- Facile N-Formylation of Amines on Magnetic Fe3O4?CuO Nanocomposites
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A facile, eco-friendly, efficient, and recyclable heterogeneous catalyst is synthesized by immobilizing copper impregnated on mesoporous magnetic nanoparticles. The surface chemistry analysis of Fe3O4?CuO nanocomposites (NCs) by XRD and XPS demonstrates the synergistic effect between Fe3O4 and CuO nanoparticles, providing mass-transfer channels for the catalytic reaction. TEM images clearly indicate the impregnation of CuO onto mesoporous Fe3O4. This hydrothermally synthesized eco-friendly and highly efficient Fe3O4?CuO NCs are applied as a magnetically retrievable heterogeneous catalyst for the N-formylation of wide range of aliphatic, aromatic, polyaromatic and heteroaromatic amines using formic acid as a formylating agent at room temperature. The catalytic activity of the NCs for N-formylation is attributable to the synergistic effect between Fe3O4 and CuO nanoparticles. The N-formylated product is further employed for the synthesis of biologically active quinolone moieties.
- Datta Khanal, Hari,Mishra, Kanchan,Rok Lee, Yong
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p. 4477 - 4484
(2021/08/30)
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- Facile access to: N-formyl imide as an N-formylating agent for the direct synthesis of N-formamides, benzimidazoles and quinazolinones
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N-Formamide synthesis using N-formyl imide with primary and secondary amines with catalytic amounts of p-toluenesulfonic acid monohydrate (TsOH·H2O) is described. This reaction is performed in water without the use of surfactants. Moreover, N-formyl imide is efficiently synthesized using acylamidines with TsOH·H2O in water. In addition, N-formyl imide was successfully used as a carbonyl source in the synthesis of benzimidazole and quinazolinone derivatives. Notable features of N-formylation of amines by using N-formyl imide include operational simplicity, oxidant- A nd metal-free conditions, structurally diverse products, and easy applicability to gram-scale operation.
- Huang, Hsin-Yi,Liang, Chien-Fu,Lin, Xiu-Yi,Yen, Shih-Yao
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supporting information
p. 5726 - 5733
(2020/08/21)
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- Organocatalytic Decarboxylation of Amino Acids as a Route to Bio-based Amines and Amides
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Amino acids obtained by fermentation or recovered from protein waste hydrolysates represent an excellent renewable resource for the production of bio-based chemicals. In an attempt to recycle both carbon and nitrogen, we report here on a chemocatalytic, metal-free approach for decarboxylation of amino acids, thereby providing a direct access to primary amines. In the presence of a carbonyl compound the amino acid is temporarily trapped into a Schiff base, from which the elimination of CO2 may proceed more easily. After evaluating different types of aldehydes and ketones on their activity at low catalyst loadings (≤5 mol%), isophorone was identified as powerful organocatalyst under mild conditions. After optimisation many amino acids with a neutral side chain were converted in 28–99 % yield in 2-propanol at 150 °C. When the reaction is performed in DMF, the amine is susceptible to N-formylation. This consecutive reaction is catalysed by the acidity of the amino acid reactant itself. In this way, many amino acids were efficiently transformed to the corresponding formamides in a one-pot catalytic system.
- Claes, Laurens,Janssen, Michiel,De Vos, Dirk E.
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p. 4297 - 4306
(2019/08/26)
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- Amine formylation with CO2 and H2 catalyzed by heterogeneous Pd/PAL catalyst
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For the first time, Pd supported on natural palygorskite was developed for amine formylation with CO2 and H2. Both secondary and primary amines with diverse structures could be converted into the desired formamides at 100 °C, and good to excellent yields were obtained.
- Dai, Xingchao,Wang, Bin,Wang,Shi, Feng
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p. 1141 - 1146
(2019/07/09)
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- Production of Formamides from CO and Amines Induced by Porphyrin Rhodium(II) Metalloradical
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It is of fundamental importance to transform carbon monoxide (CO) to petrochemical feedstocks and fine chemicals. Many strategies built on the activation of C≡O bond by π-back bonding from the transition metal center were developed during the past decades. Herein, a new CO activation method, in which the CO was converted to the active acyl-like metalloradical, [(por)Rh(CO)]? (por = porphyrin), was reported. The reactivity of [(por)Rh(CO)]? and other rhodium porphyrin compounds, such as (por)RhCHO and (por)RhC(O)NHnPr, and corresponding mechanism studies were conducted experimentally and computationally and inspired the design of a new conversion system featuring 100% atom economy that promotes carbonylation of amines to formamides using porphyrin rhodium(II) metalloradical. Following this radical based pathway, the carbonylations of a series of primary and secondary aliphatic amines were examined, and turnover numbers up to 224 were obtained.
- Zhang, Jiajing,Zhang, Wentao,Xu, Minghui,Zhang, Yang,Fu, Xuefeng,Fang, Huayi
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supporting information
p. 6656 - 6660
(2018/05/24)
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- Copper-(II) Catalyzed N-Formylation and N-Acylation of Aromatic, Aliphatic, and Heterocyclic Amines and a Preventive Study in the C-N Cross Coupling of Amines with Aryl Halides
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A Cu-(II) catalyzed N-formylation and N-acylation of amines with moderate to excellent yields, using N, N-dimethyl formamide (DMF) and N, N-dimethyl acetamide (DMA) as a formyl and acylating sources in the presence of 1,2,4-triazole is reported. This novel, highly efficient and simple protocol shows broad substrate scope for aliphatic, aromatic, and heterocyclic amines. In addition, the conditions to prevent N-formylation and N-acylation impurities in the C?N cross coupling of amines and aryl halides are described typically when DMF and DMA are used as solvents, with various catalysts, ligands, and bases.
- Sonawane, Rahul B.,Rasal, Nishant K.,Bhange, Dattatraya S.,Jagtap, Sangeeta V.
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p. 3907 - 3913
(2018/09/12)
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- Colloid and nanosized catalysts in organic synthesis: XIV. Reductive amination and amidation of carbonitriles catalyzed by nickel nanoparticles
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Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in the presence of primary amines led to the predominant formation of unsymmetrical secondary amines. In the presence of secondary amines hydrogenation of nitrites provided enamines as main products. Hydrogenation of nitriles in the presence of formamide or acetamide afforded formyl or acetyl derivatives of primary amines.
- Popov, Yu. V.,Mokhov,Shcherbakova
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p. 798 - 805
(2016/06/13)
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- Formamide Synthesis through Borinic Acid Catalysed Transamidation under Mild Conditions
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A highly efficient and mild transamidation of amides with amines co-catalysed by borinic acid and acetic acid has been reported. A wide range of functionalised formamides was synthesized in excellent yields, including important chiral α-amino acid derivatives, with minor racemisation being observed. Experiments suggested that the reaction rely on a cooperative catalysis involving an enhanced boron-derived Lewis acidity rather than an improved Br?nsted acidity of acetic acid. Amide bonds are reputedly difficult to activate due to their high resonance stabilization. An unusual mild activation of dimethylformamide and formamide by borinic acid 1 (see scheme), illustrated by a general formylation of a wide range of amines, including chiral α-amino esters, has been reported.
- Mohy El Dine, Tharwat,Evans, David,Rouden, Jacques,Blanchet, Jér?me
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supporting information
p. 5894 - 5898
(2016/04/26)
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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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- K3PO4-catalyzed carbonylation of amines to formamides
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Synthesis of formamides from the catalytic carbonylation of amines with CO is of great interest due to their wide applications of formamides as synthetic intermediates and aprotic polar solvents. Up to now, the most commonly used catalysts are either expensive noble metal compounds or difficult-to-handle alkali metal alkoxides. We have found that a solid base, K3PO4 is a highly active and selective catalyst for the carbonylation of primary and cyclic secondary amines, producing corresponding formaldehydes in yields up to 99% at relatively mild conditions. Spectroscopic and quantum mechanical calculation results indicate that such high activity of K3PO4 is closely related to the strong hydrogen bonding ability of PO43- with the amino group of an amine, thereby enhancing the nucleophilicity of the amino group enough to interact with a neutral molecule, CO and mediating proton transfer from the amino group to the carbonyl group. Characterization of spent catalyst by FT-IR and XRD implies that small portion of K3PO4 is converted into less active K2HPO4 during the carbonylation reaction.
- Kim, Young Jin,Lee, Ji Woo,Lee, Hyun Ji,Zhang, Shuyao,Lee, Je Seung,Cheong, Minserk,Kim, Hoon Sik
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p. 126 - 133
(2015/09/28)
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- N-heterocycles from chromium aminocarbenes
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The initial [2 + 2]-cycloadduct between a chromium aminocarbene and a tethered alkene undergoes a β-hydrogen elimination very efficiently when triphenylphosphine is added as a ligand. The reaction gives cyclic enamines or homoenamines depending on the sub
- Déry, Martin,Assouvie, Kevin,Heinrich, Nora,Rajotte, Isabelle,Lefebvre, Louis-Philippe D.,Legault, Marc-André,Spino, Claude
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supporting information
p. 1312 - 1315
(2015/03/14)
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- Nanoceria-catalyzed highly efficient procedure for N-formylation of amines at room temperature under solvent-free conditions
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Nanoceria-catalyzed simple and efficient protocol for the N-formylation of amines using formic acid at room temperature under solvent-free conditions shows high yield of desired product chemoselectivity and improvement in reaction time.
- Patil, Umakant B.,Singh, Abhilash S.,Nagarkar, Jayashree M.
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supporting information
p. 524 - 526
(2013/06/05)
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- Synthesis of N-formylated β-lactams using nano-sulfated TiO 2 as catalyst under solvent-free conditions
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An easily accessible catalyst, nano-sulfated titania, efficiently catalyzes the N-formylation of β-lactams and all types of amines (primary, secondary, aromatic, and aliphatic) in solvent-free conditions at room temperature.
- Hosseini-Sarvari, Mona,Safary, Ensieh,Jarrahpour, Aliasghar,Heiran, Roghaye
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p. 980 - 987
(2013/02/22)
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- Ionic liquids as benign catalysts for the carbonylation of amines to formamides
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1-Butyl-3-methylimidazolium hydrogen carbonate ([BMIm][HCO3]), prepared from the reaction of [BMIm]Cl with K2CO3 in methanol, exhibits high activity for the carbonylation of amines to produce formamides. Computational calculation results on the carbonylation reaction of methylamine implies that such high activity of [BMIm][HCO3] could be ascribed to the bi-functional actions of [HCO3]- as a hydrogen atom acceptor and a donor.
- Choi, Young-Seop,Shim, Yu Na,Lee, Jeesun,Yoon, Jung Hee,Hong, Chang Seop,Cheong, Minserk,Kim, Hoon Sik,Jang, Ho Gyeom,Lee, Je Seung
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experimental part
p. 87 - 92
(2012/02/05)
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- Inhibition of human alcohol dehydrogenases by formamides
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Human alcohol dehydrogenase (HsADH) comprises class I (α, β, and γ), class II (π), and class IV (σ) enzymes. Selective inhibitors of the enzymes could be used to prevent the metabolism of alcohols that form toxic products. Formamides are unreactive analog
- Schindler, John F.,Berst, Kristine B.,Plapp, Bryce V.
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p. 1696 - 1701
(2007/10/03)
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- Reactions of 1-acylamino-1-(trimethylsiloxy)alkanes: Versatile precursors to acylimines
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1-Acylamino-1-(trimethylsiloxy)alkanes react with carbon and heteroatom nucleophiles to give the corresponding 1-substituted-1-acylaminoalkanes. The 1-acylamino-1-(trimethylsiloxy)alkanes can also give rise to enamides, and by this route the mild antibiotic tuberin, and the isomeric (Z)-tuberin have been prepared. A further example of their reactions is illustrated with the acid-catalysed intramolecular cyclisation onto a carbon-carbon double bond. These transformations show that 1-acylamino-1-(trimethylsiloxy)alkanes are versatile precursors to synthetically useful acylimines.
- Johnson, A. Peter,Luke, Richard W. A.,Boa, Andrew N.
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p. 895 - 905
(2007/10/03)
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- DODECACARBONYLTRIRUTHENIUM CATALYSED CARBONYLATION OF AMINES AND HYDROAMIDATION OF OLEFINS
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Dodecacarbonyltriruthenium (Ru3(CO)12) is an effective homogeneous catalyst precursor for the carbonylation of amines and hydroamidation of olefins under a carbon monoxide pressure of 40 kg cm-2 at 120-180 deg C.By the carbonylation of benzylamine, N- benzylformamide was obtained in 77percent yield. 1-Octene was hydroamidated with benzylamine to N-benzylnonanamide in 67percent yield (the selectivity to its linear isomer was 81percent).These reactions appear to include ruthenium carbamoyl complex as the common key intermediate.
- Tsuji, Yasushi,Ohsumi, Tatsuya,Kondo Teruyuki,Watanabe, Yoshihisa
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p. 333 - 344
(2007/10/02)
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- Nitrogen-15 Nuclear Magnetic Rasonance Spectroscopy. Natural Abundance Nitrogen-15 Spectra of the cis and trans Isomers of Secondary Alkylformamides
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The 15N NMR chemical shifts were measured of a number of N-substituted formamides and acetamides at the natural abundance level.The ratios of the cis and trans isomers for several N-alkylformamides were also determined.Substituent effects on the 15N chemical shifts of formamides are compared with those of some other nitrogen-containing compounds.There is a consistent pattern of behavior of the one bond spin-spin coupling constants 1J(15NH)> wherein the trans isomers of N-alkylformamides are larger than those of the cis isomers.
- Nakanishi, Hiroshi,Roberts, John D.
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- Process for producing N-monosubstituted formamides
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An N-monosubstituted formamide having the formula: EQU1 in which R represents an optionally substituted aliphatic, cycloaliphatic or aromatic radical; is prepared by reacting a formaldimine having the formula: in which R is as defined above; or a hexahydrotriazine having the formula: EQU2 in which R is as defined above, with hydrogen peroxide. The reaction is generally carried out at temperatures in the range of from about 0° to about 100° C.
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