, Gurunath
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p. 724 - 728
(2020/01/23)
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- Highly Selective Ruthenium-Catalyzed Direct Oxygenation of Amines to Amides
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Reports on aerobic oxidation of amines to amides are rare, and those reported suffer from several limitations like poor yield or selectivity and make use of pure oxygen under elevated pressure. Herein, we report a practical and an efficient ruthenium-catalyzed synthetic protocol that enables selective oxidation of a broad range of primary aliphatic, heterocyclic and benzylic amines to their corresponding amides, using readily available reagents and ambient air as the sole oxidant. Secondary amines instead, yield benzamides selectively as the sole product. Mechanistic investigations reveal intermediacy of nitriles, which undergo hydration to afford amide as the final product.
- Ray, Ritwika,Hazari, Arijit Singha,Chandra, Shubhadeep,Maiti, Debabrata,Lahiri, Goutam Kumar
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supporting information
p. 1067 - 1071
(2018/01/03)
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- Mechanistic Studies of Palladium-Catalyzed Aminocarbonylation of Aryl Chlorides with Carbon Monoxide and Ammonia
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Mechanistic information on a reliable, palladium-catalyzed aminocarbonylation of aryl chlorides with ammonia is reported. The reaction occurs with ethylene complex 1 as catalyst, and mechanistic information was gained by isolation of catalytic intermediates and kinetic measurements, including the first mechanistic data on the oxidative addition of aryl chloride to a palladium(0) complex in the presence of CO. Arylpalladium and phenacylpalladium halide intermediates were synthesized, and kinetic measurements of the formation and reactions of these intermediates were undertaken to determine the mechanism of the oxidative addition of aryl bromides and chlorides to a Pd(0) dicarbonyl compound in the presence of CO and the mechanism of the reaction of ammonia with a Pd(II) phenacyl complex to form benzamide. The oxidative addition of aryl chlorides and aryl bromides was determined to occur with rate-limiting reaction of the haloarene with a three-coordinate Pd(0) species bearing a bidentate phosphine and one CO ligand. A primary 13C kinetic isotope effect suggested that this step involves cleavage of the carbon-halogen bond. Our data show that the formation of benzamide from the reaction of phenacylpalladium halide complexes with ammonia occurs by a pathway involving reversible displacement of chloride from a phenacylpalladium chloride complex by ammonia, deprotonation of the bound ammonia to form a phenacylpalladium amido complex, and reductive elimination to form the C-N bond. Consistent with this mechanism, the reaction of an aryl palladium amido complex with CO formed the corresponding primary benzamide. A catalyst deactivation pathway involving the formation of a Pd(I) dimer also was elucidated.
- Wang, Justin Y.,Strom, Alexandra E.,Hartwig, John F.
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supporting information
p. 7979 - 7993
(2018/06/11)
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- One-Pot Preparation of Aromatic Amides, 4-Arylthiazoles, and 4-Arylimidazoles from Arenes
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Simple treatment of arenes with α-bromoacetyl chloride and AlCl3, followed by the reaction with molecular iodine and aq. NH3, thioamides, or amidines gave the corresponding primary aromatic amides, 4-arylthiazoles, or 4-arylimidazoles in good yields, respectively. Aryl α-bromomethyl ketones are the key intermediates in those reactions. Primary aromatic amides were formed from arenes through the reaction of aryl α-bromomethyl ketones with molecular iodine and aq. NH3, and 4-arylthiazoles and 4-arylimidazoles were formed from arenes through the reactions of aryl α-bromomethyl ketones with thioamides and amidines, respectively, in one pot under transition-metal-free conditions.
- Yamamoto, Takahiro,Togo, Hideo
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p. 4187 - 4196
(2018/08/21)
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- Ruthenium-catalyzed oxidative decyanative cross-coupling of acetonitriles with amines in air: A general access to primary to tertiary amides under mild conditions
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Catalyzed by Ru and in the presence of air and nucleophiles such as amines or ammonia, activation of the C-CN bond could be easily achieved under mild conditions to produce primary to tertiary amides in good to excellent yields. The use of accessible and functional-group-tolerant starting materials, a cheap, low-loading and recyclable catalyst, ligand-free conditions and excellent product yields are the advantages of the method. Moreover, compared with the Ritter reaction and hydration methods, this novel reaction has more comprehensive application scope.
- Wang, Yuguang,Wu, Zhongli,Li, Qin,Zhu, Bingchun,Yu, Lei
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p. 3747 - 3757
(2017/09/07)
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- I2-Catalyzed Oxidative Amidation of Benzylamines and Benzyl Cyanides under Mild Conditions
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We report a novel and efficient method for the oxidation of benzylic carbons (amines and cyanides) into corresponding benzamides using a catalytic amount of I2 and TBHP as the green oxidant via the C-H bond cleavage of the benzylic carbon under mild reaction conditions. According to the literature survey, this is the first report for the oxidative amidation of benzylamines and decyanation of benzyl cyanides in one pot under metal-free conditions.
- Nageswara Rao, Sadu,Reddy, N. Naresh Kumar,Samanta, Supravat,Adimurthy, Subbarayappa
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p. 13632 - 13642
(2017/12/26)
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- A Convenient Palladium-Catalyzed Aminocarbonylation of Aryl Iodides to Primary Amides under Gas-Free Conditions
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A convenient procedure for the synthesis of aromatic primary amides through palladium-catalyzed aminocarbonylation of aryl iodides has been developed. With ammonium hydrogen carbonate as the solid nitrogen source and formic acid as the liquid CO source, a variety of primary amides were obtained in moderate to excellent yields under gas-free conditions.
- Qi, Xinxin,Ai, Han-Jun,Cai, Chuang-Xu,Peng, Jin-Bao,Ying, Jun,Wu, Xiao-Feng
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supporting information
p. 7222 - 7225
(2018/01/02)
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- 1,3-Dibromo-5,5-dimethylhydantoin mediated oxidative amidation of terminal alkenes in water
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A variety of terminal alkenes were converted to the corresponding amides in yields of 25 to 86% in water via treatment with 1,3-dibromo-5,5-dimethylhydantoin, followed by reaction with molecular iodine and aq. NH3 (or amine) in one pot. This metal- and organic solvent-free protocol is not only suitable for styrene derivatives, but also, for the first time, works well on terminal aliphatic alkenes.
- Ma, Chunhua,Fan, Guojie,Wu, Ping,Li, Zhi,Zhou, Yang,Ding, Qingjie,Zhang, Wei
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p. 9889 - 9894
(2017/12/12)
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- Highly efficient synthesis of primary amides: Via aldoximes rearrangement in water under air atmosphere catalyzed by an ionic ruthenium pincer complex
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The transformation of aldoximes to primary amides has been evaluated using pincer ruthenium complexes a-c, among which the ionic Ru catalyst a proved to be the most efficient in water under air atmosphere. A variety of (hetero)arene aldoximes proceeded smoothly to afford amides in high yields with good functional group compatibilities. Furthermore, a direct synthetic route of amides from aldehydes, hydroxylamine hydrochloride and sodium carbonate was also described with broad substrates including conjugated and aliphatic aldehydes. This protocol is operationally simple and proceeds with a low catalyst loading (0.5 mol%).
- Yang, Fa-Liu,Zhu, Xinju,Rao, Dun-Kang,Cao, Xiao-Niu,Li, Ke,Xu, Yan,Hao, Xin-Qi,Song, Mao-Ping
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p. 37093 - 37098
(2016/05/24)
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- A method of from [...] amide
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The invention discloses a method for synthesizing amides from oxime. The method is characterized by adding oxime, water and a water-soluble iridium complex catalyst to a reaction vessel, cooling a reactant to the room temperature after the reaction mixture reacts at 80-120 DEG C for several hours, removing water through selective evaporation, and obtaining a target product through column separation. Compared with existing methods for synthesizing amides through oxime rearrangement in water through transition metal catalysis, the method has the advantages that the used catalyst is low in load and does not contain phosphine ligands severely polluting the environment, so that the reaction can be carried out in the air, without nitrogen protection; therefore the reaction meets the green chemical requirements and has an extensive development prospect.
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-
Paragraph 0033-0037
(2017/01/31)
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- A method for synthesis of amides
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The invention discloses a synthesizing method for an amide compound shown in formula (III). The synthesizing method comprises the following steps: adopting replacing acetonitrile shown in formula (I) and amines compound shown in formula (II) as raw materials in air atmosphere; adopting Ru/C as a catalyst; conducting reaction in solvent to generate the amide compound shown in formula (III); the solvent is one selected from ethyl alcohol, furanidine, methyl sulfoxide and o-dichlorobenzene. The synthesizing method being novel synthesizing route is simple to operate, convenient in post-treatment, high in product yield, and good in product purity; particularly, the catalyst and the solvent can be used repeatedly; air is taken as oxidant; not only production cost is reduced, but also the method is environmental-friendly, and very suitable for large-scale industrialization production.
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Paragraph 0071-0074
(2017/01/31)
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- Iodine-catalyzed oxidative C-C bond cleavage for benzoic acids and benzamides from alkyl aryl ketones
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Iodine-catalyzed oxidative C-C bond cleavage has been performed for the facile synthesis of both benzoic acids and benzamides from readily available alkyl aryl ketones. Additionally benzylidene acetones and phenylacetylenes were also converted to the corresponding aromatic acids under the same conditions. This approach features the use of inexpensive iodine as a catalyst, broad substrate scope and open air conditions.
- Sathyanarayana, Pochampalli,Upare, Atul,Ravi, Owk,Muktapuram, Prathap Reddy,Bathula, Surendar Reddy
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p. 22749 - 22753
(2016/03/15)
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- Rh(III)-Catalyzed Redox-Neutral Annulation of Primary Benzamides with Diazo Compounds: Approach to Isoquinolinones
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Reported herein is a Rh-catalyzed redox-neutral annulation of primary benzamides with diazo compounds, representing an efficient and economic protocol to isoquinolinones. The procedure exhibited good functional group tolerability, scalability, and regioselectivity, obviating the need for oxidants, and only environmentally benign N2 and H2O were released. Further utilization of the method provided an alternative route to functionalized isoquinolines.
- Wu, Youzhi,Sun, Peng,Zhang, Kaifan,Yang, Tie,Yao, Hequan,Lin, Aijun
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p. 2166 - 2173
(2016/03/15)
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- Design, synthesis and fungicidal activity of N-substituted benzoyl-1,2,3,4-tetrahydroquinolyl-1-carboxamide
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To find a new lead compound with high biological activity, a series of N-substituted benzoyl-1,2,3,4-tetrahydroquinolyl-1-carboxamide were designed using linking active substructures method. The target compounds were synthesized from substituted benzoic acid by four steps and their structures were confirmed by 1H NMR, IR spectrum and elemental analysis. The in vitro bioassay results indicated that some target compounds exhibited excellent fungicidal activities, and the position of the substituents played an important role in fungicidal activities. Especially, compound 5n, exhibited better fungicidal activities than the commercial fungicide flutolanil against two tested fungi Valsa Mali and Sclerotinia sclerotiorum, with EC50 values of 3.44 and 2.63 mg/L, respectively. And it also displayed good in vivo fungicidal activity against S. sclerotiorum with the EC50 value of 29.52 mg/L.
- Lei, Peng,Xu, Yan,Du, Juan,Yang, Xin-Ling,Yuan, Hui-Zhu,Xu, Gao-Fei,Ling, Yun
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p. 2544 - 2546
(2016/07/07)
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- Direct Transformation of Ethylarenes into Primary Aromatic Amides with N -Bromosuccinimide and I2-Aqueous NH3
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A variety of ethylarenes were converted into the corresponding primary aromatic amides in good yields via treatment with N-bromosuccinimide in the presence of a catalytic amount of 2,2′-azobis(isobutyronitrile) in a mixture of ethyl acetate and water, acetonitrile and water, or chloroform and water, followed by reaction with molecular iodine and aq NH3 in one pot. It was found that aryl α-bromomethyl ketones and/or aryl methyl ketones were formed at the first reaction step and their iodoform-type reaction occurred at the second reaction step to provide primary aromatic amides. The present reaction is a useful and practical transition-metal-free method for the preparation of primary aromatic amides from ethylarenes. (Chemical Equation Presented).
- Shimokawa, Shohei,Kawagoe, Yuhsuke,Moriyama, Katsuhiko,Togo, Hideo
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supporting information
p. 784 - 787
(2016/03/01)
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- Visible Light-Induced Iodine-Catalyzed Transformation of Terminal Alkynes to Primary Amides via C≡C Bond Cleavage under Aqueous Conditions
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The visible light-induced iodine-catalyzed oxidative cleavage of the C≡C bond for transforming terminal alkynes into primary amides in the presence of ammonia under aqueous conditions is described. This metal-free protocol which ensued via initial hydroamination of the acetylene bond followed by liberation of diiodomethane (CH2I2) was found to be applicable to aromatic, heteroaromatic and aliphatic alkynes.
- Dighe, Shashikant U.,Batra, Sanjay
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p. 500 - 505
(2016/02/12)
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- Synthesis of Nitriles from Aldoximes and Primary Amides Using XtalFluor-E
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The dehydration reaction of aldoximes and amides for the synthesis of nitriles using [Et2NSF2]BF4 (XtalFluor-E) is described. Overall, the reaction proceeds rapidly (normally 1 h) at room temperature in an environmentally benign solvent (EtOAc) with only a slight excess of the dehydrating agent (1.1 equiv). A broad scope of nitriles can be prepared, including chiral nonracemic ones. In addition, in a number of cases, further purification of the nitrile after the workup was not required.
- Keita, Massaba,Vandamme, Mathilde,Paquin, Jean-Fran?ois
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p. 3758 - 3766
(2015/11/28)
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- Phosphinoferrocene ureas: Synthesis, structural characterization, and catalytic use in palladium-catalyzed cyanation of aryl bromides
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Phosphinoferrocene ureas Ph2PfcCH2NHCONR2, where NR2 = NH2 (1a), NHMe (1b), NMe2 (1c), NHCy (1d), and NHPh (1e); the analogous thiourea Ph2PfcCH2NHCSNHPh (1f); and the acetamido derivative Ph2PfcCH2NHCOMe (1g) (Cy = cyclohexyl, fc = ferrocene-1,1′-diyl) were prepared via three different approaches starting from Ph2PfcCH2NH2·HCl (3·HCl) or Ph2PfcCHO (4). The reactions of the representative ligand 1e with [PdCl2(cod)] (cod = cycloocta-1,5-diene) afforded [PdCl(μ-Cl)(1e-κP)2]2 or [PdCl2(1e-κP)2]2 depending on the metal-to-ligand stoichiometry, whereas those with [PdCl(η3-C3H5)]2 and [PdCl(LNC)]2 produced the respective bridge cleavage products, [PdCl(η3-C3H5)(1e-κP)] and [PdCl(LNC)(1e-κP)] (LNC = [(2-dimethylamino-κN)methyl]phenyl-κC1). Attempts to involve the polar pendant in coordination to the Pd(II) center were unsuccessful, indicating that the phosphinoferrocene ureas 1 bind Pd(II) preferentially as modified phosphines rather than bifunctional donors. When combined with palladium(II) acetate, the ligands give rise to active catalysts for Pd-catalyzed cyanation of aryl bromides with potassium hexacyanoferrate(II). Optimization experiments revealed that the best results are obtained in 50% aqueous dioxane with a catalyst generated from 1 mol % of palladium(II) acetate and 2 mol % of 1e in the presence of 1 equiv of Na2CO3 as the base and half molar equivalent of K4[Fe(CN)6]·3H2O. Under such optimized conditions, bromobenzenes bearing electron-donating substituents are cyanated cleanly and rapidly, affording the nitriles in very good to excellent yields. In the case of substrates bearing electron-withdrawing groups, however, the cyanation is complicated by the hydrolysis of the formed nitriles to the respective amides, which reduces the yield of the desired primary product. Amine- and nitro-substituted substrates are cyanated only to a negligible extent, the former due to their metal-scavenging ability.
- ?koch, Karel,Císa?ová, Ivana,?těpni?ka, Petr
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p. 1942 - 1956
(2015/06/08)
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- Synthesis of primary amides by aminocarbonylation of aryl/hetero halides using non-gaseous NH3 and CO sources
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Abstract A practically simple method for the synthesis of primary amides via the palladium-catalysed aminocarbonylation of aromatic halides by using solid sources of gaseous ammonia and carbon monoxide is described. The system tolerated a wide variety of hindered and functionalized aryl/hetero halides and afforded good to excellent yields (69-94%) of the amide. Pharmacologically active Exalamide and Pyrazinecarboxamide were synthesised in high yields to demonstrate the effectiveness of this method.
- Suresh,Baburajan, Poongavanam,Ahmed, Mansur
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supporting information
p. 4864 - 4867
(2015/07/28)
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- Palladium-catalyzed synthesis of primary benzamides from aryl bromides via a cyanation and hydration sequence
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An interesting and effective procedure for the synthesis of benzamides from aryl bromides has been developed. In the presence of a palladium catalyst, various primary benzamides have been produced in moderate to excellent yields in a one-pot one-step manner.
- Sharif, Muhammad,Wu, Xiao-Feng
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p. 21001 - 21004
(2015/03/30)
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- Rearrangement of aldoximes to amides in water under air atmosphere catalyzed by water-soluble iridium complex [Cp*Ir(H2O) 3][OTf]2
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In the presence of the water-soluble iridium complex [Cp*Ir(H 2O)3][OTf]2, a variety of aldoximes, including aromatic, aliphatic, conjugated unsaturated and non-conjugated unsaturated, were converted into their corresponding amides in water with good to excellent yields. Further, the one-pot synthesis of amides from aldehydes, hydroxylamine hydrochloride and sodium carbonate via a tandem condensation-rearrangement reaction in water was also accomplished. Compared with the reported organometallic catalysts for the rearrangement of aldoximes to amides in water, the present catalyst exhibited some advantages such as being phosphorus ligand-free, having low catalyst loading, and operational convenience under air atmosphere. This journal is the Partner Organisations 2014.
- Sun, Chunlou,Qu, Panpan,Li, Feng
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p. 988 - 996
(2014/04/03)
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- Copper-catalyzed aerobic oxidative C-C bond cleavage for C-N bond formation: From ketones to amides
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A novel copper-catalyzed aerobic oxidative C(CO)-C(alkyl) bond cleavage reaction of aryl alkyl ketones for C-N bond formation is described. A series of acetophenone derivatives as well as more challenging aryl ketones with long-chain alkyl substituents could be selectively cleaved and converted into the corresponding amides, which are frequently found in biologically active compounds and pharmaceuticals.
- Tang, Conghui,Jiao, Ning
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supporting information
p. 6528 - 6532
(2014/06/24)
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- Synthesis of primary Amides via Copper-Catalyzed Aerobic Decarboxylative ammoxidation of Phenylacetic Acids and α-Hydroxyphenylacetic acids with Ammonia in water
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A Cu2O-catalyzed aerobic oxidative decarboxylative ammoxidation to primary benzamides from phenylacetic acids and a-hydroxyphenylacetic acids is developed. A variety of primary benzamides could be prepared smoothly, in good to excellent yields, by means of a one-pot domino protocol combining decarboxylation, dioxygen activation, oxidative C-H bond functionalization, and amidation reactions.
- Song, Qiuling,Feng, Qiang,Yang, Kai
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supporting information
p. 624 - 627
(2014/04/03)
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- ANTIMICROBIAL SUBSTITUTED THIAZOLES AND METHODS OF USE
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Disclosed are compositions having activity against MRSA and/or VRSA, and methods of using the compositions to treat microbial infections.
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Paragraph 0049
(2014/05/08)
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- Discovery and characterization of potent thiazoles versus methicillin- and vancomycin-resistant Staphylococcus aureus
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Methicillin- and vancomycin-resistant Staphylococcus aureus (MRSA and VRSA) infections are growing global health concerns. Structure-activity relationships of phenylthiazoles as a new antimicrobial class have been addressed. We present 10 thiazole derivatives that exhibit strong activity against 18 clinical strains of MRSA and VRSA with acceptable PK profile. Three derivatives revealed an advantage over vancomycin by rapidly eliminating MRSA growth within 6 h, and no derivatives are toxic to HeLa cells at 11 μg/mL.
- Mohammad, Haroon,Mayhoub, Abdelrahman S.,Ghafoor, Adil,Soofi, Muhammad,Alajlouni, Ruba A.,Cushman, Mark,Seleem, Mohamed N.
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p. 1609 - 1615
(2014/03/21)
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- A novel oxidative procedure for the synthesis of benzamides from styrenes and amines under metal-free conditions
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An interesting procedure for the oxidative synthesis of amides from styrenes and amines has been developed. Various primary amides were formed in moderate yields (25-81%). Secondary amides can be produced in moderate yields as well (41-68%). Notably, no transition metal catalyst was needed for this transformation. This is the first example of oxidative transformation of styrenes to benzamides. This journal is the Partner Organisations 2014.
- Sharif, Muhammad,Gong, Jin-Long,Langer, Peter,Beller, Matthias,Wu, Xiao-Feng
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p. 4747 - 4750
(2014/05/06)
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- NOVEL THIOUREA OR UREA DERIVATIVE, PREPARATION METHOD THEREOF, AND PHARMACEUTICAL COMPOSITION FOR PREVENTING OR TREATING AIDS, CONTAINING SAME AS ACTIVE INGREDIENT
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Disclosed are novel thiourea or urea derivatives inhibitory of HIV activity. Also provided are a method for preparing the thiourea or urea derivatives, and a pharmaceutical composition for the prophylaxis or therapy of AIDS comprising the derivatives. Hav
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Paragraph 0186; 0187; 0188
(2013/04/24)
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- NOVEL THIOUREA OR UREA DERIVATIVE, PREPARATION METHOD THEREOF, AND PHARMACEUTICAL COMPOSITION FOR PREVENTING OR TREATING AIDS, CONTAINING SAME AS ACTIVE INGREDIENT
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Disclosed are novel thiourea or urea derivatives inhibitory of HIV activity. Also provided are a method for preparing the thiourea or urea derivatives, and a pharmaceutical composition for the prophylaxis or therapy of AIDS comprising the derivatives. Hav
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Paragraph 0049
(2013/05/09)
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- Lewis acid-catalyzed oxidation of benzylamines to benzamides
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A novel Lewis acid-catalyzed oxidation of benzylamines to the corresponding amides has been developed. Using 10 mol% of ZnBr2 or FeCl 3 as the catalyst and TBHP as the oxidant, amides were produced under mild conditions. The Royal Society of Chemistry 2012..
- Wu, Xiao-Feng,Bheeter, Charles Beromeo,Neumann, Helfried,Dixneuf, Pierre H.,Beller, Matthias
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supporting information
p. 12237 - 12239
(2013/01/16)
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- A general palladium-catalyzed aminocarbonylation of phenols to primary benzamides via in situ generation of aryl nonaflates
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Amides in mind! A novel palladium-catalyzed amino-carbonylation of in situ formed aryl nonaflates to give primary amides in moderate to excellent yields has been developed (see scheme). Copyright
- Wu, Xiao-Feng,Neumann, Helfried,Beller, Matthias
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experimental part
p. 419 - 422
(2012/02/04)
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- Selective palladium-catalyzed aminocarbonylation of aryl halides with CO and ammonia
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(Figure Presented) Wake up and smell the ammonia: A palladium-catalyzed aminocarbonylation of aryl halides with CO and ammonia has been developed (see scheme). Primary amides are accessible, under mild reaction conditions, in moderate to excellent yields.
- Wu, Xiao-Feng,Neumann, Helfried,Beller, Matthias
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scheme or table
p. 9750 - 9753
(2010/10/19)
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- Development of a second generation palladium catalyst system for the aminocarbonylation of aryl halides with CO and ammonia
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Applying a palladium/dppf catalyst system, enabled the synthesis of primary amides from aryl halides and ammonia under mild reaction conditions in moderate to excellent yields.
- Wu, Xiao-Feng,Neumann, Helfried,Beller, Matthias
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experimental part
p. 2168 - 2172
(2011/06/11)
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- One-pot synthesis of symmetrical 1,3-diarylureas or substituted benzamides directly from benzylic primary alcohols and effective oxidation of secondary alcohols to ketones using phenyliodine diacetate in combination with sodium azide
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Benzylic primary alcohols can be directly converted into symmetrical 1,3-diarylureas or substituted benzamides via an one-pot oxidative reaction using the combined reagent of phenyliodine diacetate and sodium azide. This new reaction constitutes a step-economical way to prepare symmetric 1,3-diarylureas or substituted benzamides depending upon the substituents on the phenyl rings of starting alcohols. The sodium acetate generated in situ from the ligand exchange between phenyliodine diacetate and sodium azide plays the pivotal role in the formation of 1,3-diarylureas. In addition, it is also found that various secondary alcohols can be readily oxidized to their corresponding ketones in excellent yields using the same reagent system of phenyliodine diacetate and sodium azide. Generally, secondary alcohols are preferentially oxidized to the corresponding ketones in the presence of primary ones with the limited amounts of phenyliodine diacetate and sodium azide.
- Li, Xiao-Qiang,Wang, Wei-Kun,Han, Yi-Xin,Zhang, Chi
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experimental part
p. 2588 - 2598
(2010/12/25)
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