- Visible-Light-Induced Palladium-Catalyzed Dehydrogenative Carbonylation of Amines to Oxalamides
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The palladium-catalyzed oxidative carbonylation of amines toward the synthesis of oxalamides has been established around 30 years ago and it usually needs the presence of (over)stoichiometric amounts of oxidant. In this work, the first transformation of this type in which the oxidant was replaced by visible light is described. The new approach uses a simple robust Pd complex, which can even be partially recycled. A mechanistic reason is provided and supported by control experiments and EPR studies, showing that PdI was formed and Pd0 was the active species. Both nitrogen- and the intermediate acyl radical can be detected. Moreover, the formation of hydrogen was confirmed by gas GC.
- Meyer, Tim,Rabeah, Jabor,Brückner, Angelika,Wu, Xiao-Feng
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supporting information
p. 5642 - 5647
(2021/03/09)
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- Synthesis of oxalamides by acceptorless dehydrogenative coupling of ethylene glycol and amines and the reverse hydrogenation catalyzed by ruthenium
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A sustainable, new synthesis of oxalamides, by acceptorless dehydrogenative coupling of ethylene glycol with amines, generating H2, homogeneously catalyzed by a ruthenium pincer complex, is presented. The reverse hydrogenation reaction is also accomplished using the same catalyst. A plausible reaction mechanism is proposed based on stoichiometric reactions, NMR studies, X-ray crystallography as well as observation of plausible intermediates.
- Ben-David, Yehoshoa,Diskin-Posner, Yael,Milstein, David,Zhou, Quan-Quan,Zou, You-Quan
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p. 7188 - 7193
(2020/07/23)
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- CuI/Oxalic Diamide-Catalyzed Cross-Coupling of Thiols with Aryl Bromides and Chlorides
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We report a general copper-catalyzed cross-coupling of thiols with aryl halides by using N-aryl-N′-alkyl oxalic diamide (L3) or N,N′-dialkyl oxalic diamide (L5) as the ligand. Both aryl and alkyl thiols can be coupled with unactivated aryl bromides and chlorides to give the desired products in good yields. Furthermore, this system features a broad substrate scope and good tolerance of functional groups. Importantly, the oxalic diamides are stable and can be prepared easily from commercially available and cheap starting materials.
- Chen, Chia-Wei,Chen, Yi-Ling,Reddy, Daggula Mallikarjuna,Du, Kai,Li, Chao-En,Shih, Bo-Hao,Xue, Yung-Jing,Lee, Chin-Fa
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supporting information
p. 10087 - 10091
(2017/08/01)
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- Tuning Synergistic Effect of Au-Pd Bimetallic Nanocatalyst for Aerobic Oxidative Carbonylation of Amines
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The activation and utilization of carbon monoxide is of crucial importance to C1 chemistry. Various catalytic transformation processes have been developed and studied in the last century, and oxidative carbonylation of amines is one of them. Catalysts that have been identified to date for the oxidative carbonylation of amines generally show relatively low activity and/or selectivity. Herein, a metal-organic framework (MOF), i.e., MOF-253 prepared from AlCl3·6H2O and 2,2′-bipyridine-5,5′-dicarboxylic acid, was employed as a support of gold-palladium bimetallic nanoparticles (Au-Pd/MOF) for the oxidative carbonylation of amines under mild conditions. Compared to palladium or gold monometallic catalysts, higher catalytic activity (turnover frequency up to 2573 h-1) and selectivity in the carbonylation of amines were achieved by Au-Pd/MOF bimetallic catalysts through adjusting the molar ratio of gold and palladium within the framework. A breathing effect of Au-Pd/MOF in the catalytic process was further observed from kinetic profiles and powder X-ray diffraction for the first time.
- Duan, Hui,Zeng, Yongfei,Yao, Xin,Xing, Pengyao,Liu, Jia,Zhao, Yanli
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p. 3671 - 3677
(2017/05/01)
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- CO-use CO2 Method for synthesizing N, N - dialkyl oxalate
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The invention provides a method for synthesizing N,N-dialkyl oxamide by using CO2. According to the method, in an organic or inorganic solvent, one-step synthetic reaction is performed on the CO2 and organic amine to synthesize the N,N-dialkyl oxamide, with N,N-dialkyl urea and water as byproducts, in the presence of a certain catalyst and under a certain reaction condition that the reaction pressure is 10-80atm and the reaction temperature is 100-200 DEG C. The invention discloses the method for synthesizing the N,N-dialkyl oxamide by using the CO2. According to the method, a valuable and toxic metal catalyst and a toxic and explosive gas in the prior art are not used, and reactants, products, and added components in a system are safe and environment-friendly; the yield is considerable; technically, an improvement room exists; a safe and environment-friendly new method is provided for preparing the N,N-dialkyl oxamide.
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Paragraph 0042; 0043; 0044; 0045; 0046
(2016/11/17)
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- Selective oxidative carbonylation of amines to oxamides and ureas catalyzed by palladium complexes
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A new process for converting secondary amines into N,N,N′,N′- tetraalkyloxamides under CO pressure, catalyzed by homogeneous palladium complexes in the presence of 1,4-dichloro-2-butene (DCB) as an oxidant, has been developed. The mechanism of the oxidative double-carbonylation process, consisting of the oxidation of Pd(0) to Pd(11) with DCB through a β-chloride elimination of the η3-(chloromethyl) allylpalladiuni(11) intermediate, the formation of mono- and bis(carbamoyl)palladium species, and a reductive elimination of the two carbamoyl ligands, is proposed based on studies of the behavior of carbamoylpalladium complexes. When primary amines are employed with DCB as the oxidant, N,N′-dialkyloxamide is catalytically produced, whereas urea is exclusively produced when iodine is used as the oxidant. The reaction of an N-monopropylcarbamoylpalladium complex with propylamine under CO gave N,N′-dipropylurea, whereas a treatment with diethylamine yielded unsymmetrical N,N-diethyl-N′-propylurea, implying the intermediate formation of propyl isocyanate that is converted into the urea upon a reaction with the added amine. A kinetic study on the reaction of chloro-N- propylcarbamoylpalladium with triethylamine suggested a process proceeding through a base-promoted dcprolonalion of the N-monoalkylcarbamoyl ligand to form propyl isocyanate.
- Hiwatari, Kozo,Kayaki, Yoshihito,Okita, Koshi,Ukai, Tomohiro,Shimizu, Isao,Yamamoto, Akio
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p. 2237 - 2250
(2007/10/03)
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- A novel PdCl2/ZrO2-SO42- catalyst for synthesis of carbamates by oxidative carbonylation of amines
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At 170°C and ca. 4.0 MPa, oxidative carbonylation of aromatic amines to synthesize corresponding carbamates over a novel PdCl2/ZrO2-SO42- catalyst could proceed with high conversion and selectivity.
- Shi, Feng,Deng, Youquan,SiMa, Tianlong,Yang, Hongzhou
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p. 525 - 528
(2007/10/03)
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- First gold(I) complex-catalyzed oxidative carbonylation of amines for the syntheses of carbamates
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At 200 °C and 5 MPa of initial total pressure, the oxidative carbonylation of amines for the synthesis of the corresponding carbamates by Au(I) complexes as catalysts was conducted with excellent conversion and selectivity.
- Shi,Deng
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p. 443 - 444
(2007/10/03)
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- A novel approach for the one-pot preparation of α-amino amides by pd-catalyzed double carbohydroamination
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A new domino reaction sequence, a palladium-catalyzed double carbohydroamination, which involves double carbonylation, amine condensation, and hydrogenation from an aryl iodide(1), a primary amine (2), and synthetic gas has been realized as a novel synthetic means for the one-pot synthesis of α-amino amides (3).
- Lin, Yong-Shou,Alper, Howard
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p. 779 - 781
(2007/10/03)
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- A novel ZrO2-SO42- supported palladium catalyst for syntheses of disubstituted ureas from amines by oxidative carbonylation
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The syntheses of disubstituted ureas by carbonylation of a series of amines in the presence of a sulfate modified zirconia supported palladium catalyst was investigated at an initial total pressure of 4.0 MPa and 135°C. High conversions and yields were achieved for the synthesis of symmetric dialkylureas. This supported catalyst could also be easily separated and recovered after reaction.
- Shi, Feng,Deng, Youquan,SiMa, Tianlong,Yang, Hongzhou
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p. 2161 - 2163
(2007/10/03)
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- Total synthesis of a marine imidazole alkaloid, clathridine A
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The first total synthesis of clathridine A (8), a marine imidazole alkaloid, was achieved by using a novel regioselective condensation as a key step, in which preclathridine A (2) was treated with 1-methylparabanic acid (11) in the presence of a silylating agent. (C) 2000 Elsevier Science Ltd.
- Ohta, Shunsaku,Tsuno, Naoki,Maeda, Kazushi,Nakamura, Seikou,Taguchi, Norio,Yamashita, Masayuki,Kawasaki, Ikuo
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p. 4623 - 4627
(2007/10/03)
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- Reactivity of Carbamoyl Radicals. A New, General, Convenient Free-Radical Synthesis of Isocyanates from Monoamides of Oxalic Acid
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A new, general, simple synthesis of isocyanates was developed by oxidation of monoamides of oxalix acid with peroxydisulfate catalyzed by Ag and Cu salts.The reaction was carried out in a two-phase system (water and an organic solvent), and it is suitable also for practical applications, due to the simple experimental conditions and the inexpensive as well as nontoxic reagents.The first example of homolytic intramolecular aromatic carbamoylation is also reported.
- Minisci, Francesco,Fontana, Francesca,Coppa, Fausta,Yan, Yong Ming
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p. 5430 - 5433
(2007/10/02)
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- SmI2 Promoted Coupling Reaction of Isocyanates to Oxamides
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Oxamides were obtained in moderate to good yields by the reaction of isocyanates with the SmI2/HMPA/THF system under mild conditions.The system also caused desulfurization of isothiocyanates to give isocyanides in good yields.
- Liu, Yun-Shan,Bei, Mei-Zhi,Zhou, Zhi-Hua,Takaki, Ken,Fujiwara, Yuzo
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p. 1143 - 1144
(2007/10/02)
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- OXALSAEUREDERIVATE DURCH OXIDATIVE KUPPLUNG VON KOHLENMONOXID AN NICKEL
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Carbon monoxide is oxidatively coupled by ligand nickel(II) compounds with secondary, primary amines and with alkali alkoxides to give oxalic acid derivatives.In the case of secondary amines the CO coupling can be run catalytically by adding oxidants like copper(II) salts.The yield of oxalic esters depends on the types of ligands and anions.
- Hoberg, Heinz,Fananas, F. Javier,Riegel, Hans Josef
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p. 267 - 272
(2007/10/02)
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- SYNTHESES AND REACTIONS OF SILYLATED DIAMINOSULFANES
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The synthesis of unsymmetrically substituted silylated diaminosulfane 3 a - 3 e with different alkylgroups at both nitrogen atoms are described; the reactions of 3 a, 3 b with oxalyl chloride yields the unsymmetrically substituted 2,5-dialkyl-1,2,5-thiadi
- Neidlein, Richard,Lehr, Werner
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p. 1179 - 1185
(2007/10/02)
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- Deoxygenation and Desulfurization of Organic Compounds via Transition Metal Atom Cocondensation
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Reactions resulting from the cocondensation of transition metal atoms with a variety of oxygen- and sulfur-containing organic compounds are surveyed.Alkenes are the major or exclusive volatile products when epoxides are reacted with Ti, V, Cr, Co, and Ni atoms. 2,6-Dimethylpyridine-N-oxide and dimethyl sulfoxide undergo deoxygenation upon cocondensation with chromium, but diisopropyl ether and decyl methyl ether do not.Dibenzyl ether yields bis(η6-dibenzyl ether)chromium(0) with Cr atoms, but dibenzyl sulfide undergoes desulfurization.Cyclohexanone and cycloheptanone afford low yields of reductive coupling and aldol products when cocondensed with Cr, Co, and Ni atoms.Nitro- and nitrosoarenes are deoxygenated to coupled azo and azoxy products with Cr atoms.Carbazole (3) is obtained from 2-nitrosobiphenyl, implicating nitrene or nitrenoid intermediates.Whereas isocyanides are not formed from isocyanates and metal atoms, they are produced when isothiocyanates are cocondensed with Cr and V atoms.
- Togashi, Shigeo,Fulcher, John G.,Cho, Bong Rae,Hasegawa, Minoru,Gladysz, J.A.
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p. 3044 - 3053
(2007/10/02)
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