- Selective aerobic oxidation of methanol in the coexistence of amines by nanoporous gold catalysts: Highly efficient synthesis of formamides
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Holey gold: Highly selective aerobic oxidation of methanol over alkylamines was achieved with a reusable nanoporous gold (AuNPore) catalyst that was fabricated from a Au-Ag alloy (see figure). This excellent chemoselectivity enabled direct N-formylation of alkylamines from a mixture of methanol and amines. The remarkable catalytic activity was attributed to the synergistic effect between gold and the residual silver remaining in the AuNPore. Copyright
- Tanaka, Shinya,Minato, Taketoshi,Ito, Eisuke,Hara, Masahiko,Kim, Yousoo,Yamamoto, Yoshinori,Asao, Naoki
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Read Online
- Manganese-Catalyzed N-Formylation of Amines by Methanol Liberating H2: A Catalytic and Mechanistic Study
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The first example of a base metal (manganese) catalyzed acceptorless dehydrogenative coupling of methanol and amines to form formamides is reported herein. The novel pincer complex (iPr-PNHP)Mn(H)(CO)2 catalyzes the reaction under mild conditions in the absence of any additives, bases, or hydrogen acceptors. Mechanistic insight based on the observation of an intermediate and DFT calculations is also provided.
- Chakraborty, Subrata,Gellrich, Urs,Diskin-Posner, Yael,Leitus, Gregory,Avram, Liat,Milstein, David
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Read Online
- (o-Phenylenediamino)borylstannanes: Efficient Reagents for Borylation of Various Alkyl Radical Precursors
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(o-Phenylenediamino)borylstannanes were newly synthesized to achieve radical boryl substitutions of a variety of alkyl radical precursors. Dehalogenative, deaminative, decharcogenative, and decarboxylative borylations proceeded in the presence of a radica
- Suzuki, Kensuke,Nishimoto, Yoshihiro,Yasuda, Makoto
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supporting information
p. 3968 - 3973
(2020/12/30)
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- Chromium-catalysed efficient: N -formylation of amines with a recyclable polyoxometalate-supported green catalyst
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A simple and efficient protocol for the formylation of amines with formic acid, catalyzed by a polyoxometalate-based chromium catalyst, is described. Notably, this method shows excellent activity and chemoselectivity for the formylation of primary amines; diamines have also been successfully employed. Importantly, the chromium catalyst is potentially non-toxic, environmentally benign and safer than the widely used high valence chromium catalysts such as CrO3 and K2Cr2O7. The catalyst can be recycled several times with a negligible impact on activity. Finally, a plausible mechanism is provided based on the observation of intermediate and control experiments.
- Dan, Demin,Chen, Fubo,Zhao, Whenshu,Yu, Han,Han, Sheng,Wei, Yongge
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supporting information
p. 90 - 94
(2021/01/11)
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- ZIF-67 Derived Co/NC Nanoparticles Enable Catalytic Leuckart-type Reductive Amination of Bio-based Carbonyls to N-Formyl Compounds
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It is of great significance to develop non-precious metal catalysts with excellent catalytic activity, stability, and acid resistance for biomass valorization. Herein, catalytic amination of biomass carbonyl compounds was achieved via a Leuckart-type reaction over Co nanoparticles (NPs) embedded N-doped carbon catalyst, which was prepared by thermolysis of ZIF-67 precursor at different temperatures in the N2 atmosphere. The Co/NC-800 catalyst exhibited excellent catalytic activity and recyclability in furfural reductive amination to mono-substituted formamide, which was attributed to the synergistic catalytic action of Co NPs and nitrogen base sites of the catalyst. The reductive amination mechanisms were elucidated by theoretical calculations, and showed that the initial formation of C?N bond was derived from the condensation of furfural and formamide, followed by dehydration to form C=N double bond, which was then reduced by hydrogen species Co?H? and NH+. The developed catalytic system was applicable to different carbonyls for the synthesis of corresponding N-formyl compounds with up to 99 % yield.
- Li, Chuanhui,Meng, Ye,Yang, Song,Li, Hu
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p. 5166 - 5177
(2021/10/25)
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- METHOD OF CARBON MONOXIDE FIXATION AND METHOD OF AMINE FORMYLATION
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The present invention relates to a method for fixing carbon monoxide in a metal-free condition and a method for formating amine using the same.
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Paragraph 0078; 0081-0085
(2021/02/19)
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- An efficient way for the: N -formylation of amines by inorganic-ligand supported iron catalysis
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The first example of an inorganic-ligand supported iron(iii) catalysed coupling of formic acid and amines to form formamides is reported. The pure inorganic catalyst (NH4)3[FeMo6O18(OH)6] (1), which consists of a central FeIII single-atomic core supported within a cycle-shaped inorganic ligand consisting of six MoVIO6 octahedra, shows excellent activity and selectivity, and avoids the use of complicated/commercially unavailable organic ligands. Various primary amines and secondary amines have been successfully transformed into the corresponding formamides under mild conditions, and the formylation of primary diamines has also been achieved for the first time. The Fe catalyst 1 can be reused several times without appreciable loss of activity.
- Wu, Zhikang,Zhai, Yongyan,Zhao, Wenshu,Wei, Zheyu,Yu, Han,Han, Sheng,Wei, Yongge
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supporting information
p. 737 - 741
(2020/02/25)
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- Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
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We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.
- Du, Chen-Xia,Huang, Zijun,Jiang, Xiaolin,Li, Yuehui,Makha, Mohamed,Wang, Fang,Zhao, Dongmei
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supporting information
p. 5317 - 5324
(2020/09/17)
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- Scope and limitations of reductive amination catalyzed by half-sandwich iridium complexes under mild reaction conditions
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The conversion of aldehydes and ketones to 1° amines could be promoted by half-sandwich iridium complexes using ammonium formate as both the nitrogen and hydride source. To optimize this method for green chemical synthesis, we tested various carbonyl substrates in common polar solvents at physiological temperature (37 °C) and ambient pressure. We found that in methanol, excellent selectivity for the amine over alcohol/amide products could be achieved for a broad assortment of carbonyl-containing compounds. In aqueous media, selective reduction of carbonyls to 1° amines was achieved in the absence of acids. Unfortunately, at Ir catalyst concentrations of 1 mM in water, reductive amination efficiency dropped significantly, which suggest that this catalytic methodology might be not suitable for aqueous applications where very low catalyst concentration is required (e.g., inside living cells).
- Nguyen, Dat P.,Sladek, Rudolph N.,Do, Loi H.
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supporting information
(2020/07/15)
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- Metal-free Carbon Monoxide (CO) Capture and Utilization: Formylation of Amines
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The capture and utilization of CO by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were performed in the absence of transition-metal complexes. The reaction of TBD with CO afforded TBD-CO adducts, which were converted to formylated TBD (TBD-CHO). TBD-CO adducts may include an interaction of CO with positively charged species based on NMR and IR analysis. In the presence of amines, CO was transferred from TBD-CO to amines, producing formylated amines with good yields. The reaction mechanism involving TBD-CO adducts is presented based on theoretical calculations. (Figure presented.).
- Noh, Hyeong-Wan,An, Youngjoon,Lee, Seulchan,Jung, Jaehoon,Son, Seung Uk,Jang, Hye-Young
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supporting information
(2019/04/26)
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- Graphene Oxide: A Metal-Free Carbocatalyst for the Synthesis of Diverse Amides under Solvent-Free Conditions
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An environmentally friendly, inexpensive, carbocatalyst, graphene oxide (GO) promoted efficient, metal-free transamidation of various carboxamides with aliphatic, cyclic, and aromatic amines is demonstrated. The protocol is equally applicable to phthalimide, urea, and thioamide determining its adaptability. The oxygenated functionalities such as carbonyl (?C=O), epoxy (?O?), carboxyl (?COOH) and hydroxyl (?OH), present on graphene oxide surface impart acidic properties to the catalyst. The graphene oxide being heterogeneous in nature, work efficiently under solvent-free reaction conditions providing desired products in good to excellent yields. The one-pot synthesis of 2,3-Dihydro-5H-benzo[b]-1,4-thiazepin-4-one moiety by GO catalyzed Aza Michael addition followed by intramolecular transamidation is also described. A plausible reaction mechanistic pathway involving H-bonding is discussed. The graphene oxide can be recycled and reused up to five cycles without much loss in catalytic activity. (Figure presented.).
- Patel, Khushbu P.,Gayakwad, Eknath M.,Patil, Vilas V.,Shankarling, Ganapati S.
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supporting information
p. 2107 - 2116
(2019/03/26)
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- Structure based drug design and in vitro metabolism study: Discovery of N-(4-methylthiophenyl)-N,2-dimethyl-cyclopenta[d]pyrimidine as a potent microtubule targeting agent
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We report a series of tubulin targeting agents, some of which demonstrate potent antiproliferative activities. These analogs were designed to optimize the antiproliferative activity of 1 by varying the heteroatom substituent at the 4′-position, the basicity of the 4-position amino moiety, and conformational restriction. The potential metabolites of the active compounds were also synthesized. Some compounds demonstrated single digit nanomolar IC50 values for antiproliferative effects in MDA-MB-435 melanoma cells. Particularly, the S-methyl analog 3 was more potent than 1 in MDA-MB-435 cells (IC50 = 4.6 nM). Incubation of 3 with human liver microsomes showed that the primary metabolite of the S-methyl moiety of 3 was the methyl sulfinyl group, as in analog 5. This metabolite was equipotent with the lead compound 1 in MDA-MB-435 cells (IC50 = 7.9 nM). Molecular modeling and electrostatic surface area were determined to explain the activities of the analogs. Most of the potent compounds overcome multiple mechanisms of drug resistance and compound 3 emerged as the lead compound for further SAR and preclinical development.
- Xiang, Weiguo,Choudhary, Shruti,Hamel, Ernest,Mooberry, Susan L.,Gangjee, Aleem
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p. 2437 - 2451
(2018/04/16)
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- First report on bio-catalytic N-formylation of amines using ethyl formate
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A bio-catalyzed N-formylation reaction of different amines has been developed using ethyl formate as a formylating agent. This protocol provides a facile and convenient strategy featuring mild reaction conditions, high efficacy, a broad substrate scope and recyclability of lipase. This method also works on a large scale in high yield.
- Patre, Rupesh E.,Mal, Sanjib,Nilkanth, Pankaj R.,Ghorai, Sujit K.,Deshpande, Sudhindra H.,El Qacemi, Myriem,Smejkal, Tomas,Pal, Sitaram,Manjunath, Bhanu N.
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supporting information
p. 2382 - 2385
(2017/02/23)
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- Application of polydopamine sulfamic acid-functionalized magnetic Fe3O4 nanoparticles (Fe3O4@PDA-SO3H) as a heterogeneous and recyclable nanocatalyst for the formylation of alcohols and amines under solvent-free conditions
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Herein, formylation of structurally different amines and alcohols with ethyl formate was carried out in the presence of a catalytic proportion of sulfonic acid supported on polydopamine (PDA)-encapsulated Fe3O4 nanoparticles as a heterogeneous, recyclable, and greatly efficient catalyst; this method provided the corresponding N-formyl compounds in good to excellent yields under solvent-free conditions. The magnetically catalytic system was recovered, by-passing the time-consuming filtration operation using an external magnet device. This procedure also increases the purity of the product and promises economic and ecological advantages. Furthermore, the recovery and reuse of the catalyst was demonstrated five times without detectable loss in the activity.
- Taheri, Sepideh,Veisi, Hojat,Hekmati, Malak
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p. 5075 - 5081
(2017/07/11)
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- Nonacidic Farnesoid X Receptor Modulators
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As a cellular bile acid sensor, farnesoid X receptor (FXR) participates in regulation of bile acid, lipid and glucose homeostasis, and liver protection. Clinical results have validated FXR as therapeutic target in hepatic and metabolic diseases. To date, potent FXR agonists share a negatively ionizable function that might compromise their pharmacokinetic distribution and behavior. Here we report the development and characterization of a high-affinity FXR modulator not comprising an acidic residue.
- Flesch, Daniel,Cheung, Sun-Yee,Schmidt, Jurema,Gabler, Matthias,Heitel, Pascal,Kramer, Jan,Kaiser, Astrid,Hartmann, Markus,Lindner, Mara,Lüddens-D?mgen, Kerstin,Heering, Jan,Lamers, Christina,Lüddens, Hartmut,Wurglics, Mario,Proschak, Ewgenij,Schubert-Zsilavecz, Manfred,Merk, Daniel
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supporting information
p. 7199 - 7205
(2017/09/07)
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- Enantioselective Synthesis of Quaternary Δ4- and Δ5-Dehydroprolines Based on a Two-Step Formal [3+2] Cycloaddition of α-Aryl and α-Alkyl Isocyano(thio)acetates with Vinyl Ketones
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A divergent synthesis of optically active quaternary Δ4- and Δ5-dehydro prolines is developed based on the first catalytic enantioselective conjugate addition of α-substituted isocyano(thio)acetates to vinyl ketones that is general for both α-aryl and α-alkyl isocyano(thio)acetates. The new tetrasubstituted C?N stereocenter is formed without the need of any metal salt due to a bifunctional tertiary amine/squaramide catalyst, featuring a bulky polyaryl sidearm and an unusually short squaramide diamide H???H interatomic distance in the solid state.
- Odriozola, Amaiur,Oiarbide, Mikel,Palomo, Claudio
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supporting information
p. 12758 - 12762
(2017/09/25)
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- Preparation method of the formamide
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The invention relates to a preparation method of methanamide. The method uses formamide or its derivative and amine (primary or secondary amine) as reactants, which are subjected to amidomethylation in the presence of a catalyst to prepare methanamide. The method is characterized in that solid acidic metal oxide or precious metal loaded acidic metal oxide is used as the catalyst and the reaction is carried out efficiently under mild conditions. The reaction process is as follows: mixing formamide with certain concentration or its derivatives with primary or secondary amine and a certain amount of catalyst, placing the mixture into pressure vessel without adding or additionally adding other solvent, sealing, stirring at a temperature no less than 60 DEG C, and reacting for no less than 0.5 h to obtain the reaction product methanamide. The method has the advantages of simple preparation of the catalyst, easy separation process of the catalyst and product, repeated usage of the catalyst, high controllability of the reaction process, and yield of the product formamide reaching more than 95%.
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Paragraph 0041; 0042; 0052
(2017/07/01)
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- Ru/ceria-catalyzed direct formylation of amines and CO to produce formamides
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We herein report a new strategy of directly converting amines and CO to formamides with 100% atom utilization efficiency. It is suitable for up to 25 amine substrates with no additives. Ru/ceria is found to be an excellent catalyst for this reaction due the efficient co-activation of CO and amine on Ru species.
- Wang, Yehong,Zhang, Jian,Chen, Haijun,Zhang, Zhixin,Zhang, Chaofeng,Li, Mingrun,Wang, Feng
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- Preparation method for methanamide
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The invention relates to a method for preparing methanamide compounds through carbonylation of amine. The method employs primary amine or secondary amine and carbon monoxide (CO) as reactants and prepares the methanamide compounds through a CO-inserted carbonylation reaction under the catalysis of ruthenium-loaded hydroxyapatite (Ru/HAP). Reaction conditions are that the reaction is carried out in a tank reactor under stirring; CO pouring pressure is 0.5 to 5.0 MPa; and reaction temperature is 100 to 200 DEG C. The method has the characteristics that (1) the reaction has 100% atom economy and is free of generation of any by-product; (2) the ruthenium-loaded hydroxyapatite is used as a catalyst, the catalyst is simple to prepare and efficiently catalyzes the reaction, and the yield of the methanamide compounds can reach 80% or above; and (3) the catalyst has good stability and can be cyclically used four times or more.
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Paragraph 0027; 0028
(2017/05/26)
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- MANGANESE BASED COMPLEXES AND USES THEREOF FOR HOMOGENEOUS CATALYSIS
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The present invention relates to novel manganese complexes and their use, inter alia, for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2) C-C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di- lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. (12) preparation of amides (including formamides, cyclic dipeptides, diamide, lactams, polypeptides and polyamides) by dehydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.
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Paragraph 00406; 00407
(2017/09/05)
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- Biomass-derived γ-valerolactone as an efficient solvent and catalyst for the transformation of CO2 to formamides
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Efficient conversion of carbon dioxide (CO2) into valuable chemicals is a very attractive topic. Herein, we conducted the first work on the utilization of biomass-derived γ-valerolactone (GVL) as the solvent and catalyst for transformation of CO2 with various primary and secondary amines in the presence of phenylsilane (PhSiH3), and the corresponding desired formamides were produced with high yields without any additional catalyst. Systematic studies indicated that the lactone structure of GVL played a key role in the formation of the active silyl formates and the activation of N-H bonds in amines, thus leading to the excellent performance of GVL for the catalytic reactions.
- Song, Jinliang,Zhou, Baowen,Liu, Huizhen,Xie, Chao,Meng, Qinglei,Zhang, Zhanrong,Han, Buxing
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supporting information
p. 3956 - 3961
(2016/07/21)
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- Transamidation catalysed by a magnetically separable Fe3O4 nano catalyst under solvent-free conditions
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An environmentally benign protocol for transamidation of carboxamides with different amines under solvent free conditions using magnetically separable nano Fe3O4 as a heterogeneous catalyst is developed. The series of aryl and alkyl amines with long chain alkyl substituents have been selectively converted into transamide products. The current protocol offers a diverse substrate scope with good yield of the product. The Fe3O4 nano catalyst has also been used for formylation of amines via transamidation of dimethyl formamide. Efficient transamidation, ease of work up, simple separation and reusability of the catalyst for up to six runs are the important highlights of this process.
- Thale, Pranila B.,Borase, Pravin N.,Shankarling, Ganapati S.
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p. 52724 - 52728
(2016/06/14)
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- Method for preparation of formamide through carbonylation
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The invention relates to a method for preparation of formamide. The method adopts primary amine and/or secondary amine and carbon monoxide as reactants, and under the catalysis action, formamide is prepared by a carbon monoxide carbonylation reaction. The method is characterized in that a ruthenium loaded acidic compound metal oxide is used as a catalyst, and the reaction is carried out with high efficiency under milder conditions. The reaction process comprises the steps: putting primary amine and/or secondary amine with a certain concentration and a certain amount of the catalyst in a pressure vessel, introducing CO gas, sealing, and at the temperature of more than 100 DEG C and the reaction time of more than 2 h, carrying out a stirring reaction to obtain formamide. According to the method, the catalyst is simple to prepare and high in catalytic activity, the yield of the product formamide can reach 98%, and the separation process of the product and the catalyst is simple, the catalyst can be recycled for many times, and the reaction process has high controllability.
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Paragraph 0034; 0035
(2017/03/14)
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- Supported nano-gold-catalyzed N-formylation of amines with paraformaldehyde in water under ambient conditions
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A simple and efficient Au/Al2O3 catalyst was prepared by the co-precipitation method for the oxidative N-formylation of amines with paraformaldehyde. Under the optimized reaction conditions, excellent amine conversion and N-formamide selectivity can be obtained with up to 97% yield with water as the solvent under ambient conditions. This catalyst tolerated a wide range of primary amines and second amines, and it can be reused for at least five runs without obvious deactivation.
- Ke, Zhengang,Zhang, Yan,Cui, Xinjiang,Shi, Feng
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p. 808 - 816
(2016/02/12)
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- Synthesis of imidazo[1,2-a]pyridines in a sequential one-pot Groebke-Blackburn modification using 2-aminopyridines, aldehydes and amines
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Herein we present a novel synthetic procedure for the synthesis of imidazo[1,2-a]pyridines in a modified Groebke-Blackburn fashion. In a sequential three-step one-pot protocol the commercially hardly available isocyanide-component is formed in situ using standard reagents. Cyclization to the desired products can be afforded in the same reaction mixture. The absent need of isolation of the isocyanide in this protocol eases its handling considerably and workup is only needed to finally furnish the imidazo[1,2-a]pyridines via coloumn chromatography. This protocol is a convenient way to more diverse libraries of imidazo[1,2-a]pyridines extending the functionality of the Groebke-Blackburn synthesis.
- Flesch,Schubert-Zsilavecz
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p. 507 - 510
(2015/09/15)
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- Hydrogen acceptor- and base-free N-formylation of nitriles and amines using methanol as C1 source
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An N-formylation method using methanol as the C1 source without a stoichiometric amount of activating reagent is described. Nitriles as well as amines can be directly used as substrates. The reaction is catalyzed by an N-heterocyclic carbene coordinated ruthenium(II) dihydride complex, which mediates methanol dehydrogenation, nitrile reduction, and C-N bond formation without any external base, hydrogen acceptor, or oxidant.
- Kang, Byungjoon,Hong, Soon Hyeok
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supporting information
p. 834 - 840
(2015/03/18)
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- An attractive route to transamidation catalysis: Facile synthesis of new o-aryloxide-N-heterocyclic carbene ruthenium(II) complexes containing trans triphenylphosphine donors
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Well-defined robust ruthenium(II) complexes 3a-d bearing o-aryloxide-N-heterocyclic carbene ligands with different wingtip substituents (3a (R = Me), 3b (R = Ph), 3c (R = iPr) and 3d (R = Mes)) in the imidazole ring were synthesized in good yields by the reaction of imidazolium proligands with metal precursor [RuHCl(CO)(PPh3)3] by transmetallation from the corresponding silver carbene complexes. All the Ru(II)-NHC complexes have been characterized by elemental analyses, spectroscopic methods as well as ESI mass spectrometry. The molecular structure of the complex 3a was identified by means of single-crystal X-ray diffraction analysis, which revealed that the complexes possess a distorted octahedral geometry. In order to explore the catalytic potential of the synthesized complexes, all the four [Ru-NHC] complexes [3a-d] were tested as catalysts for transamidation of carboxamides with amines. Notably, the complex 3a was found to be very efficient and versatile catalyst toward transamidation of a wide range of amides with amines.
- Nirmala, Muthukumaran,Prakash, Govindan,Viswanathamurthi, Periasamy,Malecki, Jan Grzegorz
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- Size of gold nanoparticles driving selective amide synthesis through aerobic condensation of aldehydes and amines
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Metal nanoparticles (NPs) have attracted much attention in many fields due to their intrinsic characteristics. It is generally accepted that smaller NPs (1.5-3 nm) are more active than larger NPs, and reverse cases are very rare. We report here the direct aerobic oxidative amide synthesis from aldehydes and amines catalyzed by polymer-incarcerated gold (Au) NPs. A unique correlation between imine/amide selectivity and size of NPs was discovered; Au-NPs of medium size (4.5-11 nm) were found to be optimal. High yields were obtained with a broad range of substrates, including primary amines. Au-NPs of medium size could be recovered and reused several times without loss of activity, and they showed good activity and selectivity in amide formation from alcohols and amines. Superior activity and selectivity of gold nanoparticles (Au-NPs) of medium size (4.5-11 nm) were found for the direct and selective aerobic oxidative amide synthesis from various combinations of aldehydes and amines. This is an example of an unusual correlation between the size of NPs and their activity/selectivity. These catalysts could be recovered and reused several times without loss of activity.
- Miyamura, Hiroyuki,Min, Hyemin,Soulé, Jean-Fran?ois,Kobayashi, Shu
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supporting information
p. 7564 - 7567
(2015/06/25)
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- Transformylating amine with DMF to formamide over CeO2 catalyst
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We here report a new protocol for the formylation of various amines, primary or secondary, aromatic or alkyl, cyclic or linear, mono- or di-amine, with dimethylformamide (DMF) as the formylation reagent to obtain the corresponding formamides in good to excellent yields over CeO2 catalyst. The reaction requires no homogeneous acidic or basic additives and is tolerant to water.
- Wang, Yehong,Wang, Feng,Zhang, Chaofeng,Zhang, Jian,Li, Mingrun,Xu, Jie
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supporting information
p. 2438 - 2441
(2014/03/21)
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- Direct synthesis of amides from carboxylic acids and amines using B(OCH2CF3)3
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B(OCH2CF3)3, prepared from readily available B2O3 and 2,2,2-trifluoroethanol, is as an effective reagent for the direct amidation of a variety of carboxylic acids with a broad range of amines. In most cases, the amide products can be purified by a simple filtration procedure using commercially available resins, with no need for aqueous workup or chromatography. The amidation of N-protected amino acids with both primary and secondary amines proceeds effectively, with very low levels of racemization. B(OCH2CF3)3 can also be used for the formylation of a range of amines in good to excellent yield, via transamidation of dimethylformamide.
- Lanigan, Rachel M.,Starkov, Pavel,Sheppard, Tom D.
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p. 4512 - 4523
(2013/06/05)
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- Catalytic synthesis of silyl formates with 1 atm of CO2 and their utilization for synthesis of formyl compounds and formic acid
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In the presence of simple Rh2(OAc)4 and K 2CO3, the hydrosilylation of CO2 (1 atm) with various hydrosilanes efficiently proceeded to afford the corresponding silyl formates in moderate to high yields (53-90% yields). By using the dimethylphenylsilyl formate produced by the hydrosilylation, formamides, formic acid, and a secondary alcohol (via an aldehyde) could be synthesized by the reaction with various nucleophilic reagents such as amines, aniline, water, and the Grignard reagent.
- Itagaki, Shintaro,Yamaguchi, Kazuya,Mizuno, Noritaka
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p. 347 - 352
(2013/02/22)
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- A novel and simple transamidation of carboxamides in 1,4-dioxane without a catalyst
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An easy acylation and formylation of amines has been achieved via transamidation using 1,4-dioxane. The investigation works efficiently without an added catalyst and completes within short time under microwave irradiation.
- Vanjari, Rajeshwer,Allam, Bharat Kumar,Singh, Krishna Nand
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p. 2553 - 2555
(2013/06/05)
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- Catalytic enantioselective Michael addition of α-aryl-α- isocyanoacetates to vinyl selenone: Synthesis of α,α-disubstituted α-amino acids and (+)- and (-)-trigonoliimine A
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Be like Mike: The title reaction in the presence of the catalyst 1 afforded Michael adducts in excellent yields and enantioselectivities. The adducts were readily converted into α,α′-disubstituted α-amino acids. The enantioselective total synthesis of bot
- Buyck, Thomas,Wang, Qian,Zhu, Jieping
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supporting information
p. 12714 - 12718
(2013/12/04)
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- N-Formylation of amines by methanol activation
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The homogeneous catalyzed dehydrogenation of methanol in a synthetically valuable cross-coupling reaction was achieved. By the use of a simple ruthenium-N-heterocyclic carbene complex, MeOH and primary or secondary amines can be converted into formamides.
- Ortega, Nuria,Richter, Christian,Glorius, Frank
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supporting information
p. 1776 - 1779
(2013/06/26)
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- Sulfur and selenium derivatives of quinazoline and pyrido[2,3-d]pyrimidine: Synthesis and study of their potential cytotoxic activity in vitro
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The synthesis, cytotoxic activities and selectivities of 35 derivatives related to quinazoline and pyrido[2,3-d]pyrimidine are described. The synthesized compounds were screened in vitro against four tumoral cell lines - leukemia (CCRF-CEM), colon (HT-29), lung (HTB-54) and breast (MCF-7) - and two cell lines derived from non-malignant cell lines, one mammary (184B5) and one from bronchial epithelium (BEAS-2B). MCF-7 and HTB-54 were the most sensitive cell lines with GI50 values below 10 μM for eleven and ten compounds, respectively. Two compounds (2o and 3a) were identified that evoked a marked cytotoxic effect in all cell lines tested and one compound, 7h, was potent and selective against MCF-7. A preliminary study into the mechanism of the potent derivatives 2o, 3a and 7h indicated that the cytotoxic activities of these compounds might be mediated by inducing cell death without affecting cell cycle phases.
- Moreno, Esther,Plano, Daniel,Lamberto, Iranzu,Font, María,Encío, Ignacio,Palop, Juan Antonio,Sanmartín, Carmen
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experimental part
p. 283 - 298
(2012/02/16)
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- Transamidation of primary amides with amines catalyzed by zirconocene dichloride
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Zirconocene dichloride (Cp2ZrCl2) has been shown to be an effective catalyst for the transamidation of primary amides with amines in cyclohexane at 80°C in 5-24 hours. For favourable substrates, the reaction can be performed at temperatures as low as 30°C.
- Atkinson, Benjamin N.,Chhatwal, A. Rosie,Lomax, Helen V.,Walton, James W.,Williams, Jonathan M. J.
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supporting information
p. 11626 - 11628,3
(2012/12/12)
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- Transamidation of primary amides with amines catalyzed by zirconocene dichloride
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Zirconocene dichloride (Cp2ZrCl2) has been shown to be an effective catalyst for the transamidation of primary amides with amines in cyclohexane at 80°C in 5-24 hours. For favourable substrates, the reaction can be performed at temperatures as low as 30°C.
- Atkinson, Benjamin N.,Chhatwal, A. Rosie,Lomax, Helen V.,Walton, James W.,Williams, Jonathan M. J.
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supporting information
p. 11626 - 11628
(2013/01/15)
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- Iridium-catalyzed formylation of amines with paraformaldehyde
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Amines have been formylated using aqueous formaldehyde or paraformaldehyde and the iridium catalyst [CpIrI2]2. Paraformaldehyde acts as both a formylating agent and an oxidant.
- Saidi, Ourida,Bamford, Mark J.,Blacker, A. John,Lynch, James,Marsden, Stephen P.,Plucinski, Pawel,Watson, Robert J.,Williams, Jonathan M.J.
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supporting information; experimental part
p. 5804 - 5806
(2010/11/05)
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- Silica-bonded N-propyl sulfamic acid as an efficient catalyst for the formylation and acetylation of alcohols and amines under heterogeneous conditions
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A simple and efficient procedure for the preparation of silica-bonded N-propyl sulfamic acid (SBNPSA) by the reaction of 3-aminopropylsilica (1) and chlorosulfonic acid in chloroform is described. This solid acid is employed as a new catalyst for the formylation of alcohols and amines with ethyl formate under mild and heterogeneous conditions at room temperature with good to excellent yields. Also, SBNPSA catalyzed acetylation of various alcohols and amines with acetic anhydride at room temperature.
- Niknam, Khodabakhsh,Saberi, Dariush
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experimental part
p. 5210 - 5214
(2009/12/06)
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- NaIO4-oxidized carbonylation of amines to ureas
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Oxidative carbonylation of amines using NaIO4 as the oxidant and NaI as a promoter affords good to excellent yields of ureas from primary amines in the absence of transition metal catalysts. The Royal Society of Chemistry 2009.
- Shelton, Phillip A.,Zhang, Yue,Nguyen, Thi Hoang Ha,McElwee-White, Lisa
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supporting information; experimental part
p. 947 - 949
(2009/07/10)
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- A new, simple procedure for the synthesis of formyl amides
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A simple and mild method for the N-formylation of amines and α-amino esters is described via reaction with 2-chloro-4,6-dimethoxy[1,3,5]triazine and formic acid. The reaction can be accelerated under microwave irradiation and yields the N-formyl species in high yields and without racemization in the case of optically active α-amino esters.
- De Luca, Lidia,Giacomelli, Giampaolo,Porcheddu, Andrea,Salaris, Margherita
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p. 2570 - 2572
(2007/10/03)
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- Benzamidines, alkamidines and formamidines formed by use of aryl- and alkyliminodimagnesium: Molar ratio and structure of reagent governing the reaction
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In order to extend the the method for preparation of amidines using N-Mg reagents, aryl- and alkyliminodimagnesium [IDMg, ArN(MgBr)2 and RN(MgBr)2] were reacted with esters, amides, ortho- esters, acetals, aminoacetal and arene- and
- Okubo, Masao,Omote, Yasumasa
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p. 212 - 220
(2007/10/03)
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- Mutagenicity and Chemistry of N-Nitroso-N-(p-substituted-benzyl)methylamines
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The relative mutagenicities of N-nitroso-N-(p-substituted-benzyl)methylamines in Salmonella typhimurium TA 1535 were tested in order to determine whether biological activity is affected by the electron density at a nitrosamine α carbon.The order of potency was as follows: X = Cl > CN > Br > NO2 > H > CH3O > CH3 > F >> COOH.No direct correlation was apparent, nor was there obvious correlation between biological activity and the extent of base-catalysed hydrogen-deuterium exchange at the α-carbons.
- Singer, George M.,Andrews, A.W.
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p. 309 - 312
(2007/10/02)
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