- 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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- 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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- 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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- 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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- 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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- Small-compound enhancers for functional O-mannosylation of alpha-dystroglycan, and uses thereof
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The present invention provides compounds that can enhance functional O-mannosylation of proteins including alpha-dystroglycan. Also provided are methods of preparation of the compounds defined by the formula I. Also provided are the methods of using the compounds or the pharmaceutical acceptable salts or prodrugs thereof in treating and preventing subjects suffering from the diseases including muscular dystrophies and cancers.
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Page/Page column 12
(2019/03/14)
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- N-Formylation of Amines with CO2 and H2 by Using NHC–Iridium Coordination Assemblies as Solid Molecular Catalysts
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One of the NHC–iridium coordination assemblies containing 1,5-cyclooctadiene (COD) and iodide ion has been demonstrated as robust, efficient, recyclable solid molecular catalyst for N-formylation of diverse primary and secondary amines with CO2 and H2 under mild reaction conditions. Remarkably, in the case of N,N-dimethylformamide production, even at 0.1 mol % catalyst loading under solvent-free conditions, the solid catalyst can be readily recovered by simply filtration and reused more than 10 runs without noticeable loss of activity.
- Zhang, Yang,Wang, Jiaquan,Zhu, Haibo,Tu, Tao
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supporting information
p. 3018 - 3021
(2018/09/06)
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- Rapid synthesis method of biomass-based amide
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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%.
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Paragraph 0030-0032; 0035-0039
(2019/01/15)
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- Formyloxyacetoxyphenylmethane as an N-Formylating Reagent for Amines, Amino Acids, and Peptides
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Formyloxyacetoxyphenylmethane is a stable, water-tolerant, N-formylating reagent for primary and secondary amines that can be used under solvent-free conditions at room temperature to prepare a range of N-formamides, N-formylanilines, N-formyl-α-amino acids, N-formylpeptides, and an isocyanide.
- Chapman, Robert S. L.,Lawrence, Ruth,Williams, Jonathan M. J.,Bull, Steven D.
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supporting information
p. 4908 - 4911
(2017/09/23)
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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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- 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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- Chemoselective Schwartz Reagent Mediated Reduction of Isocyanates to Formamides
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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
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supporting information
p. 2750 - 2753
(2016/06/15)
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- Isonitrile alkylations: A rapid route to imidazo[1,5-a]pyridines
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Metalated arylmethylisonitriles readily add to 2-chloropyridines to afford imidazo[1,5-a]pyridines. Analogous additions to imidoyl chlorides and a chloroquinoline provide imidazoles and an imidazo[1,5-a]quinolone which, like imidazo[1,5-a]pyridines, are v
- Li, Yajun,Chao, Allen,Fleming, Fraser F.
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supporting information
p. 2111 - 2113
(2016/02/05)
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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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- Efficient isocyanide-less isocyanide-based multicomponent reactions
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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
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supporting information
p. 2002 - 2005
(2015/04/27)
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- C-N and N-H Bond Metathesis Reactions Mediated by Carbon Dioxide
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Herein, we report CO2-mediated metathesis reactions between amines and DMF to synthesize formamides. More than 20 amines, including primary, secondary, aromatic, and heterocyclic amines, diamines, and amino acids, are converted to the corresponding formamides with good-to-excellent conversions and selectivities under mild conditions. This strategy employs CO2 as a mediator to activate the amine under metal-free conditions. The experimental data and in situ NMR and attenuated total reflectance IR spectroscopy measurements support the formation of the N-carbamic acid as an intermediate through the weak acid-base interaction between CO2 and the amine. The metathesis reaction is driven by the formation of a stable carbamate, and a reaction mechanism is proposed.
- Wang, Yehong,Zhang, Jian,Liu, Jing,Zhang, Chaofeng,Zhang, Zhixin,Xu, Jie,Xu, Shutao,Wang, Fangjun,Wang, Feng
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p. 2066 - 2072
(2015/06/30)
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- Microwave-promoted direct amidation of unactivated esters catalyzed by heteropolyanion-based ionic liquids under solvent-free conditions
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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
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p. 4527 - 4531
(2015/06/30)
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- Small molecules enhance functional O-mannosylation of Alpha-dystroglycan
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Alpha-dystroglycan (α-DG), a highly glycosylated receptor for extracellular matrix proteins, plays a critical role in many biological processes. Hypoglycosylation of α-DG results in various types of muscular dystrophies and is also highly associated with progression of majority of cancers. Currently, there are no effective treatments for those devastating diseases. Enhancing functional O-mannosyl glycans (FOG) of α-DG on the cell surfaces is a potential approach to address this unmet challenge. Based on the hypothesis that the cells can up-regulate FOG of α-DG in response to certain chemical stimuli, we developed a cell-based high-throughput screening (HTS) platform for searching chemical enhancers of FOG of α-DG from a large chemical library with 364,168 compounds. Sequential validation of the hits from a primary screening campaign and chemical works led to identification of a cluster of compounds that positively modulate FOG of α-DG on various cell surfaces including patient-derived myoblasts. These compounds enhance FOG of α-DG by almost ten folds, which provide us powerful tools for O-mannosylation studies and potential starting points for the development of drug to treat dystroglycanopathy.
- Lv, Fengping,Li, Zhi-Fang,Hu, Wenhao,Wu, Xiaohua
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supporting information
p. 7661 - 7670
(2015/12/18)
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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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- Microwave-assisted heteropolyanion-based ionic liquids catalyzed transamidation of non-activated carboxamides with amines under solvent-free conditions
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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
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p. 9492 - 9499
(2015/03/04)
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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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- Enhancing the scope of the Diels-Alder reaction through isonitrile chemistry: Emergence of a new class of acyl-activated dienophiles
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α,β-Unsaturated imides, formylated at the nitrogen atom, comprise a new and valuable family of dienophiles for servicing Diels-Alder reactions. These systems are assembled through extension of recently discovered isonitrile chemistry to the domain of α,β-unsaturated acids. Cycloadditions are facilitated by Et2AlCl, presumably via chelation between the two carbonyl groups of the N-formyl amide. Applications of the isonitrile/Diels-Alder logic to the IMDA reaction, as well as methodologies to modify the N-formyl amide of the resultant cycloaddition product, are described. It is expected that this easily executed chemistry will provide a significant enhancement for application of Diels-Alder reactions to many synthetic targets.
- Townsend, Steven D.,Wu, Xiangyang,Danishefsky, Samuel J.
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supporting information; experimental part
p. 10659 - 10663
(2012/08/08)
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- Facile and highly efficient N-formylation of amines using a catalytic amount of iodine under solvent-free conditions
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We developed a simple, practical, and catalytic method for the N-formylation of a wide variety of amines in the presence of molecular iodine as a catalyst under solvent-free conditions. This reaction is applicable to the chemoselective N-formylation of amino groups and -amino acid esters without epimerization.
- Kim, Joong-Gon,Jang, Doo Ok
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experimental part
p. 2093 - 2096
(2010/10/03)
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- Formylation without catalyst and solvent at 80 °C
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A simple and efficient protocol for N-formylation of aliphatic and heterocyclic amines has been described with formic acid in the absence of catalyst and solvent.
- Rahman, Matiur,Kundu, Dhiman,Hajra, Alakananda,Majee, Adinath
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experimental part
p. 2896 - 2899
(2010/06/14)
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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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- Convenient one-pot method for formylation of amines and alcohols using formic acid and 1,1'-oxalyldiimidazole
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1,1'-Oxalyldiimidazole (7) reacts with formic acid (8) in acetonitrile at room temperature to give N-formylimidazole (5), which promptly undergoes aminolysis and alcoholysis to yield formamides (2) or formates (4).
- Kitagawa,Arita,Nagahata
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p. 1655 - 1657
(2007/10/02)
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- Improved procedure for N-formylation of amines to formamides using formic acid, oxalyl chloride and imidazole
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The reaction of imidazole (15) with formyl chloride (14), generated in situ by the action of oxalyl chloride (10) on formic acid (3), afforded N-formylimidazole (7), which is a convenient formylating reagent. This procedure was used to prepare N-formyl derivatives (2) of aliphatic, aromatic and heteroaromatic amines (1) under mild conditions.
- Kitagawa,Ito,Tsutsui
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p. 1931 - 1934
(2007/10/02)
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- Difunctional furan derivatives
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Compounds of the formula (I) STR1 in which R1 and R2 are the same or different and are selected from hydrogen, substituted or unsubstituted methyl or ethyl radicals, and substituted or unsubstituted vinyl radicals, X is a --NH2 or --NCO group, and n is 0 or 1 with the proviso that n is not 0 when X is --NH2.
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