cas 93-61-8, N-Methylformanilide | Articles data

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Fieser,Jones
p. 66
(1940)
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Additive-free selective methylation of secondary amines with formic acid over a Pd/In2O3 catalyst
Formic acid is used as the sole carbon and hydrogen source in the methylation of aromatic and aliphatic amines to methylamines. The reaction proceeds via a formylation/transfer hydrogenation pathway over a solid Pd/In2O3 catalyst without the need for any additive.
Benaissa, Idir,Cantat, Thibault,Genre, Caroline,Godou, Timothé,Pinault, Mathieu
p. 57 - 61
(2022/01/19)

Olefin functionalized IPr.HCl monomer as well as preparation method and application thereof
The invention relates to an olefin functionalized IPr.HCl monomer, a preparation method thereof, a method for preparing an N-heterocyclic carbene functionalized organic polymer (PS-IPr-x) by using the olefin functionalized IPr.HCl monomer, and application of the N-heterocyclic carbene functionalized organic polymer as a heterogeneous catalyst for catalyzing reduction N-formylation of carbon dioxide and amine. A heterogeneous catalyst is prepared by using cheap and easily available DVB as a polymerization cross-linking agent through an AIBN-initiated olefin polymerization method, and has the advantages of low preparation cost and simple preparation method. Meanwhile, the catalytic activity of the catalyst is obviously higher than that of reported catalysts, and the catalyst has a wide practical application prospect.
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Paragraph 0069-0073; 0075; 0078

(2021/06/21)

HCl-mediated transamidation of unactivated formamides using aromatic amines in aqueous media
We report transamidation protocol to synthesize a range of secondary and tertiary amides from weakly nucleophilic aromatic and hetero-aryl amines with low reactive formamide derivatives, utilizing hydrochloric acid as catalyst. This current acid mediated strategy is beneficial because it eliminates the need for a metal catalyst, promoter or additives in the reaction, simplifies isolation and purification. Notably, this approach conventionally used to synthesize molecules on gram scales with excellent yields and a high tolerance for functional groups.
Dhawan, Sanjeev,Girase, Pankaj Sanjay,Kumar, Vishal,Karpoormath, Rajshekhar
p. 3729 - 3739
(2021/10/14)

Unreactive C-N Bond Activation of Anilines via Photoinduced Aerobic Borylation
Unreactive C-N bond activation of anilines was achieved by photoinduced aerobic borylation. A diverse range of tertiary and secondary anilines were converted to aryl boronate esters in moderate to good yields with wide functional group tolerance under simple and ambient photochemical conditions. This transformation achieved the direct and facile C-N bond activation of unreactive anilines, providing a convenient and practical route transforming widely available anilines into useful aryl boronate esters.
Ji, Shuohan,Luo, Lu,Qin, Shengxiang,Yin, Chunyu,Zhang, Hua
supporting information

(2021/12/27)

Catalyst-free photoinduced selective oxidative C(sp3)-C(sp3) bond cleavage in arylamines
Due to the directional nature of sp3-hybridized orbitals and the absence of π-orbitals, the oxidative cleavage of the kinetically and thermodynamically stable C(sp3)-C(sp3) bond is extremely difficult and remains scarcely explored. In this work, under the double argument of quantum mechanics (QM) computations and meticulous experiments on our well-designed C-C single bond cleavage mechanism, we discovered a means of photoinduced selective oxidative C(sp3)-C(sp3) bond cleavage in arylamines, easily achieved by simple visible light irradiation using O2as a benign oxidant under very mild conditions. The utility of our methodology was demonstrated by the C(sp3)-C(sp3) bond cleavage in morpholine/piperazine arylamines with excellent functional group tolerance. Importantly, our methodology is noteworthy, not only in that it does not require any catalysts, but also in that it provides valuable possibilities for the scalable functionalization of clinical drugs and natural products.
Duan, Wentao,Lian, Qi,Wang, Songping,Wei, Wentao,Zhou, Jingwei
supporting information
p. 3261 - 3267
(2021/05/21)

Supported CuII Single-Ion Catalyst for Total Carbon Utilization of C2 and C3 Biomass-Based Platform Molecules in the N-Formylation of Amines
The shift from fossil carbon sources to renewable ones is vital for developing sustainable chemical processes to produce valuable chemicals. In this work, value-added formamides were synthesized in good yields by the reaction of amines with C2 and C3 biomass-based platform molecules such as glycolic acid, 1,3-dihydroxyacetone and glyceraldehyde. These feedstocks were selectively converted by catalysts based on Cu-containing zeolite 5A through the in situ formation of carbonyl-containing intermediates. To the best of our knowledge, this is the first example in which all the carbon atoms in biomass-based feedstocks could be amidated to produce formamide. Combined catalyst characterization results revealed preferably single CuII sites on the surface of Cu/5A, some of which form small clusters, but without direct linking via oxygen bridges. By combining the results of electron paramagnetic resonance (EPR) spin-trapping, operando attenuated total reflection (ATR) IR spectroscopy and control experiments, it was found that the formation of formamides might involve a HCOOH-like intermediate and .NHPh radicals, in which the selective formation of .OOH radicals might play a key role.
Brückner, Angelika,Dai, Xingchao,Kreyenschulte, Carsten,Rabeah, Jabor,Shi, Feng,Wang, Xinzhi
p. 16889 - 16895
(2021/09/25)

Nickel-Catalyzed Amination of Aryl Chlorides with Amides
A nickel-catalyzed amination of aryl chlorides with diverse amides via C-N bond cleavage has been realized under mild conditions. A broad substrate scope with excellent functional group tolerance at a low catalyst loading makes the protocol powerful for synthesizing various aromatic amines. The aryl chlorides could selectively couple to the amino fragments rather than the carbonyl moieties of amides. Our protocol complements the conventional amination of aryl chlorides and expands the usage of inactive amides.
Li, Jinpeng,Huang, Changyu,Wen, Daheng,Zheng, Qingshu,Tu, Bo,Tu, Tao
supporting information
p. 687 - 691
(2021/01/09)

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
(2020/08/22)

Germyliumylidene: A Versatile Low Valent Group 14 Catalyst
Bis-NHC stabilized germyliumylidenes [RGe(NHC)2]+ are typically Lewis basic (LB) in nature, owing to their lone pair and coordination of two NHCs to the vacant p-orbitals of the germanium center. However, they can also show Lewis acidity (LA) via Ge?CNHC σ* orbital. Utilizing this unique electronic feature, we report the first example of bis-NHC-stabilized germyliumylidene [MesTerGe(NHC)2]Cl (1), (MesTer=2,6-(2,4,6-Me3C6H2)2C6H3; NHC= IMe4=1,3,4,5-tetramethylimidazol-2-ylidene) catalyzed reduction of CO2 with amines and arylsilane, which proceeds via its Lewis basic nature. In contrast, the Lewis acid nature of 1 is utilized in the catalyzed hydroboration and cyanosilylation of carbonyls, thus highlighting the versatile ambiphilic nature of bis-NHC stabilized germyliumylidenes.
Sarkar, Debotra,Dutta, Sayan,Weetman, Catherine,Schubert, Emeric,Koley, Debasis,Inoue, Shigeyoshi
supporting information
p. 13072 - 13078
(2021/08/09)

Study on the mild, rapid and selective difluorocarbene-mediated triclassification of iododifluoroacetophenone with secondary amines and tree model for product classification
Difluorocarbene is a very active and widely used intermediate in organic synthesis. In this work, a room temperature difluorocarbene-mediated triclassification reaction of iododifluoroacetophenone (2) and secondary amines with mild condition, short reaction time (only 10 min) and high selectivity had been studied, which produced one of the following three substances: N-CF2H derivatives (up to 87% yield), formamides (82–89% yield) or the recycled starting secondary amines. This phenomenon was related to the structural stability of the corresponding products. If unstable, it would be hydrolyzed to formamides first, and then further hydrolyzed to starting amines. Based on the geometric structure of the raw materials, the corresponding prediction tree model was established, which provided guidance for the further application of difluoromethylation of Vemurafenib (1ee) and AZD9291 (1ff).
Chen, Xiu-Ping,Han, Jie,Hu, Yin-Jie,Li, Yun-Fang,Wang, Xiang-Cong,Ran, Jian-Xiong,Wang, Zhong-Hua,Wu, Fan-Hong
(2020/12/14)

Acid-catalyzed chemodivergent reactions of 2,2-dimethoxyacetaldehyde and anilines
Chemodivergent reactions of 2,2-dimethoxyacetaldehyde and anilines were described, which were established on the basis of either a C[sbnd]C bond cleavage or a rearrangement process of a reaction intermediate. These reactions proceeded in a condition-determined manner with good functional group tolerance. In the first model, 2,2-dimethoxyacetaldehyde reacted with aniline to form a new C[sbnd]N bond, in the presence of O2, via a C[sbnd]C bond cleavage reaction. However, in the second model, by performing the reaction in the absence of O2, Heyns rearrangement occurred and generated a new C[sbnd]O bond to form methyl phenylglycinate. Such condition-determined reactions not only offered the new way for value-added conversion of biomass-derived platform molecule, 2, 2-dimethoxyacetaldehyde, but also provided efficient methods for the synthesis of N-arylformamides and methyl phenylglycinates.
Guo, Luxia,Chen, Zihao,Zhu, Hongmei,Li, Minghao,Gu, Yanlong
supporting information
p. 1419 - 1422
(2020/11/12)

Engineering of Microcage Carbon Nanotube Architectures with Decoupled Multimodal Porosity and Amplified Catalytic Performance
New approaches for the engineering of the 3D microstructure, pore modality, and chemical functionality of hierarchically porous nanocarbon assemblies are key to develop the next generation of functional aerogel and membrane materials. Here, interfacially driven assembly of carbon nanotubes (CNT) is exploited to fabricate structurally directed aerogels with highly controlled internal architectures, composed of pseudo-monolayer, CNT microcages. CNT Pickering emulsions enable engineering at fundamentally different length scales, whereby the microporosity, mesoporosity, and macroporosity are decoupled and individually controlled through CNT type, CNT number density, and process energy, respectively. In addition, metal nanocatalysts (Cu, Pd, and Ru) are embedded within the architectures through an elegant sublimation and shock-decomposition approach; introducing the first approach that enables through-volume functionalization of intricate, pre-designed aerogels without microstructural degradation. Catalytic structure–function relationships are explored in a pharma-important amidation reaction; providing insights on how the engineered frameworks enhance catalyst activity. A sophisticated array of advanced tomographic, spectroscopic, and microscopic techniques reveal an intricate 3D assembly of CNT building-blocks and their influence on the functional properties of the enhanced nanocatalysts. These advances set a basis to modulate structure and chemistry of functional aerogel materials independently in a controlled fashion for a variety of applications, including energy conversion and storage, smart electronics, and (electro)catalysis.
Brydson, Rik,Cairns, Gareth A.,Chamberlain, Thomas W.,Flahaut, Emmanuel,Hondow, Nicole,Mannering, Jamie,Menzel, Robert,Stones, Rebecca,Sykes, Daniel,Xia, Dong
(2021/06/01)

Iodine-imine Synergistic Promoted Povarov-Type Multicomponent Reaction for the Synthesis of 2,2′-Biquinolines and Their Application to a Copper/Ligand Catalytic System
An efficient iodine-imine synergistic promoted Povarov-type multicomponent reaction was reported for the synthesis of a practical 2,2′-biquinoline scaffold. The tandem annulation has reconciled iodination, Kornblum oxidation, and Povarov aromatization, where the methyl group of the methyl azaarenes represents uniquely reactive input in the Povarov reaction. This method has broad substrate scope and mild conditions. Furthermore, these 2,2′-biquinoline derivatives had been directly used as bidentate ligands in metal-catalyzed reactions.
Hu, Qi-Qi,Gao, Yan-Ting,Sun, Jia-Chen,Gao, Jing-Jing,Mu, Hong-Xiao,Li, Yi-Ming,Zheng, Ya-Nan,Yang, Kai-Rui,Zhu, Yan-Ping
supporting information
p. 9000 - 9005
(2021/11/24)

Method for preparing formamide compound by using MCOF to catalyze CO2 as carbon source at normal temperature and pressure
The invention provides a method for preparing a formamide compound by using MCOF to catalyze CO2 as a carbon source at normal temperature and pressure, and belongs to the technical field of chemistry and chemical engineering. Under the conditions of normal temperature and normal pressure, CO2 is used as a carbon source to realize N-formylation reaction of various amine substrates. The method has the advantages that the reaction system uses the metal ion-doped two-dimensional covalent organic framework MCOF as the catalyst, CO2 is reduced at normal temperature and normal pressure to provide acyl, high-pressure hydrogen and toxic CO are prevented from being used, and the reaction conditions are mild (normal temperature and normal pressure). According to the method for preparing the formamide, the greenhouse gas carbon dioxide serves as a carbon source, the cost is low, operation is easy, reaction conditions are mild (normal temperature and normal pressure), the yield of the prepared formamide product is excellent (99%), and a green synthesis method is provided for N-acylation reaction.
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Paragraph 0026-0028

(2021/06/09)

N-formylation of amines using phenylsilane and CO2 over ZnO catalyst under mild condition
Several research studies have been conducted on N-formylation of amines using phenylsilane and CO2. However, most of these studies involved tedious processes of catalyst preparation or complex procedures. In the present study, we describe the use of a simple and commercially available ZnO catalyst for selective N-formylation of amines under mild condition. High-yielding N-formylation products with good recyclability and wide substrate scope were obtained, which can promote fine chemical synthesis and CO2 capture.
Cheng, Yujie,Gan, Tao,He, Qian,He, Xiaohui,Ji, Hongbing,Sun, Qingdi,Wang, Pengbo,Zhang, Hao
(2020/10/27)

Selective N-formylation of amines catalysed by Ag NPs festooned over amine functionalized SBA-15 utilizing CO2 as C1 source
N-formylation of amines using CO2 as C1 source has been an uphill transformation in the catalysis research as it involves the utilization of abundant thermodyanamically stable and kinetically inert CO2 to form the N-formylated products, which are potential intermediates for the synthesis of valuable chemicals. Previously various noble as well as non-noble metal nanoparticles have been employed for N-formylation of amines. However, herein for the first time we explored N-formylation reaction under lenient conditions utilizing silver nanoparticles, which are decorated over amine functionalized periodically ordered 2D-hexagonal SBA-15 material, serving as a robust heterogeneous catalyst. The AgNPs@SBA-15-NH2 has been intensively characterized by powder XRD, Brunauer-Emmett-Teller (BET), FEG-TEM, SEM, XPS, TGA, CO2-TPD, FTIR and UV–vis spectroscopic analyses. This supported AgNPs material showed remarkable catalytic activity for N-formylation over a wide range of amines under 0.5 MPa CO2 pressure and at mild temperature (35 °C) conditions. In addition, this AgNPs@SBA-15-NH2 material exhibited high chemical stability and reusability, suggesting its promising future in the CO2 fixation reactions.
Azad, Shiyana,Bal, Rajaram,Bhattacharjee, Sudip,Bhaumik, Asim,Chongdar, Sayantan
(2021/11/08)

Mesoporous Sn(IV) Doping DFNS Supported BaMnO3 Nanoparticles for Formylation of Amines Using Carbon Dioxide
Abstract: In the present paper, Sn(IV) doping DFNS (SnD) supported nanoparticles of BaMnO3 (BaMnO3/SnD) and using as a catalyst for the N-formylation of amines by CO2 hydrogenation. In this catalyst, the SnD with the ratios of Si/Sn in the range of from 6 to 50 were obtained with method of direct hydrothermal synthesis (DHS) as well as the nanoparticles of BaMnO3 were on the surfaces of SnD in situ reduced. Scanning electron microscope (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray energy dispersive spectroscopy (EDS), and transmission electron microscopy (TEM) were utilized for characterizing the nanostructures BaMnO3/SnD. It is found that the nanostructures of BaMnO3/SnD can be a nominate due to its effective and novel catalytic behavior in N-formylation of amines through hydrogenation of CO2. Graphic Abstract: [Figure not available: see fulltext.]
Yang, Jie,Wang, Liujie,Sun, Aili,Zhiani, Rahele
p. 573 - 581
(2020/07/27)

A substituent- And temperature-controllable NHC-derived zwitterionic catalyst enables CO2upgrading for high-efficiency construction of formamides and benzimidazoles
Chemocatalytic upgrading of the greenhouse gas CO2 to valuable chemicals and biofuels has attracted broad attention in recent years. Among the reported approaches, N-formylation of CO2 with an amine is of great significance due to its versatility in the construction of N-containing linear and cyclic skeletons. Herein, a stable N-heterocyclic carbene-carboxyl adduct (NHC-CO2) was facilely prepared and could be used as a recyclable zwitterionic catalyst for efficient CO2 reductive upgrading via either N-formylation or further coupling with cyclization under mild conditions (25 °C, 1 atm CO2) using hydrosilane as a hydrogen source. More than 30 different alkyl and aromatic amines could be transformed into the corresponding formamides or benzimidazoles with remarkable yields (74%-98%). The electronic effect of the introduced substituent on NHC-CO2 was found to evidently affect the thermostability and nucleophilicity of the zwitterionic catalyst, which is directly correlated with its catalytic activity. Moreover, NHC-CO2 could supply CO2 by in situ decarboxylation at a specific temperature that is dependent on the introduced substituent type. Experimental and computational studies showed that the carboxyl species on NHC-CO2 was not only a nucleophilic center, but also a C1 source which rapidly captures or substitutes ambient CO2 during hydrosilylation. In addition, a simple and green conceptual process was designed for the product purification and catalyst recycling, with a good feasibility for small-scale production.
Li, Hu,Li, Zhengyi,Wu, Hongguo,Yang, Song,Yu, Zhaozhuo,Zhang, Lilong,Zhu, Kaixun
supporting information
p. 5759 - 5765
(2021/08/23)

Preparation method of formamide compound
The invention belongs to CO. 2 The invention relates to the technical field of activation conversion and related chemistry, and provides a preparation method of a formamide compound, which uses carbon dioxide. The amide compound and phenylsilane are used as raw materials, and the formamide compound is synthesized under the action of the nano porous palladium catalyst. The invention mainly provides a novel simple catalytic system and utilizes CO. 2 C1 The catalytic system has the advantages of mild reaction conditions, simple experiment operation, good functional group compatibility and the like. Because carbon dioxide is abundant, cheap and easily available and renewable C1 , The invention has great application value and social economic benefits.
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Paragraph 0035-0038

(2021/10/27)

Ionization of Porous Hypercrosslinked Polymers for Catalyzing Room-Temperature CO2 Reduction via Formamides Synthesis
Porous materials with heterogeneous nature occupy a pivotal position in the chemical industry. This work described a facile pre- and post-synthetic approach to modify porous hypercrosslinked polymer with quaternary ammonium bromide, rendering it as efficient catalyst for CO2 conversion. The as-prepared porous ionic polymer (PiP@QA) displayed an improved specific surface area of 301 m2·g?1 with hierarchically porous structure, good selective adsorption of CO2, as well as high ion density. Accordingly, PiP@QA catalyst exhibited excellent catalytic performances for the solvent-free synthesis of various formamides from CO2, amines and phenylsilane under 35?°C and 0.5?MPa. We speculated that the superior catalytic efficiency and broad substrate scope of this catalyst could be resulted from the synergistic effect of flexible ionic sites with unique nanoporous channel that might increase the collision probability of reactants and active sites as well as enhance the diffusion of reactants and products during the reaction process. With the good reusability, PiP@QA was also available for the efficient conversion of simulated flue gas (15% CO2 in N2, v/v) into target formamides with quantitative selectivity at room temperature, which further highlighted its industrial application potential in chemical recycling the real-word CO2 to valuable products. Graphic Abstract: [Figure not available: see fulltext.].
Ren, Qinggang,Chen, Yaju,Qiu, Yongjian,Tao, Leiming,Ji, Hongbing
p. 2919 - 2927
(2021/02/01)

A N-Phosphinoamidinato NHC-Diborene Catalyst for Hydroboration
The use of the N-phosphinoamidinato NHC-diborene catalyst 2 for hydroboration is described. The N-phosphinoamidine tBu2PN(H)C(Ph)= N(2,6-iPr2C6H3) was reacted with nBuLi in Et2O to afford the lithium derivative, which was then treated with B2Br4(SMe2)2 in toluene to form the N-phosphinoamidinate-bridged diborane 1. It was reacted with the N-heterocyclic carbene IMe (:C{N(CH3)C(CH3)}2) and excess potassium graphite at room temperature in toluene to give the N-phosphinoamidinato NHC-diborene compound 2. It can stoichiometrically activate ammonia-borane and carbon dioxide. It also showed catalytic capability. A 2 mol % portion of 2 catalyzed the hydroboration of carbon dioxide (CO2) with pinacolborane (HBpin) in deuterated benzene (C6D6) at 110 °C (conversion >99%), which afforded the methoxyborane [pinBOMe] (yield 97.8%, TOF 33.3 h-1) and the bis(boryl) oxide [(pinB)2O]. In addition, 5 mol % of 2 catalyzed the N-formylation of secondary and primary amines by carbon dioxide and pinacolborane to yield the N-formamides (average yield 91.6%, TOF 25.9 h-1). Moreover, 2 showed chemoselectivity toward catalytic hydroboration of carbonyl compounds. In mechanistic studies, the B= B double bond in compound 2 activated the substrates, the intermediates of which then underwent hydroboration with pinacolborane to yield the products and regenerate catalyst 2.
Fan, Jun,Mah, Jian-Qiang,Yang, Ming-Chung,Su, Ming-Der,So, Cheuk-Wai
p. 4993 - 5002
(2021/02/01)

Recyclable Oxofluorovanadate-Catalyzed Formylation of Amines by Reductive Functionalization of CO2 with Hydrosilanes
An efficient method has been developed for the reductive amination of CO2 by using readily available and recyclable oxofluorovanadates as catalysts. Various amines are transformed into the desired N-formylated products in moderate to excellent yields at room temperature in the presence of phenylsilane. Mechanistic studies based on in situ infrared spectroscopy suggest a reaction pathway initiated through F?Si interactions. The activated phenylsilane allows for CO2 insertion to produce phenylsilyl formate, which undergoes attack by the amine to generate the target product.
Wu, Shanxuan,Huang, Zijun,Jiang, Xiaolin,Yan, Fachao,Li, Yuehui,Du, Chen-Xia
p. 1763 - 1766
(2021/03/01)

Immobilized Zn(OAc)2on bipyridine-based periodic mesoporous organosilica for N -formylation of amines with CO2and hydrosilanes
Zinc acetate (Zn(OAc)2) was successfully immobilized on a bipyridine-based periodic mesoporous organosilica (BPy-PMO-TMS), as confirmed by solid-state NMR and energy-dispersive X-ray spectroscopies, X-ray diffractometry, and nitrogen adsorption/desorption isotherm analyses. The immobilized Zn complex, Zn(OAc)2(BPy-PMO-TMS), exhibited good catalytic activity during the N-formylations of amines and amides with CO2 and PhSiH3 to produce the corresponding formamides. Zn(OAc)2(BPy-PMO-TMS) with a lower Zn loading was found to exhibit higher catalytic activity.
Lin, Xiao-Tao,Matsumoto, Kazuhiro,Maegawa, Yoshifumi,Takeuchi, Katsuhiko,Fukaya, Norihisa,Sato, Kazuhiko,Inagaki, Shinji,Choi, Jun-Chul
p. 9501 - 9505
(2021/06/14)

METHOD OF CARBON MONOXIDE FIXATION AND METHOD OF AMINE FORMYLATION
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; 0100-0102

(2021/02/19)

Design of Lewis base functionalized ionic liquids for the N-formylation of amines with CO2 and hydrosilane: The cation effects
A series of functionalized ionic liquids (ILs) were developed for the reductive functionalization of CO2 with amine and hydrosilane to afford formamides under mild conditions. It was found that 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)-based IL i.e. [DBUC12]Br showed high efficiency for the N-formylation reaction of amines without using any organic solvents or additives. Furthermore, control experiments suggested the cations with active hydrogen may weaken the nucleophilicity of anions through ion pairing interactions, thereby affecting the activation of hydrosilane. The reaction mechanism was then investigated by Density Functional Theory (DFT) calculations. This protocol represents a highly efficient and environmentally friendly example for catalytic conversion of CO2 into value-added chemicals such as formamide derivatives by employing DBU functionalized ILs.
Li, Xiao-Ya,Fu, Hong-Chen,Liu, Xiao-Fang,Yang, Shu-Han,Chen, Kai-Hong,He, Liang-Nian
p. 563 - 569
(2020/02/05)

N-Formylation of amines using arylhydrazones of malononitrile and a Cu(II) complex under eco-friendly conditions at room temperature
In this work, we report the synthesis of formamides via solvent free N-formylation of amines using known arylhydrazones of malononitrile including sodium 2-(2-(dicyanomethylene)hydrazinyl)benzenesulfonate (I), 2-(2-(dicyanomethylene)hydrazinyl) benzoic acid (II) and its Cu(II) complex (III) as catalysts at room temperature. These catalysts are highly active and the scope of the method was investigated using several heterocyclic, aromatic and aliphatic amines as substrates, which produced the corresponding formamides in high yields. The remarkable advantages of this method are the elimination of toxic solvents, operational simplicity, easy workup procedure, excellent yields and avoidance of column chromatography.
Nasrollahzadeh, Mahmoud,Bidgoli, Nayyereh Sadat Soheili,Rocha, Bruno G.M.,Pombeiro, Armando J.L.,Mahmudov, Kamran T.
(2020/08/14)

Selective mono-N-methylation of nitroarenes with methanol catalyzed by atomically dispersed NHC-Ir solid assemblies
A series of N-heterocyclic carbene-iridium (NHC-Ir) coordination assemblies based on bis-pyrenoimidazolium salts are prepared, and shown to function as efficient solid molecular catalysts in selective mono-N-methylation of nitroarenes with methanol under mild conditions. The atomically dispersed active Ir(I) centers and the large π-conjugation rings endow the solid catalysts with an exceptionally high activity and selectivity for a broad substrate scope. Such solid NHC-Ir coordination assemblies are robust, which can be easily recovered and reused more than 10 runs without significant loss of their catalytic activity and selectivity. When combined with a subsequent formylation using the same solid catalysts under ambient conditions, this novel protocol can afford diverse formamides in excellent yields, further highlighting the applicability of the present solid catalysts for an efficient diversification of nitroarenes to a broad number of functional amines.
Chen, Jiangbo,Chen, Zhe-Ning,Tu, Tao,Wang, Jiaquan,Wen, Daheng,Wu, Jiajie,Xu, Xin,Zheng, Qingshu
p. 337 - 344
(2020/07/03)

Synthesis of silyl formates, formamides, and aldehydesviasolvent-free organocatalytic hydrosilylation of CO2
Carbon dioxide (CO2) was used as a C1 source to prepare silyl formates, formamides, and aldehydes. Tetrabutylammonium acetate (TBAA) catalyzed the solvent-freeN-formylation of amines with CO2and hydrosilane to give formamides including Weinreb formamide, Me(MeO)NCHO, which was successively converted into aldehydes by one-pot reactions with Grignard reagents.
Ema, Tadashi,Hasegawa, Jun-Ya,Hiyoshi, Mahoko,Murata, Takumi,Ratanasak, Manussada
supporting information
p. 5783 - 5786
(2020/06/03)

N-Heterocyclic Carbene-Stabilized Germa-acylium Ion: Reactivity and Utility in Catalytic CO2Functionalizations
The first acceptor-free heavier germanium analogue of an acylium ion, [RGe(O)(NHC)2]X (R = MesTer = 2,6-(2,4,6-Me3C6H2)2C6H3; NHC = IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene; X = (Cl or BArF = {(3,5-(CF3)2C6H5)4B}), was isolated by reacting [RGe(NHC)2]X with N2O. Conversion of the germa-acylium ion to the first solely donor-stabilized germanium ester [(NHC)RGe(O)(OSiPh3)] and corresponding heavier analogues ([RGe(S)(NHC)2]X and [RGe(Se)(NHC)2]X) demonstrated its classical acylium-like behavior. The polarized terminal GeO bond in the germa-acylium ion was utilized to activate CO2 and silane, with the former found to be an example of reversible activation of CO2, thus mimicking the behavior of transition metal oxides. Furthermore, its transition-metal-like nature is demonstrated as it was found to be an active catalyst in both CO2 hydrosilylation and reductive N-functionalization of amines using CO2 as the C1 source. Mechanistic studies were undertaken both experimentally and computationally, which revealed that the reaction proceeds via an N-heterocyclic carbene (NHC) siloxygermylene [(NHC)RGe(OSiHPh2)].
Sarkar, Debotra,Weetman, Catherine,Dutta, Sayan,Schubert, Emeric,Jandl, Christian,Koley, Debasis,Inoue, Shigeyoshi
supporting information
p. 15403 - 15411
(2020/10/20)

Engineering Porphyrin Metal-Organic Framework Composites as Multifunctional Platforms for CO2Adsorption and Activation
As an effective solution toward the establishment of a sustainable society, the reductive transformation of CO2 into value-added products is certainly important and imperative. Herein, we report a porphyrin metal-organic framework composite Au@Ir-PCN-222, which is obtained through the in situ formation of Au nanoparticles in the coordination interspaces of Ir-PCN-222. Catalytic results show that Au@Ir-PCN-222 is highly efficient for CO2 reduction and aminolysis, giving rise to formamides in high yields and selectivities under room temperature and atmospheric pressure. Mechanistic studies disclose that the high efficiency of Au@Ir-PCN-222 is due to the synergistic catalysis of Au NPs and Ir-PCN-222, in which Au NPs can adsorb CO2 molecules on their surfaces and then increase the CO2 concentration in the cavities of the framework, and at the same time, Au NPs transfer electrons to Ir-porphyrin units and therefore increase the interactions with CO2 molecules.
Liu, Jiewei,Fan, Yan-Zhong,Zhang, Kun,Zhang, Li,Su, Cheng-Yong
p. 14548 - 14556
(2020/10/13)

Catalyst-free selective: N -formylation and N -methylation of amines using CO2 as a sustainable C1 source
We herein describe catalyst-free selective N-formylation and N-methylation of amines using CO2 as a sustainable C1 source. By tuning the reaction solvent and temperature, the selective synthesis of formamides and methylamines is achieved in good to excellent yields using sodium borohydride (NaBH4) as a sustainable reductant.
Zou, Qizhuang,Long, Guangcai,Zhao, Tianxiang,Hu, Xingbang
supporting information
p. 1134 - 1138
(2020/03/11)

Ligand-protected Au4Ru2and Au5Ru2nanoclusters: Distinct structures and implications for site-cooperation catalysis
We report two ligand-protected Au4Ru2 and Au5Ru2 nanoclusters with distinct atomic-packing modes and electronic structures, both of which act as ideal model catalysts for identifying the catalytically active sites of catalysts on the nanoclusters. Au5Ru2 exhibits superior catalytic performances to Au4Ru2 for N-methylation of N-methylaniline to N-methylformanili, which is likely due to the site-cooperation catalysis of Au5Ru2. This journal is
Sun, Yongnan,Yang, Dan,Zhang, Yuying,Hu, Weigang,Cheng, Xinglian,Liu, Xu,Chen, Mingyang,Zhu, Yan
supporting information
p. 12833 - 12836
(2020/11/02)

Hydroboration of carbon dioxide enabled by molecular zinc dihydrides
Neutral molecular zinc(ii) dihydrides supported by N-heterocyclic carbene ligands bearing a pendant phosphine group were synthesized and then reacted with carbon dioxide to afford zinc diformates. The zinc dihydrides were found to be active catalysts for hydroboration of carbon dioxide under mild conditions, selectively giving boryl formate, bis(boryl)acetal, or methoxy borane compounds by changing the nature of the borane reductant.
Chang, Kejian,Wang, Xiaoming,Xu, Xin
supporting information
p. 7324 - 7327
(2020/06/21)

A NHC-silyliumylidene cation for catalytic N?formylation of amines using carbon dioxide
This study describes the use of a silicon(II) complex, namely, the NHC-silyliumylidene cation complex [(IMe)2SiH]I (1, IMe =:C{N(Me)C(Me)}2), to catalyze the chemoselective N-formylation of primary and secondary amines using CO2 and PhSiH3 under mild conditions to afford the corresponding formamides as a sole product (average reaction time: 4.5 h; primary amines, average yield: 95%, average TOF: 8 h?1; secondary amines, average yield: 98%, average TOF: 17 h?1). The activity of 1 and product yields outperform the currently available non-transition-metal catalysts used for this catalysis. Mechanistic studies show that the silicon(II) center in complex 1 catalyzes the C?N bond formation via a different pathway in comparison with non-transition-metal catalysts. It sequentially activates CO2, PhSiH3, and amines, which proceeds via a dihydrogen elimination mechanism, to form formamides, siloxanes, and dihydrogen gas.
Leong, Bi-Xiang,Teo, Yeow-Chuan,Condamines, Cloe,Yang, Ming-Chung,Su, Ming-Der,So, Cheuk-Wai
p. 14824 - 14833
(2020/12/21)

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)

Selective: N-formylation/N-methylation of amines and N-formylation of amides and carbamates with carbon dioxide and hydrosilanes: Promotion of the basic counter anions of the zinc catalyst
A catalyst composed of commercially available Zn(OAc)2 and 1,10-phenanthroline (phen) was effective in the N-formylation/N-methylation of amines using CO2 as the C1 source in the presence of hydrosilanes. An equimolar reaction of N-methylaniline with PhSiH3 under a CO2 atmosphere yielded the N-formylation product in 92% yield at 25 °C. Scale-up of the reaction using 10 mmol substrate was also successful in affording the desired product in 83% yield (1.1 g). This catalyst exhibits a high thermal stability and a turnover number (TON) of 385000 at 150 °C. In addition, the reaction of N-methylaniline in the presence of excess Ph2SiH2 produced N,N-dimethylaniline. Furthermore, our catalytic protocol was developed for the N-formylation of amides and carbamates, which have smaller pKa values and lower reactivities than the corresponding amines. The present Zn(OAc)2/phen catalyst was found to show versatility in the conversion of CO2 and amines into several functionalized organic chemicals under mild conditions. We propose that the basic counter anion (i.e., the acetate) of the catalyst activates both the Si-H and N-H bonds.
Zhang, Qiao,Lin, Xiao-Tao,Fukaya, Norihisa,Fujitani, Tadahiro,Sato, Kazuhiko,Choi, Jun-Chul
supporting information
p. 8414 - 8422
(2020/12/29)

L-Serine?ZnO as an efficient and reusable catalyst for synthesis of cyclic carbonates and formamides in presence of CO2 atmosphere
The highly efficient carbon dioxide (CO2) fixation into value-added organic carbonates has gained enormous attention in the last few decades. This work reports, synthesis and characterization of amino acids (AAs) assisted ZnO nano catalyst and Its application for the cyclic carbonates and formamides synthesis with CO2 atmosphere. The prepared catalysts are characterized by IR, SEM, TEM, XRD, DSC-TGA XPS analysis. L-Serine?ZnO exhibits excellent catalytic activity for transformation of CO2 into value-added chemicals namely formamides and cyclic carbonates. The catalytic systems which work in the presence of CO2 balloon atmosphere for the synthesis of cyclic carbonates are rarely explored. This catalytic system shows excellent activity under the CO2 balloon atmosphere for carbonate synthesis. The developed methodology demonstrates broad substrate scope as well as excellent functional group tolerance for carbonates and formamides synthesis. Additionally, the synthesized catalyst was recyclable up to five recycling runs without considerable loss in its catalytic activity, thus makes this protocol cost-effective and sustainable.
Ahire, Jayendra P.,Bhanage, Bhalchandra M.,Phatake, Vishal V.
(2020/06/03)

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)

Zinc Powder Catalysed Formylation and Urealation of Amines Using CO2 as a C1 Building Block?
Transformation of CO2 into valuable organic compounds catalysed by cheap and biocompatible metal catalysts is one of important topics of current organic synthesis and catalysis. Herein, we report the zinc powder catalysed formylation and urealation of amines with CO2 and (EtO)3SiH under solvent free condition. Using 2 molpercent zinc powder as the catalyst, a series of secondary amines, both the aromatic ones and the aliphatic ones, can be formylated into formamides. When primary aromatic amines were used as the substrates, the reactions produce urea derivatives. The electronic and steric effects from the substrates on the formylation and urealation reactions were observed and discussed. The recovery and reusability of zinc powder were investigated, showing the zinc powder can be reused in the formylation reaction without loss of catalytic activity. The analysis on the reactants/products mixture after filtering out the zinc powder showed the zinc concentration in the mixture is low to 1 ppm. The pathways for the formylation and urealation of amines with this catalytic system were also investigated, and related to the different substrates.
Du, Chongyang,Chen, Yaofeng
p. 1057 - 1064
(2020/06/30)

Building N-Heterocyclic Carbene into Triazine-Linked Polymer for Multiple CO2 Utilization
The development of new CO2 detection technologies and CO2 “capture-conversion” materials is of great significance due to the growing environmental crisis. Here, multifunctional triazine-linked polymers with built-in N-heterocyclic carbene (NHC) sites (designated as NHC-triazine@polymer) are presented for simultaneous CO2 detection, capture, activation, and catalytic conversion. NHC-triazine@polymer were readily obtained through polymerization of cyanophenyl-substituted NHC. The obtained film-like polymers exhibited interesting CO2-triggered fluorescence “turn-on” response and CO2-sensitive reversible color change. Both NHC and triazine sites could act as efficient binding sites for CO2, and the CO2 uptake of NHC and triazine reached 1.52 and 1.36 mmol g?1, respectively. Notably, after being captured by NHC, CO2 was activated into a zwitterionic adduct NHC?CO2 that could be easily transformed into cyclic carbonate in the presence of epoxides. Moreover, NHC-triazine@polymer were stable and active catalysts for the conversion of low-concentration CO2 in a gas mixture (7 vol %) into cyclic carbonates as well as for hydrosilylation of CO2 to formamides.
Yue, Chengtao,Wang, Wenlong,Li, Fuwei
p. 5996 - 6004
(2020/10/06)

Zn(ii)@TFP-DAQ COF: An efficient mesoporous catalyst for the synthesis of: N -methylated amine and carbamate through chemical fixation of CO2
Selective N-methylation and carbamate formation reactions were demonstrated via the chemical incorporation of CO2 using a Zn-loaded TFP-DAQ COF (covalent organic framework) as an active catalyst under mild reaction conditions. The selective N-methylation and N-formylation reactions were performed by simply varying the type of solvent. The Zn(ii)@TFP-DAQ COF catalyst was characterized via different characterization techniques such as PXRD, FTIR, UV-vis, N2 adsorption-desorption studies, FESEM and TEM. The catalyst material showed pores in the mesoporous region with a high surface area of 1117.375 m2 g-1. The as-synthesized material was applied as a cheap catalyst for the N-methylation of secondary amines and in carbamate formation reactions with high yields of the desired products up to 98.5% and 97%, respectively, with >99% selectivity. The catalyst was found to be completely heterogeneous and reusable for multiple reaction cycles.
Sarkar, Priyanka,Chowdhury, Arpita Hazra,Riyajuddin, Sk.,Biswas, Surajit,Ghosh, Kaushik,Islam, Sk. Manirul
p. 744 - 752
(2020/01/31)

Selective N-Methylation of N-Methylaniline with CO2 and H2 over TiO2-Supported PdZn Catalyst
A series of Pd-ZnO/TiO2, Pd/TiO2, and Pd/ZnO catalysts were synthesized and investigated for N-methylation of N-methylaniline (MA) to N,N-dimethylaniline (DMA) with CO2 and H2. A high performance was observed with a Pd-ZnO/TiO2 catalyst, with 99.9% DMA selectivity at 94% MA conversion. By contrast, both Pd/TiO2 and Pd/ZnO were less active and/or selective. The catalytic performance of Pd-ZnO/TiO2 largely depended on reduction temperature and ZnO loading. The rates for MA conversion (rateMA) and DMA production (rateDMA) increased linearly with the amount of PdZn alloy formed. The reaction was likely to take place via intermediates of N-methylformanilide (MFA) and formate. Formate was produced through the reduction of CO2 with H2 as confirmed by in situ diffuse reflectance Fourier transform infrared spectroscopy and then added to MA producing MFA, and finally, MFA was subsequently adsorbed and hydrogenated to DMA. All these steps were promoted by the PdZn alloy. The hydrogenation of MFA to DMA was much faster than the N-methylation of MA to MFA; DMA was stable, so the selectivity to DMA was almost 100% over the Pd-ZnO/TiO2 catalyst.
Arai, Masahiko,Cheng, Haiyang,Lin, Weiwei,Wu, Qifan,Zhang, Chao,Zhao, Fengyu
p. 3285 - 3296
(2020/03/10)

Alkyl-substituted ethyl acetate-based guanidine ionic liquid as well as preparation and application thereof
The invention discloses alkyl-substituted ethyl acetate-based guanidine ionic liquid as well as preparation and application thereof, which are characterized in that tetramethylguanidine and 2-bromo ester are ionized to obtain alkyl-substituted ethyl acetate-based guanidine ionic liquid, and the alkyl-substituted ethyl acetate-based guanidine ionic liquid is applied as a catalyst to formylation and methylation reactions of carbon dioxide, N-methylaniline and derivatives of the N-methylaniline to selectively generate N-methylformylaniline or N, N-dimethylaniline and derivatives thereof. Compared with the prior art, the alkyl-substituted ethyl acetate-based guanidine ionic liquid has the advantages of good catalytic performance, mild reaction conditions, simple post-treatment, simple synthesis, low cost, greenness and high efficiency, avoids the use of a large amount of organic solvents when being used as a solvent and a catalyst at the same time, and has important meanings in the research of medicinal chemistry and medical intermediate compounds.
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Paragraph 0030-0033

(2020/07/21)

Method for catalytically oxidizing amine to be synthesized into amide through dipyridyl-type manganese catalyst
The invention discloses a methodfor catalytically oxidizing amine to be synthesized into amide througha dipyridyl-type manganese catalyst. According to the method, a dipyridyl manganese complex formedafter coordination of a dipyridyl-type complex and cheap metal manganese serves as the catalyst, clean and environment-friendly hydrogen peroxide serves as an oxidizing agent, oxidation of N ortho-position sp3 C-H bonds catalyzed by the cheap metal manganese is achieved, and the amine is directly oxidized to obtain the amide. Compared with existing methods, the method has the advantages that theadopted catalyst is low in price, the preparing method is simple, raw materials are easy to obtain, the use level of the catalyst is low, the substrate range is wide, the reaction condition is mild, the operation is simple and environmentally friendly, the reaction time is short, the yield is high, the selectivity is high, and the industrialization cost is low.
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Paragraph 0017-0027; 0085-0087

(2019/06/30)

TBSOTf-promoted versatile N-formylation using DMF at room temperature
Hydrazides and amines were N-formylated by DMF in the presence of tert-butyldimethylsilyl triflate (TBSOTf) at room temperature, in good to excellent yields.
Sakurai, Masayoshi,Kawakami, Rina,Kihara, Nobuhiro
supporting information
p. 1291 - 1294
(2019/04/10)

Catalytic and stoichiometric oxidation of N,N-dimethylanilines mediated by nonheme oxoiron(IV) complex with tetrapyridyl ligand
Nonheme iron(II) complex, [(N4Py*)FeII(CH3CN)](ClO4)2 (1) with pentadentate tetrapyridyl ligand (N4Py* = N,N-bis(2-pyridylmethyl)-1,2-di(2-pyridyl)ethylamine) has been shown to catalyze the oxidation of N,N-dimethylaniline (DMA) with H2O2, tert-butyl hydroperoxide (TBHP), peracetic acid (PAA), meta-chloroperoxybenzoic acid (mCPBA) and PhIO resulting N-methylaniline (MA) as the predominant product with N-methylformanilide (MFA) as a result of a free-radical chain process. The product composition (MA/MFA) is remarkably influenced by the electron density on the substrate, especially in the 1/mCPBA system, and by the co-oxidants used. No formation of MFA occurred when the oxidation of DMA was carried out in the presence of 1 with PhIO as co-oxidants under argon. Based on spectral investigation (UV–Vis) of reaction systems above, oxoiron(IV) intermediate, [FeIV(N4Py*)(O)]2+ (2) has been suggested to be the key active species of the N-dealkylation reaction in all catalytic systems. The shift in the λmax value of the oxoiron(IV) species in the presence of DMA from 705 to 750 nm, and the new intense absorption in the range of 5–600 nm indicates a complexation and charge-transfer (CT) type interactions between the oxidant and substrate. The stoichiometric oxidation of various N,N-dimethylaniline derivatives with 2 provided clear evidence (Hammett correlation with ρ = ?1.99, and the large negative slope (?4.1) from the logkobs versus Eoox (DMAs) plot) for the rate-determining electron transfer (ET) followed by a proton transfer (PT) process.
Lakk-Bogáth, Dóra,Kripli, Balázs,Meena, Bashdar I.,Speier, Gábor,Kaizer, József
p. 169 - 175
(2019/05/29)

Amide Bond Formation Catalyzed by Recyclable Copper Nanoparticles Supported on Zeolite Y under Mild Conditions
A series of catalysts based on supported copper nanoparticles have been prepared and tested in the amide bond formation from tertiary amines and acid anhydrides, in the presence of tert-butyl hydroperoxide as an oxidant. Copper nanoparticles on zeolite Y (CuNPs/ZY) was found to be the most efficient catalyst for the synthesis of amides, working in acetonitrile as solvent, under ligand- and base-free conditions in air. The products were obtained in good to excellent yields and in short reaction times. The CuNPs/ZY system also exhibited higher catalytic activity than some commercially available copper and iron sources and it was reused in ten reaction cycles without any further pre-treatment. This methodology has been successfully scaled-up to a gram scale with no detriment to the yield.
Moglie, Yanina,Buxaderas, Eduardo,Mancini, Agustina,Alonso, Francisco,Radivoy, Gabriel
p. 1487 - 1494
(2019/02/16)

Methyl-Selective α-Oxygenation of Tertiary Amines to Formamides by Employing Copper/Moderately Hindered Nitroxyl Radical (DMN-AZADO or 1-Me-AZADO)
Methyl-selective α-oxygenation of tertiary amines is a highly attractive approach for synthesizing formamides while preserving the amine substrate skeletons. Therefore, the development of efficient catalysts that can advance regioselective α-oxygenation at the N-methyl positions using molecular oxygen (O2) as the terminal oxidant is an important subject. In this study, we successfully developed a highly regioselective and efficient aerobic methyl-selective α-oxygenation of tertiary amines by employing a Cu/nitroxyl radical catalyst system. The use of moderately hindered nitroxyl radicals, such as 1,5-dimethyl-9-azanoradamantane N-oxyl (DMN-AZADO) and 1-methyl-2-azaadamanane N-oxyl (1-Me-AZADO), was very important to promote the oxygenation effectively mainly because these N-oxyls have longer life-times than less hindered N-oxyls. Various types of tertiary N-methylamines were selectively converted to the corresponding formamides. A plausible reaction mechanism is also discussed on the basis of experimental evidence, together with DFT calculations. The high regioselectivity of this catalyst system stems from steric restriction of the amine-N-oxyl interactions.
Nakai, Satoru,Yatabe, Takafumi,Suzuki, Kosuke,Sasano, Yusuke,Iwabuchi, Yoshiharu,Hasegawa, Jun-ya,Mizuno, Noritaka,Yamaguchi, Kazuya
supporting information
p. 16651 - 16659
(2019/11/11)

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)