- ZIF-67 Derived Co/NC Nanoparticles Enable Catalytic Leuckart-type Reductive Amination of Bio-based Carbonyls to N-Formyl Compounds
-
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
-
p. 5166 - 5177
(2021/10/25)
-
- Facile N-Formylation of Amines on Magnetic Fe3O4?CuO Nanocomposites
-
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
-
p. 4477 - 4484
(2021/08/30)
-
- Preparation and catalytic evaluation of a palladium catalyst deposited over modified clinoptilolite (Pd&at;MCP) for chemoselective N-formylation and N-acylation of amines
-
Novel palladium nanoparticles stabilized by clinoptilolite as a natural inexpensive zeolite prepared and used for N-formylation and N-acylation of amines at room temperature at environmentally benign reaction conditions in good to excellent yields. Pd (II) was immobilized on the surface of clinoptilolite via facile multi-step amine functionalization to obtain a sustainable, recoverable, and highly active nano-catalyst. The structural and morphological characterizations of the catalyst carried out using XRD, FT-IR, BET and TEM techniques. Moreover, the catalyst is easily recovered using simple filtration and reused for 7 consecutive runs without any loss in activity.
- Amirsoleimani, Mina,Khalilzadeh, Mohammad A.,Zareyee, Daryoush
-
-
- Oxidation Under Reductive Conditions: From Benzylic Ethers to Acetals with Perfect Atom-Economy by Titanocene(III) Catalysis
-
Described here is a titanocene-catalyzed reaction for the synthesis of acetals and hemiaminals from benzylic ethers and benzylic amines, respectively, with pendant epoxides. The reaction proceeds by catalysis in single-electron steps. The oxidative addition comprises an epoxide opening. An H-atom transfer, to generate a benzylic radical, serves as a radical translocation step, and an organometallic oxygen rebound as a reductive elimination. The reaction mechanism was studied by high-level dispersion corrected hybrid functional DFT with implicit solvation. The low-energy conformational space was searched by the efficient CREST program. The stereoselectivity was deduced from the lowest lying benzylic radical structures and their conformations are controlled by hyperconjugative interactions and steric interactions between the titanocene catalyst and the aryl groups of the substrate. An interesting mechanistic aspect is that the oxidation of the benzylic center occurs under reducing conditions.
- Funk, Pierre,Richrath, Ruben B.,Bohle, Fabian,Grimme, Stefan,Gans?uer, Andreas
-
supporting information
p. 5482 - 5488
(2021/02/03)
-
- Catalyst freeN-formylation of aromatic and aliphatic amines exploiting reductive formylation of CO2using NaBH4
-
Herein, we report a sustainable approach forN-formylation of aromatic as well as aliphatic amines using sodium borohydride and carbon dioxide gas. The developed approach is catalyst free, and does not need pressure or a specialized reaction assembly. The reductive formylation of CO2with sodium borohydride generates formoxy borohydride speciesin situ, as confirmed by1H and11B NMR spectroscopy. Thein situformation of formoxy borohydride species is prominent in formamide based solvents and is critical for the success of theN-formylation reactions. The formoxy borohydride is also found to promote transamidation reactions as a competitive pathway along with reductive functionalization of CO2with amine leading toN-formylation of amines.
- Kumar, Arun,Kumar, Yashwant,Mahajan, Dinesh,Sharma, Nidhi,Sharma, Pankaj
-
p. 25777 - 25787
(2021/08/05)
-
- Concentration-dependent circularly polarized luminescence of chiral cyclometalated platinum(II) complexes for electroluminescence
-
Circularly polarized organic light-emitting diodes (CP-OLEDs) have been attracting increasing attention due to the direct generation of CP light, and they show the improved image contrast and luminous efficiency in OLEDs displays. In this work, a pair of chiral Pt(II) complexes with methylbenzylisocyanide and 1,3-bis(2-pyridyl)benzene as a tridentate N∧C∧N ligand were synthesized. Both of them exhibited bright green emission in dilute acetonitrile solution, while strong orange emission in high concentration of acetonitrile solution. However, when the complexes were doped into polymethyl methacrylate, the green emission originated from intrinsic single molecule can be changed to the red emission from excimer by adjusting the doping ratios. More importantly, the amplification of CPL signal can be achieved compared with the solution state. Furthermore, the monochrome devices were fabricated by utilizing these two enantiomers as emitters.
- Guo, Song,Han, Jianmei,Liu, Shujuan,Lu, Hu,Tao, Peng,Xu, Yanan,Zhang, Xinwen,Zhao, Qiang,Zheng, Xiaokang
-
-
- UiO-66 as an efficient catalyst for N-formylation of amines with CO2 and dimethylamine borane as a reducing agent
-
The most effective way to make the best use of CO2, is the reductive formylation of amines, as formamides have many applications in industry. A new protocol has been developed for reductive N-formylation of amines with CO2 as a C1 carbon source and DMAB (Dimethylamine borane) as a reducing agent in the presence of Zr-containing metal–organic framework (MOF) as an efficient, heterogeneous recyclable catalyst. We used UiO-66 and UiO-66-NH2 as catalysts for N-formylation of amines and observed that both the catalyst performs equally. Therefore, we continued our studies with UiO-66 as a catalyst. The UiO-66 MOF shows good catalytic activity and affording the desired formamides in good to excellent yield. This catalytic system is very efficient for several amines including primary and secondary aliphatic cyclic and aromatic amines. Moreover, the prepared catalyst was recycled up to four recycled without a considerable decrease in catalytic activity.
- Phatake, Vishal V.,Mishra, Ashish A.,Bhanage, Bhalchandra M.
-
supporting information
(2019/12/11)
-
- Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
-
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
-
supporting information
p. 5317 - 5324
(2020/09/17)
-
- Copper-Catalyzed Formylation of Amines by using Methanol as the C1 Source
-
Cu/TEMPO catalyst systems are known for the selective transformation of alcohols to aldehydes, as well as for the simultaneous coupling of alcohols and amines to imines under oxidative conditions. In this study, such a Cu/TEMPO catalyst system is found to catalyze the N-formylation of a variety of amines by initial oxidative activation of methanol as the carbonyl source via formaldehyde and formation of N,O-hemiacetals and oxidation of the latter under very mild conditions. A vast range of amines, including aromatic and aliphatic, primary and secondary, and linear and cyclic amines are formylated under these conditions with good to excellent yields. Moreover, paraformaldehyde can be used instead of methanol for the N-formylation.
- Pichardo, Manuel Carmona,Tavakoli, Ghazal,Armstrong, Jessica E.,Wilczek, Tobias,Thomas, Bradley E.,Prechtl, Martin H. G.
-
p. 882 - 887
(2020/02/11)
-
- Bifunctional Pincer Catalysts for Chemoselective Transfer Hydrogenation and Related Reactions
-
A comparative study on the chemoselective transfer hydrogenation of nitroarenes to anilines and related processes using FA as the hydrogen source is described; these processes are catalyzed by a series of pincer catalysts equipped with different functional groups in the secondary coordination sphere. Some new (4 and 5) as well as previously reported (1–3) catalysts belonging to the family of bifunctional PC(sp3)P pincer complexes were employed in this study The reported compounds exhibited remarkably different catalytic activity behavior, depending on the nature of the functional groups. Transfer hydrogenation of nitrobenzene with FA as a hydrogen source was probed using iridium complexes 3 or 4 as a catalyst. Under the same conditions, the analogous palladium complex was found to be useful for the selective amidation of aniline with light carboxylic acids.
- Cohen, Shirel,Bilyachenko, Alexey N.,Gelman, Dmitri
-
p. 3203 - 3209
(2019/02/09)
-
- Citric acid stabilized on the surface of magnetic nanoparticles as an efficient and recyclable catalyst for transamidation of carboxamides, phthalimide, urea and thiourea with amines under neat conditions
-
Abstract: Citric acid-coated magnetic nanoparticles (Fe3O4–CA NPs) were successfully prepared and characterized. This magnetic nanocatalyst was employed as an efficient, recyclable, and environmentally benign heterogeneous catalyst for the transamidation of carboxamides, phthalimide, urea and thiourea with amines. Several derivatives of formylated and transamidated products were synthesized in good to excellent yields in the presence of this catalytic system. And, the catalyst could be easily separated from the reaction mixture using an external magnet and can be reused six times without any significant loss in its catalytic activity. Graphical abstract: [Figure not available: see fulltext.].
- Arefi, Marzban,Kazemi Miraki, Maryam,Mostafalu, Ramin,Satari, Mohammad,Heydari, Akbar
-
p. 393 - 400
(2019/01/28)
-
- Reductive amination of ketonic compounds catalyzed by Cp*Ir(III) complexes bearing a picolinamidato ligand
-
Cp*Ir complexes bearing a 2-picolinamide moiety serve as effective catalysts for the direct reductive amination of ketonic compounds to give primary amines under transfer hydrogenation conditions using ammonium formate as both the nitrogen and hydrogen source. The clean and operationally simple transformation proceeds with a substrate to catalyst molar ratio (S/C) of up to 20,000 at relatively low temperature and exhibits excellent chemoselectivity toward primary amines.
- Tanaka, Kouichi,Miki, Takashi,Murata, Kunihiko,Yamaguchi, Ayumi,Kayaki, Yoshihito,Kuwata, Shigeki,Ikariya, Takao,Watanabe, Masahito
-
p. 10962 - 10977
(2019/09/03)
-
- Amine formylation with CO2 and H2 catalyzed by heterogeneous Pd/PAL catalyst
-
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
-
p. 1141 - 1146
(2019/07/09)
-
- Mn(II)-Catalyzed N -Acylation of Amines
-
A practical protocol has been developed here for the Mn(II)-catalyzed N -acylation of amines with high yields using N, N -dimethylformamide and other amides as the carbonyl source. The protocol is simple, does not require any acid, base, ligand, or other additives, and encompasses a broad substrate scope for primary, secondary, and heterocyclic amines.
- Ma, Juan,Zhang, Jingyu,Gong, Hang
-
p. 693 - 703
(2019/01/23)
-
- Catalyst-Free Transamidation of Aromatic Amines with Formamide Derivatives and Tertiary Amides with Aliphatic Amines
-
A simple catalyst- and promoter-free protocol has been developed for the transamidation of weakly nucleophilic aromatic amines with formamide derivatives and low-reactivity tertiary amides with aliphatic amines. This strategy is advantageous because no catalyst or promoters are needed, no additives are required, separation and purification is easy, and the reaction is scalable. Significantly, this strategy was further applied to synthesize several pharmaceutical molecules on a gram scale, and excellent yields were achieved.
- Yin, Jiawen,Zhang, Jingyu,Cai, Changqun,Deng, Guo-Jun,Gong, Hang
-
supporting information
p. 387 - 392
(2019/01/11)
-
- Rapid synthesis method of biomass-based amide
-
The invention discloses a rapid synthesis method of biomass-based amide, which comprises the steps: formamide is used as an amine source, formic acid is used as a hydrogen source, biomass aldehyde andketone is used as a raw material, the direct addition of formamide and aldehyde and ketone components and the reduction of formic acid is promoted to prepare the corresponding formamide derivative byrapidly heating under microwave-assisted heating and in the absence of a solvent and a catalyst; the formamide derivative is selectively converted to the corresponding primary amide by alcoholysis under the action of a base. The microwave assisted heating reaction system of the invention has higher catalytic efficiency than the corresponding oil bath system, greatly shortens the reaction time, remarkably improves the selectivity. The conversion rate of the biomass aldehyde or ketone compound is at least 99%, and the yield of the formamide derivative can reach 85 to 99%; the formamide can be synthesized by alcoholysis to obtain a primary amide with a yield of 92 to 99%.
- -
-
Paragraph 0070-0072; 0075
(2019/01/15)
-
- N-formylation of amine using graphene oxide as a sole recyclable metal-free carbocatalyst
-
Abstract: Graphene oxide (GO), an inexpensive, environment-friendly, and metal-free carbocatalyst, used for the N-formylation of amines is developed. In this reaction, GO shows good activity, selectivity, and recyclability. This strategy has an array of advantages, such as being metal free, without additive, wide-scope protocol, scalable with a low catalyst loading of 3?wt%, use of readily available and recyclable carbocatalyst, and DMF as a readily available formyl source. Furthermore, this strategy provides an avenue for the convenient hydroformylation of various amines. Graphical abstract: [Figure not available: see fulltext.].
- Ma, Juan,Zhang, Jingyu,Zhou, Xiao,Wang, Jiawei,Gong, Hang
-
p. 2851 - 2860
(2018/10/31)
-
- Method for synthesizing formamide derivatives by molybdenum catalyzed formylation reaction
-
The invention discloses a method for synthesizing formamide derivatives by molybdenum catalyzed formylation reaction. The method includes that the formamide derivatives are generated by one-pot reaction of amine compounds and formamide compounds under the catalytic action of molybdenum salts and/or molybdenum oxides. Reaction methods and catalysts are cheap and easy to acquire, reaction steps andoperations are simple, the method has advantages of high reaction selectivity, high yield, expandability in reaction and the like, and defects of high toxicity of reaction agents, expensive catalysts,complex reaction steps, high quality of by-products and the like in the prior art are overcome.
- -
-
Paragraph 0073; 0074
(2018/05/16)
-
- Diverse catalytic reactivity of a dearomatized PN3P?-nickel hydride pincer complex towards CO2 reduction
-
A dearomatized PN3P?-nickel hydride complex has been prepared using an oxidative addition process. The first nickel-catalyzed hydrosilylation of CO2 to methanol has been achieved, with unprecedented turnover numbers. Selective methylation and formylation of amines with CO2 were demonstrated by such a PN3P?-nickel hydride complex, highlighting its versatile functions in CO2 reduction.
- Li, Huaifeng,Gon?alves, Théo P.,Zhao, Qianyi,Gong, Dirong,Lai, Zhiping,Wang, Zhixiang,Zheng, Junrong,Huang, Kuo-Wei
-
supporting information
p. 11395 - 11398
(2018/10/20)
-
- An Efficient Ruthenium Catalyst Bearing Tetradentate Ligand for Hydrogenations of Carbon Dioxide
-
A ruthenium complex with a tetradentate bipyridine ligand was proved to be a highly efficient catalyst for the conversions of CO2. Turnover numbers up to 300 000, 9800, and 2100 were achieved for the hydrogenations of CO2 to formamides, formamides to methanol and amines, and the direct hydrogenation of CO2 to methanol, respectively.
- Zhang, Feng-Hua,Liu, Chong,Li, Wei,Tian, Gui-Long,Xie, Jian-Hua,Zhou, Qi-Lin
-
supporting information
p. 1000 - 1002
(2018/09/21)
-
- 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
-
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.
-
p. 3907 - 3913
(2018/09/12)
-
- Method for synthesis of formamide derivatives by cobalt catalysis of formylation reaction
-
The invention discloses a method for synthesis of formamide derivatives by cobalt catalysis of formylation reaction. The method comprises that the formamide derivatives are produced by one-pot reaction of amine compounds and formamide compounds under the catalysis of cobalt salts; the method has the advantages of cheap and easily obtained reaction raw materials and catalysts, simple reaction stepsand operation, high reaction selectivity, high yield, extendable reaction and the like, and overcomes the defects of high reaction reagent toxicity, expensive catalysts, more reaction steps, more byproducts and the like in the prior art.
- -
-
Paragraph 0074; 0075
(2018/04/21)
-
- Method of using graphene oxide to catalyze formylation reaction to synthesize formamide derivative
-
The invention discloses a method of using graphene oxide to catalyze formylation reaction to synthesize a formamide derivative. The method includes: allowing amine compound and formamide compound to be in one-pot reaction under catalytic action of graphene oxide to generate the formamide derivative. Reaction raw materials and a catalyst are low in cost and easy to obtain, the catalyst can be recycled, reaction steps and operations are simple, the method has the advantages of high reaction selectivity, high yield and supportiveness of expanding reaction, and the defects that reaction reagents are high in toxicity, catalysts are expensive, the number of reaction steps is large and the number of byproducts is large in the prior art are overcome.
- -
-
Paragraph 0072; 0073
(2018/05/16)
-
- Cobalt(II)-Catalyzed N-Acylation of Amines through a Transamidation Reaction
-
A practical protocol has been developed for a Co(OAc)2·4H2O-catalyzed transamidation reaction. The reaction gives high yields and uses N,N-dimethylformamide and other amides as carbonyl sources. The protocol is rapid and simple, and it does not require any acids, bases, ligands, or other additives. It works well for a wide range of primary, secondary, and heterocyclic amines.
- Ma, Juan,Zhang, Feng,Zhang, Jingyu,Gong, Hang
-
p. 4940 - 4948
(2018/09/25)
-
- Method for synthesizing formamide derivative through Mn-catalyzed formylation reaction
-
The invention discloses a method for synthesizing a formamide derivative through Mn-catalyzed formylation reaction. The method disclosed by the invention is characterized in that an amine compound anda formamide compound are subjected to one-pot reaction under the catalytic action of manganese salt to generate the formamide derivative. The method disclosed by the invention has the beneficial effects that reaction raw materials and a catalyst are cheap and easy to get, reaction steps and operation are simple, the advantages of high reaction selectivity, high yield and expandable reaction are achieved, and the defects that a reagent is high in toxicity, the catalyst is expensive, reaction steps are tedious and byproducts are more in the prior art are overcome.
- -
-
Paragraph 0069; 0070
(2018/05/16)
-
- Tetraethylorthosilicate as a mild dehydrating reagent for the synthesis of N-formamides with formic acid
-
The synthesis of N-formamides with formic acid as a formyl source under mild conditions was achieved using tetraethylorthosilicate (TEOS), a low cost and environmentally benign reagent. The mild conditions in this system enable the formylation of a variety of amino acid derivatives including stereochemically labile phenylglycine ethyl ester with 96% ee. This new protocol could also be applied to simple amines including weakly basic aniline derivatives, giving various primary and secondary formamides.
- Nishikawa, Yasuhiro,Nakamura, Hidetsugu,Ukai, Norimitsu,Adachi, Wakana,Hara, Osamu
-
supporting information
p. 860 - 863
(2017/02/10)
-
- First report on bio-catalytic N-formylation of amines using ethyl formate
-
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.
-
supporting information
p. 2382 - 2385
(2017/02/23)
-
- Ru/ceria-catalyzed direct formylation of amines and CO to produce formamides
-
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
-
-
- Nonacidic Farnesoid X Receptor Modulators
-
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
-
supporting information
p. 7199 - 7205
(2017/09/07)
-
- An efficient reduction of N-substituted carbonylimidazolides into formamides by NaBH4
-
A novel, simple and versatile protocol was investigated for highly efficient synthesis of formamides through reducing N-substituted carbonylimidazolides by NaBH4 under mild reaction conditions. By this method, not only carboxylic acids or isocyanates, but also amines can readily access formamides with high yields.
- Chen, Zhiyong,Cao, Yiming,Tian, Zeyu,Zhou, Xuan,Xu, Wenjin,Yang, Jia,Teng, Hanbing
-
p. 2166 - 2170
(2017/05/10)
-
- Transamidation of primary carboxamides, phthalimide, urea and thiourea with amines using Fe(OH)3@Fe3O4 magnetic nanoparticles as an efficient recyclable catalyst
-
The highly efficient transamidation of primary amides, phthalimide, urea and thiourea with amines catalyzed by magnetic Fe(OH)3@Fe3O4 nanoparticles is described. This magnetic nanocomposite is able to catalyze transamidation reactions of a wide range of the above-mentioned substrates with amines, generating a new amide bond in moderate to good yields. The catalyst exhibited very good recyclability and reusability up to five runs without significant loss of its catalytic activity.
- Arefi, Marzban,Heydari, Akbar
-
p. 24684 - 24689
(2016/03/16)
-
- Chemoselective Schwartz Reagent Mediated Reduction of Isocyanates to Formamides
-
Addition of the in situ generated Schwartz reagent to widely available isocyanates constitutes a chemoselective, high-yielding, and versatile approach to the synthesis of variously functionalized formamides. Steric and electronic factors or the presence of sensitive functionalities (esters, nitro groups, nitriles, alkenes) do not compromise the potential of the method. Full preservation of the stereochemical information contained in the starting materials is observed. The use of formamides in the nucleophilic addition of organometallic reagents (Chida-Sato allylation, Charette-Huang addition to imidoyl triflate activated amides, Matteson homologation of boronic esters) is briefly investigated.
- Pace, Vittorio,De La Vega-Hernández, Karen,Urban, Ernst,Langer, Thierry
-
supporting information
p. 2750 - 2753
(2016/06/15)
-
- Transamidation catalysed by a magnetically separable Fe3O4 nano catalyst under solvent-free conditions
-
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.
-
p. 52724 - 52728
(2016/06/14)
-
- Formamide Synthesis through Borinic Acid Catalysed Transamidation under Mild Conditions
-
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
-
supporting information
p. 5894 - 5898
(2016/04/26)
-
- Supported nano-gold-catalyzed N-formylation of amines with paraformaldehyde in water under ambient conditions
-
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
-
p. 808 - 816
(2016/02/12)
-
- Bioinspired organocatalytic aerobic C-H oxidation of amines with an ortho -quinone catalyst
-
A simple bioinspired ortho-quinone catalyst for the aerobic oxidative dehydrogenation of amines to imines is reported. Without any metal cocatalysts, the identified optimal ortho-quinone catalyst enables the oxidations of α-branched primary amines and cyclic secondary amines. Mechanistic studies have disclosed the origins of different performances of ortho-quinone vs para-quinone in biomimetic amine oxidations.
- Qin, Yan,Zhang, Long,Lv, Jian,Luo, Sanzhong,Cheng, Jin-Pei
-
supporting information
p. 1469 - 1472
(2015/03/30)
-
- Microwave-promoted direct amidation of unactivated esters catalyzed by heteropolyanion-based ionic liquids under solvent-free conditions
-
Abstract A simple and efficient procedure for the synthesis of amides directly from unactivated esters and amines catalyzed by heteropolyanion-based ionic liquids under microwave-promoted and solvent-free conditions has been reported. The practical protocol was found to be compatible with different structurally diverse substrates. Moderate to excellent yields, solvent-free media, and operational simplicity are the main highlights. Furthermore, the heteropolyanion-based ionic liquids were easily reusable for this amidation.
- Fu, Renzhong,Yang, Yang,Ma, Yunsheng,Yang, Fei,Li, Jingjing,Chai, Wen,Wang, Quan,Yuan, Rongxin
-
p. 4527 - 4531
(2015/06/30)
-
- Efficient isocyanide-less isocyanide-based multicomponent reactions
-
Isocyanides are the Jekyll and Hyde of organic chemistry allowing for extremely interesting transformations that are not only extremely odorous but also noxious. Therefore, an isocyanide-less isocyanide-based multicomponent reaction (IMCR) has been developed, and this protocol is expected to replace many of the old procedures in the future not only in IMCR but in other areas of organic chemistry as well.
- Neochoritis, Constantinos G.,Stotani, Silvia,Mishra, Bhupendra,D?mling, Alexander
-
supporting information
p. 2002 - 2005
(2015/04/27)
-
- Effective Formylation of Amines with Carbon Dioxide and Diphenylsilane Catalyzed by Chelating bis(tzNHC) Rhodium Complexes
-
The reductive formylation of amines using CO2 and hydrosilanes is an attractive method for incorporating CO2 into valuable organic compounds. However, previous systems required either high catalyst loadings or high temperatures to achieve high efficiency, and the substrate scope was mostly limited to simple amines. To address these problems, a series of alkyl bridged chelating bis(NHC) rhodium complexes (NHC=N-heterocyclic carbene) have been synthesized and applied to the reductive formylation of amines using CO2 and Ph2SiH2. A rhodium-based bis(tzNHC) complex (tz=1,2,3-triazol-5-ylidene) was identified to be highly effective at a low catalyst loading and ambient temperature, and a wide substrate scope, including amines with reducible functional groups, were compatible. Beyond the norm: Rhodium complexes bearing a strong electron-donating bis(1,2,3-triazol-5-ylidene) ligand were found to be excellent catalysts for the reductive formylation of amines with CO2 and Ph2SiH2 at ambient temperature. The catalyst system possesses a broad substrate scope which tolerates a variety of reducible functional groups and is suitable for the synthesis of bioactive compounds. Tf=trifuoromethanesulfonyl.
- Nguyen, Thanh V. Q.,Yoo, Woo-Jin,Kobayashi
-
supporting information
p. 9209 - 9212
(2015/08/06)
-
- Enantioselective addition of diethylzinc to aldehydes catalyzed by (R)-1-phenylethylamine-derived 1,4-amino alcohols
-
A series of o-xylylene-type 1,4-amino alcohols, synthesized from (R)-1-phenylethylamine, were used as chiral ligands for the enantioselective addition of diethylzinc to benzaldehyde. (S)-1-Phenyl-1-propanol was obtained with high enantioselectivity in all cases since the stereochemical outcome of the reaction was controlled by the chiral benzylic carbon bearing amino group. Highest catalytic activity was obtained by using (R)-1-{2-[1-(pyrrolidin-1-yl)ethyl]phenyl}cyclohexan-1-ol (1n) derived from (R)-1-(1-phenylethyl)pyrrolidine and cyclohexanone. Various chiral secondary alcohols were obtained by the reaction of diethylzinc and aldehydes in the presence of 1n within 2 h with good to high enantioselectivities.
- Asami, Masatoshi,Miyairi, Naomichi,Sasahara, Yukihiro,Ichikawa, Ken-Ichi,Hosoda, Naoya,Ito, Suguru
-
p. 6796 - 6802
(2015/08/24)
-
- Microwave-assisted heteropolyanion-based ionic liquids catalyzed transamidation of non-activated carboxamides with amines under solvent-free conditions
-
An environmentally benign and highly efficient protocol for the transamidation of non-activated carboxamides with amines using heteropolyanion-based ionic liquids as catalysts under microwave-assisted and solvent-free conditions has been developed. As evaluated by the reactions of a structurally diverse set of amides and amines, the scope and utility of the transamidation proved to be quite general. Operational simplicity, solvent-free media, the potential reusability of catalysts and wide functional group tolerance are attractive features. This method provides a much improved protocol over the existing methods.
- Fu, Renzhong,Yang, Yang,Chen, Zhikai,Lai, Wenchen,Ma, Yongfeng,Wang, Quan,Yuan, Rongxin
-
p. 9492 - 9499
(2015/03/04)
-
- Formylation of amines through catalyst- and solvent-free transamidation reaction
-
The transamidation between formamide and various amines proceeds under heating, without any catalyst nor solvent, providing thus green and neutral conditions for the formylation of primary and secondary amines. The resulting amide product can be directly transformed, in a one pot sequence, into monomethylamine.
- Lebleu, Thomas,Kotsuki, Hiyoshizo,Maddaluno, Jacques,Legros, Julien
-
supporting information
p. 362 - 364
(2014/01/06)
-
- Transformylating amine with DMF to formamide over CeO2 catalyst
-
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
-
supporting information
p. 2438 - 2441
(2014/03/21)
-
- A simple method for preparation of ZnO nanoparticles as a highly efficient nanocatalyst for N-formylation of primary and secondary amines under solvent-free condition
-
A convenient reaction between alky, aryl, and heteroalkyl amines and formic acid as a formylating agent in the presence of catalytic amount of mechanochemically synthesized zinc oxide nanoparticles under solvent-free condition for the synthesis of corresponding N-formyl derivatives is described. Copyright Taylor and Francis Group, LLC.
- Alinezhad, Heshmatollah,Salehian, Fatemeh
-
p. 532 - 538
(2013/07/19)
-
- Sulfated tungstate: A highly efficient catalyst for transamidation of carboxamides with amines
-
An environmentally benign protocol for the transamidation of carboxamides with amines using sulfated tungstate, as a heterogeneous catalyst, has been developed. The method has been successfully applied to the synthesis of a wide range of aromatic and aliphatic amides and phthalimides. Efficient transformation, mild reaction conditions, easy product isolation and the potential reusability of the catalyst are attractive features.
- Pathare, Sagar P.,Jain, Ashish Kumar H.,Akamanchi, Krishnacharya G.
-
p. 7697 - 7703
(2013/06/27)
-
- A convenient procedure for N-formylation of amines
-
A simple and convenient method for the N-formylation of primary and secondary amines including amino acids has been developed utilizing formamide and sodium methoxide in moderate to excellent yield. This reagent is also utilized for one pot conversion of compounds having amino esters to N-formyl amides.
- Joseph, Sony,Das, Prasenjit,Srivastava, Bindu,Nizar, Hashim,Prasad, Mohan
-
p. 929 - 931
(2013/02/25)
-
- Direct synthesis of amides from carboxylic acids and amines using B(OCH2CF3)3
-
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.
-
p. 4512 - 4523
(2013/06/05)
-
- Copper-catalyzed hydroboration of carbon dioxide
-
A copper/N-heterocyclic carbene catalyzed hydroboration of carbon dioxide has been developed to give a formic acid derivative selectively under mild conditions. Investigations directed toward understanding the catalytic cycle of this process have been carried out, and the hydroboration product can be directly used as a formylation reagent for various amines.
- Shintani, Ryo,Nozaki, Kyoko
-
supporting information
p. 2459 - 2462
(2013/06/27)
-
- N-Formylation of amines by methanol activation
-
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
-
supporting information
p. 1776 - 1779
(2013/06/26)
-
- Chain branching approach in structure modification of TRPV1 receptor antagonist MK056 and its analogs
-
A series of chain branched 1,3-dibenzylthiourea derivatives were designed, synthesized, and evaluated for their antagonist activity against TRPV1. The synthesized chain branched 1,3dibenzylthioureas 9a-g were tested for their antagonist activities against TRPV1 by 45 Ca 2+ influx assay using neonatal rat cultured spinal sensory neurons. Fluorinated ethyl-branched analog 9g showed the most potent antagonist activity with an IC50 value of 0.41 μM, but all of the chain branched analogs were less potent than the parent compounds MK-056 and SC0030, indicating that chain branching on the benzylic position of B-ring is detrimental to potency. Optimized receptor binding seems to be interfered by chain branching, and resulted in decrease in potency.
- Jang, Mijung,Ryu, Chong Hyun,Park, Young-Ho,Kim, Hee-Doo
-
scheme or table
p. 321 - 326
(2012/08/29)
-