- Mesoporous silica SBA-15 functionalized with acidic deep eutectic solvent: A highly active heterogeneous N-formylation catalyst under solvent-free conditions
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Mesoporous silica SBA-15 functionalized with N-methylpyrrolidonium-zinc chloride based deep eutectic solvent (DES) is found to be a more efficient and reusable catalyst for a convenient N-formylation of a variety of amines at room temperature. N-Formylation of primary, secondary as well as heterocyclic amines have been carried out in good to excellent yields by treatment with formic acid in low loading of DES/SBA-15 an environmentally benign catalyst for the first time. The DES/SBA-15 catalyst, which possesses both Br?nsted and Lewis acidities as well as an active SBA-15 support, makes this procedure quite simple, reusable, more convenient and practical. This catalyst was tolerant of a wide range of functional groups, and it can be reused for four runs without obvious deactivation.
- Azizi, Najmedin,Edrisi, Mahtab,Abbasi, Faezeh
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- N-Formylbenzotriazole: A stable and convenient N- and O-formylating agent
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N-Formylbenzotriazole, prepared by the reaction of benzotriazole and formic acid in the presence of dicyclohexylcarbodiimide, is demonstrated to be a superior N- and O-formylating agent.
- Katritzky,Chang,Yang
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- Engineering Porphyrin Metal-Organic Framework Composites as Multifunctional Platforms for CO2Adsorption and Activation
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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
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- Mild and convenient N-formylation protocol in water-containing solvents
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We have realized that N-formylations of free amines of some drug leads can improve PK/PD property of parent molecules without decreasing their biological activities. In order to selectively formylate primary amines of polyfunctional molecules, we have sought a mild and convenient formylation reaction. In our screening of N-formylation of an α-amino acid, l-phenylalanine, none of formylation conditions reported to date yielded the desired HCO-l-Phe-OH with satisfactory yield. N-formylations of amino acids with HCO2H require a water-containing media and suppress polymerization reactions due to the competitive reactions among carboxylic acids. We found that N-formylations of α-amino acids could be achieved with a water-soluble peptide coupling additive, an Oxyma derivative, (2,2-dimethyl-1,3-dioxolan-4-yl)methyl-2-cyano-2- (hydroxyimino)acetate (2), EDCI, and NaHCO3 in water or a mixture of water and DMF system, yielding N-formylated α-amino acids with excellent yields. Moreover, these conditions could selectively formylate primary amines over secondary amines at a controlled temperature. A usefulness of these conditions was demonstrated by selective formylation of daptomycin antibiotic which contains three different amino groups.
- Aleiwi, Bilal A.,Mitachi, Katsuhiko,Kurosu, Michio
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- Building N-Heterocyclic Carbene into Triazine-Linked Polymer for Multiple CO2 Utilization
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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
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- Synthesis of Substituted Thioamides from gem-Dibromoalkenes and Sodiumsulfide
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A three-component reaction of 1,1-dibromoalkenes, sodium sulfide, and N-substituted formamide for the synthesis of disubstituted thioamides has been developed. Various dibromoalkenes were found to be compatible under these conditions and gave corresponding thioamides in good to excellent yields.
- Morri, Ashok K.,Thummala, Yadagiri,Adepu, Ramesh,Sharma, Gangavaram V. M.,Ghosh, Subhash,Doddi, Venkata Ramana
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- Iridium-Catalyzed Direct Amidation of Imidazoles at the C-2 Position with Isocyanates in the Presence of Hydrosilanes Leading to Imidazole-2-Carboxamides
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Regioselective coupling reaction of N -substituted imidazoles with isocyanates in the presence of a stoichiometric amount of hydrosilanes catalyzed by Ir 4(CO) 12to give imidazole-2-carboxamides is reported. Imidazoles bearing an (O -silyl)carboximidate group at the 2-position appear to be initially formed in the reaction; these are then hydrolyzed to the final products in situ. The addition of the hydrosilane was essential for the catalytic reaction to proceed. Substituents on the imidazole ring had no effect on the reaction, except for certain bulky substituents such as tBu and Ph groups at the 4-position. Triazoles such as 4-methyl-4 H -1,2,4-triazole and 1-methyl-1 H -1,2,4-triazole were also applicable to this C-H amidation, and the latter reaction proceeded regioselectively at the carbon atom between the sp 3and sp 2nitrogen atoms of the ring, and not between the two sp 2nitrogen atoms.
- Fukumoto, Yoshiya,Shiratani, Motohiro,Noguchi, Hikaru,Chatani, Naoto
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- 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
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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
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- Co3O4 nanoparticles prepared by oxidative precipitation method: an efficient and reusable heterogeneous catalyst for N-formylation of amines
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Abstract: N-formylation of different amines was carried out with formic acid in the presence of the Co3O4 nanoparticles as an efficient, stable heterogeneous catalyst to give the corresponding formamides under solvent-free conditions. This method has advantages over the reported methods such as high yields, mild conditions, easy work-up and short reaction times. The catalyst was characterized by different techniques such as XRD, SEM and FT-IR spectroscopy. Graphical Abstract: [Figure not available: see fulltext.]
- Marjani, Ahmad Poursattar,Hosseini, Seyed Ali,Shokri, Zahra,Maleki, Nasim
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- Highly efficient rhodium-catalyzed transfer hydrogenation of nitroarenes into amines and formanilides
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An efficient and selective rhodium-catalyzed transfer hydrogenation of nitroarenes with formic acid as the hydrogen source to give amines or formanilides has been developed. The addition of iodide ion accelerates the reaction, which can take place at room temperature. Georg Thieme Verlag Stuttgart New York.
- Wei, Yawen,Wu, Jianjun,Xue, Dong,Wang, Chao,Liu, Zhaotie,Zhang, Zhuozhuo,Chen, Guangfu,Xiao, Jianliang
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- Enhanced catalytic performance of cobalt nanoparticles coated with a N,P-codoped carbon shell derived from biomass for transfer hydrogenation of functionalized nitroarenes
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The development of abundantly available base metal catalysts for organic transformations remains an important goal of chemical research. Herein, we report the first facile fabrication of active, inexpensive, and reusable cobalt nanoparticles (NPs) coated with a N,P-codoped carbon shell derived from naturally renewable biomass and earth-abundant, low-cost cobalt salt and PPh3. The entire process is operationally simple, straightforward, cost-effective and environmentally benign and can be used in mass production for practical application. The resultant catalysts allow for highly efficient and selective transfer hydrogenation of functionalized nitroarenes to the corresponding anilines using formic acid or ammonium formate as the hydrogen donor. Uniformly incorporated N and P into the carbon lattices exhibited synergistic effects with the encapsulated Co NPs to engineer the structure and composition of the catalyst, thereby substantially boosting the catalytic efficiency. The most active catalyst Co@NPC-800 exhibited outstanding activity and exclusive selectivity for the reduction of functionalized nitroarenes to anilines, especially those decorated with readily reducible functional groups. The catalyst demonstrated high stability and can be easily separated by using an external magnet for successive reuses without significant loss in both activity and selectivity.
- Duan, Yanan,Song, Tao,Dong, Xiaosu,Yang, Yong
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- Copper promoted aerobic oxidative c(sp3)-c(sp3) bond cleavage of n-(2-(pyridin-2-yl)-ethyl)anilines
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A strategy of aerobic oxidative C(sp3)-C(sp3) bond cleavage of N-ethylaniline derivatives bearing azaarenes for the synthesis of N-aryl formamides has been developed. This approach was carried out smoothly with the CuI/TEMPO/air system to give N-aryl formamides in yields of 50-90%. With this methodology, a mutagenically active compound was constructed in 90% yield. Moreover, the reaction also provided a one-pot synthetic tool for accessing a promoter of hematopoietic stem cells by difunctionalization in 61% yield.
- Yu, Yang,Zhang, Yong,Sun, Chengyu,Shi, Lei,Wang, Wei,Li, Hao
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- A Practical Approach for the Transamidation of N, N-Dimethyl Amides with Primary Amines Promoted by Sodium tert-Butoxide under Solvent-Free Conditions
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A practical sodium tert-butoxide (NaO t Bu)-mediated protocol is disclosed for the transamidation of various N, N-dimethyl amides with primary amines to afford the corresponding amides in moderate to good yields at room temperature under solvent-free conditions. This protocol features a facile work-up procedure and good functional group compatibility, especially for N, N-dimethyl amides with long-chain alkyl groups and heteroatom-containing amines. Notably, a few representative gram-scale reactions proceed smoothly to furnish the desired amides in high yields, which demonstrates the potential of this process for further practical applications. Several control experiments are carried out and a plausible mechanism is provided.
- Zhang, Rui,Zhang, Jun-Chao,Zhang, Wei-Yi,He, Yu-Qing,Cheng, Hua,Chen, Cheng,Gu, Yu-Cheng
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- Aerobic oxidation of cyclic amines to lactams catalyzed by PVP-stabilized nanogold
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Gold nanoclusters stabilized by poly(N-vinyl-2-pyrrolidone) (Au:PVP) are active and selective catalysts under aerobic conditions for oxidation of cyclic secondary amines at the -position of the nitrogen atom. The catalyst accelerates the formation of the imines by oxidation of the amines in aqueous solvent to afford the corresponding lactams. Georg Thieme Verlag Stuttgart - New York.
- Preedasuriyachai, Patcharee,Chavasiri, Warinthorn,Sakurai, Hidehiro
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- Reductive Formylation of Nitroarenes using HCOOH over Bimetallic C?N Framework Derived from the Integration of MOF and COF
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CoZn embedded C?N framework is prepared by the carbonization of CoZn containing MOF integrated with COF porous architecture in Ar atmosphere. The graphitic nature of porous carbon is confirmed from Raman analysis. The porosity and nanostructure information are retrieved from N2-sorption and transmission electron microscopic analysis, respectively. The incorporation of different metals and their oxidation states and types of nitrogen present in the C?N framework are confirmed from X-ray photoelectron spectroscopy. The basicity of the materials is determined from a CO2-temperature programmed desorption. ZnCo embedded C?N framework exhibits excellent activity in the selective reductive formylation using HCOOH. For comparison, more than 15 materials are prepared, and their activities are compared. Several control experiments are performed to establish a structure-activity relation. The recycling experiment, hot-filtration test, and poisoning experiment demonstrate the metal embedded porous C?N framework‘s recyclability and stability. A reaction mechanism for the reductive N-formylation of nitroaromatics is presented based on structure-activity relationship, control reactions, and physicochemical characterizations. The development of interesting MOF-COF-derived metal nanoclusters embedded C?N framework for selective reductive formylation of nitroaromatics using formic acid will be highly attractive to catalysis researchers and industrialists.
- Kumar Kar, Ashish,Srivastava, Rajendra
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- Thermal and microwave-assisted N-formylation using solid-supported reagents
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A rapid and easy route to formamides by microwave assisted N-formylation of primary and secondary amines is described. Using an insoluble polymer or an inorganic solid-supported reagent as a formylating agent, microwave irradiation furnished the corresponding formamides in high yields, with reduced reaction time and solvent volume over the conventional approach.
- Desai, Bimbisar,Danks, Timothy N.,Wagner, Gabriele
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- Mesoporous Sn(IV) Doping DFNS Supported BaMnO3 Nanoparticles for Formylation of Amines Using Carbon Dioxide
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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
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- Biocatalytic α-Oxidation of Cyclic Amines and N-Methylanilines for the Synthesis of Lactams and Formamides
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An environmentally friendly method for the synthesis of lactams and formamides through the biocatalytic α-oxidation of amines was developed by employing Pseudomonas plecoglossicida ZMU-T04 as a biocatalyst. In this biocatalytic process, the α-oxidation of cyclic amines and N-methylanilines proceeded smoothly to give the corresponding amides in low to high yields. Furthermore, it was demonstrated that synthetic 3,4-dihydroquinolin-2(1H)-one could be used as a key precursor of antidepressant bioactive molecules. The mechanism of this biocatalytic α-oxidation process was investigated by isotope- labeling experiments.
- Zheng, Daijun,Zhou, Xiaojian,Cui, Baodong,Han, Wenyong,Wan, Nanwei,Chen, Yongzheng
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- Synthesis, characterization, antibacterial and catalytic activity of a nanopolymer supported copper(ii) complex as a highly active and recyclable catalyst for the formamidation of arylboronic acids under aerobic conditions
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This paper reports on the synthesis and use of a nanopolymer supported copper(ii) complex, as a separable catalyst for the formamidation of arylboronic acids under aerobic conditions. The catalyst was characterized using powder XRD, SEM, EDS, TGA-DTG and FT-IR spectroscopy. This method has the advantages of high yields, elimination of homogeneous catalysts, simple methodology and easy work up. Catalytic efficiency remains unaltered even after several repeated cycles. The synthesized catalyst is found to be more highly toxic towards Gram-positive bacteria than Gram-negative bacteria. This journal is the Partner Organisations 2014.
- Nasrollahzadeh, Mahmoud,Zahraei, Ali,Ehsani, Ali,Khalaj, Mehdi
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- Electrochemical N -Formylation of Amines via Decarboxylation of Glyoxylic Acid
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A new method for the synthesis of formamides has been developed through electrochemical decarboxylative N-formylation of amines with glyoxylic acid. This protocol provides an efficient approach to formamides with a broad range of functional group tolerance under ambient conditions.
- Lin, Dian-Zhao,Huang, Jing-Mei
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- Catalyst freeN-formylation of aromatic and aliphatic amines exploiting reductive formylation of CO2using NaBH4
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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
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- An imidazolium based ionic liquid supported on Fe3O4@SiO2 nanoparticles as an efficient heterogeneous catalyst for N-formylation of amines
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An imidazolium based ionic liquid, 1-methyl-3-(3-triethoxysilylpropyl) imidazolium chloride, could be immobilized on the surface of silica-coated ferrite nanoparticles (Fe3O4@SiO2-IL) and could be evaluated as a recyclable catalyst for the N-formylation of amines using formic acid under solvent-free conditions. The prepared organic-inorganic hybrid material could be characterized by various techniques such as Fourier Transform Infrared Spectroscopy (FT-IR), X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDS) and Vibrating Sample Magnetometer (VSM) studies. Utilizing the ferromagnetic nature of Fe3O4, the prepared catalyst could be easily recovered after completion of the reaction by using an external magnetic field. The catalyst could be reused for up to five runs with remarkable catalytic activity. The described methodology has various advantages when compared with other methods that rely on homogeneous catalysts.
- Garkoti, Charu,Shabir, Javaid,Mozumdar, Subho
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- Atomically Dispersed Zn-Nx Sites in N-Doped Carbon for Reductive N-formylation of Nitroarenes with Formic Acid
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Replacement of noble metal catalysts with low-cost, non-noble heterogeneous catalysts is highly desirable. Herein, we prepared a reactive, inexpensive and stable isolated single-atom Zn/N-doped porous carbon (ZnNC) catalyst derived from a versatile zeolitic imidazolate framework precursor. The optimized ZnNC-1000 with Zn-Nx species possesses high zinc loading (5.2 wtpercent) and nitrogen content (6.73 wtpercent), exhibits efficient catalytic performance in the one-pot N-formylation of nitroarene to the corresponding formamides by using formic acid as the hydrogen donor and formylation agent. H2-D2 exchange reaction and HCOOH-chemisorption experiments demonstrated that atomically dispersed Zn-Nx species are essential for the activation of hydrogen and HCOOH molecules, which finally contributed to the highest catalytic activity of ZnNC-1000 for the reductive N-formylation reaction.
- Li, Jinlei,Li, Cunyao,Feng, Siquan,Zhao, Ziang,Zhu, Hejun,Ding, Yunjie
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- Oxidative coupling of alcohols and amines over bimetallic unsupported nanoporous gold: Tailored activity through mechanistic predictability
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An unsupported nanoporous gold catalyst is employed for the direct coupling of primary alcohols and amines to the corresponding amides in the liquid phase. Among others, the reaction of methanol and dimethylamine to the industrially relevant dimethylformamide proceeds smoothly at 40°C (turnover frequency≈40 h-1). The activation of molecular oxygen is identified as a key parameter. Doping of the unsupported catalyst by an admetal (Ru, Ag) is used to increase the activity of the catalyst considerably for this reaction (turnover frequency ≈ 100 h-1).
- Wichmann, Andre,B?umer, Marcus,Wittstock, Arne
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- Ruthenium-cluster-catalysed Reductive Carbonylation of Nitrobenzene: X-Rsay Structure of , a Catalytic Intermediate
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The ruthenium cluster has been structurally characterised and shown to play an important role, along with its precursor , in the hydroxyde- or methoxide-promoted reductive carbonylation of nitrobenzene.
- Bhaduri, Sumit,Khwaja, Hanif,Sharma, Krishna,Jones, Peter G.
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- Metal-free Carbon Monoxide (CO) Capture and Utilization: Formylation of Amines
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The capture and utilization of CO by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were performed in the absence of transition-metal complexes. The reaction of TBD with CO afforded TBD-CO adducts, which were converted to formylated TBD (TBD-CHO). TBD-CO adducts may include an interaction of CO with positively charged species based on NMR and IR analysis. In the presence of amines, CO was transferred from TBD-CO to amines, producing formylated amines with good yields. The reaction mechanism involving TBD-CO adducts is presented based on theoretical calculations. (Figure presented.).
- Noh, Hyeong-Wan,An, Youngjoon,Lee, Seulchan,Jung, Jaehoon,Son, Seung Uk,Jang, Hye-Young
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- Formylation of amines and alcohols using aminopropylated mesoporous SBA-15 silica (APMS) as an efficient and recyclable catalyst
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Aminopropylated mesoporous SBA-15 silica (APMS) is introduced as a new, recyclable and efficient catalyst for the formylation of a variety of amines and alcohols by using readily available formic acid under solvent-free conditions.
- Malakooti, Reihaneh,Sobhani, Sara,Razavi, Nasrin,Shafiei, Soheila,Mokhtari, Rezvan
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- Sulfonic acid supported on hydroxyapatite-encapsulated-γ-Fe2O3 nanocrystallites as a magnetically Br?nsted acid for N-formylation of amines
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Treatment of aqueous formic acid (85%) with structurally diverse amines in the presence of a catalytic amount of sulfonic acid supported on hydroxyapatite-encapsulated-γ-Fe2O3 [HAp@-γ-Fe2O3] (0.9 mol.%) as a heterogeneous, reusable and highly efficient catalyst gave the corresponding formamides in good to excellent yields at room temperature. The magnetically catalytic system was recovered by-passing time consuming filtration operation by using an external magnet device. In addition to facility, this methodology, it also enhances product purity and promises economic as well as environmental benefits.
- Ma'mani, Leila,Sheykhan, Mehdi,Heydari, Akbar,Faraji, Mohammad,Yamini, Yadollah
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- Immobilized Zn(OAc)2on bipyridine-based periodic mesoporous organosilica for N -formylation of amines with CO2and hydrosilanes
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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
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- Thiazolium carbene catalysts for the fixation of CO2 onto amines
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The catalytic N-formylation and N-methylation of amines using CO2 as the carbon source represents a facile and sustainable approach for the synthesis of pharmaceuticals and natural products. Herein, we describe highly effective and inexpensive thiazolium carbene-based catalysts derived from vitamin B1 for the N-formylation and N-methylation of amines, using polymethylhydrosiloxane (PMHS) as a reducing agent, which operate under ambient conditions.
- Das, Shoubhik,Bobbink, Felix D.,Bulut, Safak,Soudani, Mylène,Dyson, Paul J.
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- Catalysis and reaction mechanisms of N-formylation of amines using Fe(III)-exchanged sepiolite
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This study presents a rapid, economical and "green" N-formylation of anilines with formic acid (FA) using Fe(III)-exchanged sepiolite (IES) as a catalyst. The IES exhibited excellent catalytic properties and the reactions were complete within 20-90 min to afford products with high yields. The adsorption mechanism of FA on the IES sample was studied by infrared (IR) spectroscopy at a temperature range of 120-400°C. The thermal desorption of pyridine was detected by the IR technique to estimate the acidity of IES. Lewis acid-bound pyridine bands at 1618-1631 cm-1 and 1443-1445 cm -1 were observed even after the IES sample was heated above 400°C.
- Eren, Bilge,Aydin, Reyhan,Eren, Erdal
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- Evaluation of thioamides, thiolactams and thioureas as hydrogen sulfide (H2S)donors for lowering blood pressure
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Hydrogen sulfide (H2S)is a biologically important gaseous molecule that exhibits promising protective effects against a variety of pathological processes. For example, it was recognized as a blood pressure lowering agent. Aligned with the need for easily modifiable platforms for the H2S supply, we report here the preparation and the H2S release kinetics from a series of structurally diversified thioamides, thiolactams and thioureas. Three different thionation methods based on the usage of a phosphorus pentasulfide and Lawesson reagent were applied to prepare the target thioamides and thiolactams. Furthermore, obtained H2S donors were evaluated both in in vivo and in vitro studies. The kinetic parameters of the liberating H2S was determined and compared with NaHS and GYY4137 using two different detection technics i.e.; fluorescence labeling 7-azido-4-methyl-2H-chromen-2-one and 5,5‘-dithiobis (2-nitrobenzoic acid), sulfhydryl probe, also known as the Ellman's reagent. We have proved that the amount of releasing H2S from these compounds is controllable through structural modifications. Finally, the present study shows a hypotensive response to an intravenous administration of the developed donors in the anesthetized rats.
- Zaorska, Ewelina,Hutsch, Tomasz,Gawry?-Kopczyńska, Marta,Ostaszewski, Ryszard,Ufnal, Marcin,Koszelewski, Dominik
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- Synthesis of N-arylcarboxamides by the efficient transamidation of DMF and derivatives with anilines
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A novel protocol for the transamidation of DMF and derivatives with weakly nucleophilic anilines has been developed, utilizing a catalytic amount of Pd(OAc)2 and 2,2′-bipyridine, and with PivOH and BF3·Et2O as additives. This methodology has a broad substrate scope, and various corresponding transamidation products were prepared in good to excellent yields from commercially available DMF derivatives and anilines. The synthetic utility of the reported protocol was further demonstrated with a gram-scale experiment. Control experiments suggested the efficient transformation of DMF and derivatives with anilines might owe to the synergistic effect of palladium complex, PivOH, and BF3·Et2O.
- Gu, Da-Wei,Guo, Xun-Xiang
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- A NHC-silyliumylidene cation for catalytic N?formylation of amines using carbon dioxide
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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
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- Catalysis of amide hydrolysis and formation under neutral conditions by a zwitterionic imidazolium thiolate
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As a simple model for the hydrolysis of peptides mediated by the cysteine proteases, 2-(mercaptomethyl)-1-methylimidazole (1) was used to catalyze the hydrolysis of four nonactivated amides, namely, formamide, dimethylformamide, N-formylmorpholine, and formanilide (3a-d), at 98 °C, pD 7.6-8.0, μ = 1.0 (KC1). Progress of the hydrolysis reactions was followed by 1H NMR, and the kinetics as a function of added [1] were used to determine the second-order catalytic rate constants (kcat). A putative intermediate 5-formyl thiolester of 1 (4) was not observed to build up during the course of the hydrolysis: the partitioning of authentic 4 between H2O and morpholine and between H2O and aniline was determined (98 °C, pD 8.0). The hydrolysis of N-formylmorpholine was observed to be catalyzed by added phosphate buffer under the same conditions. When the hydrolysis of a 200 mM D2O solution of N-formylmorpholine was allowed to proceed to completion, an equilibrium position of 33 mM amide, 167 mM HCO2H, and 167 mM morpholine was attained: that same equilibrium position was obtained starting with a solution 200 mM in each of HCO2H and morpholine. The conditional equilibrium constant, K′eq = [NFM]/([HCO2H]tot-[morpholine]tot), was found to be 1.2 M-1.
- Keillor,Neverov,Brown
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- NaY zeolite functionalized by sulfamic acid/Cu(OAc)2 as a new and reusable heterogeneous hybrid catalyst for efficient solvent-free formylation of amines
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NaY zeolite functionalized by sulfamic acid/Cu(OAc)2 [NaY/SA/Cu(II)] was synthesized and used as a new, efficient and recyclable catalyst for preparation of formamides. This novel organic-inorganic hybrid catalyst was characterized by several techniques such as FT-IR, XRD, SEM, EDX and TG analysis. Chemoselectivity, easy procedure, excellent yields, very short reaction times, solvent-free and mild reaction conditions are some benefits of this new protocol.
- Kazemi, Samira,Mobinikhaledi, Akbar,Zendehdel, Mojgan
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- Amine modified mesoporous Al2O3@MCM-41: An efficient, synergetic and recyclable catalyst for the formylation of amines using carbon dioxide and DMAB under mild reaction conditions
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This work reports an amine modified meso Al2O3@MCM-41, particularly the ordered mesoporous silica, as a catalyst for the formylation of amines with carbon dioxide (CO2) and with dimethylamine-borane (DMAB) as a green reducing source. This newly developed catalytic system represents a heterogeneous and environmentally benign protocol. Besides this, the catalyst could be reused for five consecutive cycles without any significant loss in its catalytic activity towards the synthesis of formamides. The amine modified meso Al2O3@MCM-41 catalysts were well characterized by high and low angle XRD, temperature programmed desorption (TPD), BET-surface area, TGA/DTA and FT-IR analysis techniques. The effect of various reaction parameters such as temperature, CO2 pressure, time and the ratio of substrates to DMAB for the synthesis of formamides has been investigated. The developed protocol can be applicable for the synthesis of most important key intermediates like formoterol, orlistat, leucovarin and iguratimod in biologically active compounds.
- Nale, Deepak B.,Rath, Dharitri,Parida,Gajengi, Aravind,Bhanage, Bhalchandra M.
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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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- Green synthesis of formamides using the Natrolite zeolite as a natural, efficient and recyclable catalyst
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Chemoselective N-formylation of different amines was carried out with formic acid in the presence of the Natrolite zeolite as an efficient, stable and natural heterogeneous catalyst to give the corresponding formamides at room temperature under solvent-free conditions. This method has the advantages of high yields, mild conditions, simple methodology, easy work up and short reaction times. The catalyst was characterized by different techniques such as powder XRD, XRF, TGA-DTA, SEM and FT-IR spectroscopy. The Natrolite zeolite was recovered and reused several times without the significant loss of its catalytic performance.
- Habibi, Davood,Nasrollahzadeh, Mahmoud,Sahebekhtiari, Hesam
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- Copper-Catalyzed N-Formylation of Amines through Tandem Amination/Hydrolysis/Decarboxylation Reaction of Ethyl Bromodifluoroacetate
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Ethyl bromodifluoroacetate (BrCF2COOEt) was first used as the N-formylating reagent in the copper-catalyzed N-formylation of amines. A range of primary, secondary, cyclic arylamines, and aliphatic amines underwent the N-formylation smoothly to furnish the N-formamides in moderate-to-excellent yields.
- Li, Xiao-Fang,Zhang, Xing-Guo,Chen, Fan,Zhang, Xiao-Hong
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- L-Serine?ZnO as an efficient and reusable catalyst for synthesis of cyclic carbonates and formamides in presence of CO2 atmosphere
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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.
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- An efficient method for the N-formylation of amines under catalyst- and additive-free conditions
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A simple catalyst- and additive-free method for the N-formylation of amines has been developed. The advantages of this protocol include a wide range of functional group tolerance, high efficiency and a lack of required extra promoters under mild conditions. This convenient strategy will provide a facile synthesis towards N-formamide natural products and pharmaceutical derivatives. A mechanism that involves difluorocarbene is proposed for this reaction.
- Xu, Zhuo-Wei,Xu, Wen-Yi,Pei, Xiao-Jun,Tang, Fei,Feng, Yi-Si
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- Mechanistic Study of the N-Formylation of Amines with Carbon Dioxide and Hydrosilanes
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N-formylation of amines with CO2 and hydrosilane reducing agents proceeds via fast and complex chemical equilibria, which hinder easy analysis of the reaction pathways. In situ reaction monitoring and kinetic studies reveal that three proposed pathways, via direct- and amine-assisted formoxysilane formation (pathways 1 and 2, respectively) and via a silylcarbamate intermediate (pathway 3), are possible depending on the reaction conditions and the substrates. While pathway 1 is favored for non-nucleophilic amines in the absence of a catalyst, a base catalyst results in noninnocent behavior of the amine in the CO2 reduction step toward the formoxysilane intermediate. The reaction pathway is altered by strongly nucleophilic amines, which form stable adducts with CO2. Silylcarbamate intermediates form, which can be directly reduced to the N-formylated products by excess hydrosilane. Nevertheless, without excess hydrosilane, the silylcarbamate is an additional intermediate en route to formoxysilanes along pathway 2. Exchange NMR spectroscopy (EXSY) revealed extensive substituent exchange around the hydrosilane silicon center, which confirms its activation during the reaction and supports the proposed reaction mechanisms. Numerous side reactions were also identified, which help to establish the reaction equilibria in the N-formylation reactions.
- Hulla, Martin,Laurenczy, Gabor,Dyson, Paul J.
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- Recyclable Oxofluorovanadate-Catalyzed Formylation of Amines by Reductive Functionalization of CO2 with Hydrosilanes
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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
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- Ammonium iodide-catalyzed radical-mediated tandem cyclization of aromatic aldehydes, arylamines and 1,4-dioxane
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We have developed a novel approach for the construction of 2-((2-arylquinolin-4-yl)oxy)ethan-1-ol derivatives by an NH4I-catalyzed radical-mediated tandem cyclization of three components including aromatic aldehydes, arylamines and 1,4-dioxane.
- Deng, Jiyong,Liao, Yunfeng,Qi, Hongrui,Tao, Qiang,Xie, Yanjun,Yan, Yiyan,Yi, Bing,Zhang, Weijie
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p. 959 - 965
(2022/02/03)
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- Additive-free selective methylation of secondary amines with formic acid over a Pd/In2O3 catalyst
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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
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- Olefin functionalized IPr.HCl monomer as well as preparation method and application thereof
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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; 0078
(2021/06/21)
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- Selective N-formylation of amines catalysed by Ag NPs festooned over amine functionalized SBA-15 utilizing CO2 as C1 source
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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
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- Method for preparing formamide compound by using MCOF to catalyze CO2 as carbon source at normal temperature and pressure
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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 0029
(2021/06/09)
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- Palladium supported on MRGO@CoAl-LDH catalyzed reductive carbonylation of nitroarenes and carbonylative Suzuki coupling reactions using formic acid as liquid CO and H2 source
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In the present study, a heterogeneous palladium catalyst system, Pd nanoparticles supported on MRGO@CoAl-LDH, was synthesized and employed in reductive carbonylation of nitroarenes and carbonylative Suzuki coupling reactions using formic acid as CO and H2 source. The as-obtained heterogeneous catalyst was characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDAX), thermal gravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The nanocatalyst was reused for 5 cycles with a negligible reduction in the yield of products. All reactions were carried out with high yields and under suitable and safe conditions. Also, we have successfully applied formic acid as a good and safe alternative to CO and H2 gases.
- Jadidi Nejad, Masoumeh,Heydari, Akbar
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- Supported CuII Single-Ion Catalyst for Total Carbon Utilization of C2 and C3 Biomass-Based Platform Molecules in the N-Formylation of Amines
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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
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supporting information
p. 16889 - 16895
(2021/09/25)
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- 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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- Functionalizing HY zeolite with sulfonic acid, a micro-meso structure reusable catalyst for organic transformations
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A new class of sulfonic acid functionalized HY zeolite (HY-N-SA) catalyst has been prepared and characterized by some method such as XRD, FT-IR, FESEM, TEM, TGA, NH3-TPD and N2 physisorption. The result shows the micro-meso structure for catalyst without ordering in the mesophase. Then, the HY-N-SA micro-meso structure was used as an acidic catalyst to synthesize of coumarins via Pechmann reaction and facile transformation of amines to formamides under solvent-free condition. To consider the effect of acidity and kind and size of porous on the catalyst activity, this catalyst was compared with NaY-N-SA and MCM-N-SA and pure porous material (NaY and MCM-41). The significant advantages of HY-N-SA with respect to other catalysts are short reaction times, high yields, pure products, mild conditions and easy work-up. In addition, we report an original and environmentally friendly solvent-free procedure which reusability of catalyst makes this method nearly green and environmentally friendly.
- Tavakoli, Fatemeh,Zendehdel, Mojgan
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- Preparation and catalytic evaluation of a palladium catalyst deposited over modified clinoptilolite (Pd&at;MCP) for chemoselective N-formylation and N-acylation of amines
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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
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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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- HCl-mediated transamidation of unactivated formamides using aromatic amines in aqueous media
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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
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p. 3729 - 3739
(2021/10/14)
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- Copper-Catalyzed Cascade N-Dealkylation/N-Methyl Oxidation of Aromatic Amines by Using TEMPO and Oxygen as Oxidants
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A novel tandem N-dealkylation and N-methyl aerobic oxidation of tertiary aromatic amines to N-arylformamides using copper and TEMPO has been developed. This methodology suggested an alternative synthetic route from N-methylarylamines to N-arylformamides.
- Li, Dianjun,Wang, Shihaozhi,Yang, Jiale,Yang, Jinhui
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supporting information
p. 6768 - 6772
(2021/12/31)
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- Highly efficient one pot synthesis of benzimidazoles from 2-nitroaniline and PhSiH3 as reducing agent catalyzed by Pd/C as a heterogeneous catalyst
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This work reports an efficient route for the synthesis of benzimidazole from o-nitroaniline in the presence of carbon dioxide atmosphere, PhSiH3 as a reducing agent catalyzed by Pd/C as a catalyst. Benzimidazoles have become the focus of organic chemists, as benzimidazole is an important intermediate in medicinal chemistry. We have developed more efficient route for the synthesis benzimidazole and various substituted benzimidazoles have been synthesized in good to excellent yield. The TBD (1,5,7-Triazabicyclo [4.4.0] dec-5-ene) is selected as a base as it promotes the CO2 insertion. Benzimidazoles were synthesized through reduction of nitro group followed by cyclization of amine using CO2 as a carbon source. Moreover, the Pd/C catalyst can be recycled up to five recycle run without significant changes in the yield of the product.
- Phatake, Vishal V.,Bhanage, Bhalchandra M.
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- Acid-catalyzed chemodivergent reactions of 2,2-dimethoxyacetaldehyde and anilines
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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
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supporting information
p. 1419 - 1422
(2020/11/12)
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- DMF·HCl as a versatile and straightforward N- and O-formylating agent
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Inspired by the serendipitous isolation of N-formylpiperazines when we attempted the synthesis of a series of piperazines, we have developed a straightforward methodology for the N- and O- formylation of secondary cyclic amines, anilines and steroids, respectively. Such approach is based on the hitherto non-reported use of DMF·HCl complex, as a versatile and easily-available formylating system that can be stored without apparent loss of activity.
- Ramírez-Vázquez, Dulce G.,Vi?as-Bravo, Omar,Martínez-Pascual, Roxana,Pérez-Picaso, Lemuel,Castro-Cerritos, Karla Viridiana
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supporting information
p. 585 - 592
(2020/11/19)
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- Visible-light induced one-pot hydrogenation and amidation of nitroaromatics with carboxylic acids over 2D MXene-derived Pt/N-TiO2/Ti3C2
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Pt nanoparticles supported on N doped titanium dioxide/titanium carbide (MXene) heterojunctions were employed as photocatalysts for the tandem reactions between aromatic nitro compounds and carboxylic acids to produce amide products. The 3%Pt/N-TiO2/Ti3C2 heterojunction was prepared by in situ grew TiO2 on Ti3C2 nanosheets and then N doped TiO2 with melamine, Pt nanoparticles with 3.3 nm mean diameter well dispersed on N-TiO2/Ti3C2. 3%Pt/N-TiO2/Ti3C2 had excellent amidation activity and chemoselectivity under visible-light irradiation. The elevated catalytic performance of 3%Pt/N-TiO2/Ti3C2 was owing to the improvement in photogenerated electron and hole separation efficiency through charge short-range directional transmission caused by the intimate contact between the TiO2 and the conductive Ti3C2. This direct hydrogenation along with amidation between nitroaromatics and carboxylic acids own actual merits in the amides produce with no harmful byproducts. In situ DRIFTS spectra verified that the amidation activation with visible light irradiation at 25 °C was much faster than heating.
- Jiang, Heyan,Hu, Zujie,Gan, Chuan,Sun, Bin,Kong, Shuzhen,Bian, Fengxia
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- BF3·Et2O as a metal-free catalyst for direct reductive amination of aldehydes with amines using formic acid as a reductant
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A versatile metal- and base-free direct reductive amination of aldehydes with amines using formic acid as a reductant under the catalysis of inexpensive BF3·Et2O has been developed. A wide range of primary and secondary amines and diversely substituted aldehydes are compatible with this transformation, allowing facile access to various secondary and tertiary amines in high yields with wide functional group tolerance. Moreover, the method is convenient for the late-stage functionalization of bioactive compounds and preparation of commercialized drug molecules and biologically relevant N-heterocycles. The procedure has the advantages of simple operation and workup and easy scale-up, and does not require dry conditions, an inert atmosphere or a water scavenger. Mechanistic studies reveal the involvement of imine activation by BF3and hydride transfer from formic acid.
- Fan, Qing-Hua,Liu, Xintong,Luo, Zhenli,Pan, Yixiao,Xu, Lijin,Yang, Ji,Yao, Zhen,Zhang, Xin
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supporting information
p. 5205 - 5211
(2021/07/29)
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- An Environmentally Benign, Catalyst-Free N?C Bond Cleavage/Formation of Primary, Secondary, and Tertiary Unactivated Amides
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Herein, we report an operationally simple, cheap, and catalyst-free method for the transamidation of a diverse range of unactivated amides furnishing the desired products in excellent yields. This protocol is environmentally friendly and operates under extremely mild conditions without using any promoter or additives. Significantly, this strategy has been implied in the chemoselective synthesis of a pharmaceutical molecule, paracetamol, on a gram-scale with excellent yield. We anticipate that this universally applicable strategy will be of great interest in drug discovery, biochemistry, and organic synthesis.
- Kumar, Vishal,Dhawan, Sanjeev,Girase, Pankaj Sanjay,Singh, Parvesh,Karpoormath, Rajshekhar
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p. 5627 - 5639
(2021/11/11)
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- Nickel-Catalyzed Reductive Cross-Coupling of N-Acyl and N-Sulfonyl Benzotriazoles with Diverse Nitro Compounds: Rapid Access to Amides and Sulfonamides
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Herein we report a Ni-catalyzed reductive transamidation of conveniently available N-acyl benzotriazoles with alkyl, alkenyl, and aryl nitro compounds, which afforded various amides with good yields and a broad substrate scope. The same catalytic reaction conditions were also applicable for N-sulfonyl benzotriazoles, which could undergo smooth reductive coupling with nitroarenes and nitroalkanes to afford the corresponding sulfonamides.
- Bai, Jin,Li, Shangzhang,Li, Wanfang,Qu, Erdong,Zheng, Yan
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supporting information
(2021/12/27)
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- Effective and selective direct aminoformylation of nitroarenes utilizing palladium nanoparticles assisted by fibrous-structured silica nanospheres
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Abstract: Palladium nanoparticles (~ 1–3?nm, 0.4?wtpercent Pd) were uniformly distributed over the surface of fibrous silica nanospheres (KCC-1) modified via aminopropyltriethoxysilane using a fast and cost-effective palladium (II) chloride reduction process. The Pd nanoparticles (Pd NPs) distribution over the ensuing catalyst Pd/KCC-1-NH2 showed much more uniform distribution, and smaller size compared with the tedious hydrothermal reduction method. The morphological, chemical, and size analyses of Pd/KCC-1-NH2 by BET, UV–Vis spectra, XRD, HR-TEM, EDS and XPS analysis revealed that the succeeding material consist of a distinct fibrous silica nanospheres support adorn with Pd NPs. The resultant nanocatalyst was tested for the one-step reductive aminoformylation of aromatic nitro compounds using formic acid. A wide range of substituted nitroarenes including electron withdrawing, releasing, sterically hindered and multifunctional groups have been converted to corresponding aryl formamide in quantitative yields (yields up to 98percent) at moderate temperature (70?°C). Optimization study has proved that the 6 equivalent of formic acid is required and toluene was found to be the better solvent. The established practice is beneficial due to the use of formic acid as H2 source and formylating agent, easiness in handling of the catalyst and simple workup procedure with efficient catalyst reusability. Graphic abstract: [Figure not available: see fulltext.].
- Jaseer, E. A.,Qureshi, Ziyauddin S.
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- Biomass-derived Fe-NC hybrid for hydrogenation with formic acid: Control of Fe-based nanoparticle distribution
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A series of Fe-NC catalysts were synthesized by pyrolyzing an Fe complex and wheat flour at 500 °C. All of them were characterized and applied in the catalytic transfer hydrogenation of nitroarenes with formic acid. It was found that the catalytic activity was significantly affected by the size and distribution of Fe-based nanoparticles (NPs), which could be easily regulated by altering the Fe source. Meanwhile, more basic nitrogen sites were preserved on the catalyst so that the reaction ran smoothly without base additives. Among all catalysts, Fe-NC-FeCl2 exhibited the best catalytic performance due to smaller Fe3O4 NPs and greater N doping. Moreover, it showed excellent applicability for diverse nitroarenes. Obviously, this work demonstrates the importance of the metallic NPs' size and distribution, providing a new insight into the design of M-NC catalysts. The catalyst is economical and eco-friendly, and shows potential application value in industry.
- Chen, Ligong,Gao, Ruixiao,Li, Yang,Liu, Lu,Wang, Bowei,Xu, Wensheng,Yan, Xilong,Zhang, Dan
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p. 10689 - 10694
(2020/03/27)
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- UiO-66 as an efficient catalyst for N-formylation of amines with CO2 and dimethylamine borane as a reducing agent
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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.
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supporting information
(2019/12/11)
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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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- 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
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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
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supporting information
p. 8414 - 8422
(2020/12/29)
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- Direct: N -formylation of nitroarenes with CO2
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Herein we describe a straightforward N-formylation of nitroarenes with CO2 to access N-aryl formamides exclusively in the presence of iron and hydrosilane as additives. This protocol showcases a good tolerance of a wide range of nitroarenes and nitroheteroarenes.
- Shen, Ni,Zhai, Shi-Jing,Cheung, Chi Wai,Ma, Jun-An
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p. 9620 - 9623
(2020/09/03)
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- Application of Ag/TFPG-DMB COF in carbamates synthesis via CO2 fixation reaction and one-pot reductive N-formylation of nitroarenes under sunlight
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We have designed mesoporous AgNPs decorated COF (Ag/TFPG-DMB COF) nanomaterial which has been formed by an easy ex-situ synthetic method. The synthesized material is characterized by FTIR, PXRD, UV–vis, N2 adsorption–desorption studies, TEM, FESEM and XPS. The material showed the generation of identical mesopore at 3.9 nm. It is observed that the material can perform as both thermally and photochemically active catalyst for carbamate synthesis and one-pot reduction and N-formylation of nitroarenes respectively. The catalytic activity of the Ag/ TFPG-DMB COF nanomaterial is checked for green synthesis of carbamates from different amines and alcohols under 1 atmospheric pressure of CO2 with excellent yield (upto 95 %) as well as with high TOF value (182 h?1) and high selectivity. Additionally, the Ag/ TFPG-DMB COF nanomaterial is also applied as a potentially active photocatalyst for one-pot nitroarene reduction along with N-formylation reaction under sunlight irradiation in green reaction conditions with exceptionally high yield of formylated products upto 99 % as well as with high TOF value (762 h ?1). The catalyst efficiently reduced and formylated para-nitrophenol, a potential water pollutant, which elaborates its scope as an efficient catalyst for water purification also. The catalyst recyclability is also checked for five reaction cycles for both the reactions and the Ag/TFPG-DMB COF material showed outstanding recycling ability without any noticeable leaching of active metal or catalyst degradation.
- Biswas, Surajit,Hazra Chowdhury, Arpita,Hazra Chowdhury, Ipsita,Islam, Sk. Manirul
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- Fe3O4@GlcA@Cu-MOF: A Magnetic Metal-Organic Framework as a Recoverable Catalyst for the Hydration of Nitriles and Reduction of Isothiocyanates, Isocyanates, and Isocyanides
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A novel magnetic metal-organic framework (Fe3O4@GlcA@Cu-MOF) has been prepared and characterized by spectroscopic, microscopic, and magnetic techniques. This magnetically separable catalyst exhibited high catalytic activity for nitrile hydration and the ability to reduce isothiocyanates, isocyanates, and isocyanides with excellent activity and selectivity without any additional reducing agent.
- Ghorbani-Choghamarani, Arash,Taherinia, Zahra
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supporting information
p. 902 - 909
(2020/11/30)
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- Efficient: N -formylation of primary aromatic amines using novel solid acid magnetic nanocatalyst
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Sulfonic acid functionalized over biguanidine fabricated silica-coated heterogeneous magnetic nanoparticles (NP?SO3H) have been synthesized, well characterized and explored for the first time, as an efficient and recyclable catalyst for N-formylation of primary amines under mild reaction conditions. Exploiting the magnetic nature of Fe3O4, the prepared catalyst was readily recovered from the reaction mixture via an external magnet. The catalyst can be reused for up to six cycles without any substantial loss of catalytic activity. The cost effectiveness, simple methodology, wide substrate tolerance, excellent yield and easy work-up are the additional advantages of present catalytic system. This journal is
- Agarwal, Alka,Awasthi, Satish K.,Yadav, Jitendra Kumar,Yadav, Priyanka
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p. 41229 - 41236
(2020/11/23)
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- N-Formylation of amines using arylhydrazones of malononitrile and a Cu(II) complex under eco-friendly conditions at room temperature
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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.
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- Silver-Catalyzed Selective Multicomponent Coupling Reactions of Arynes with Nitriles and Isonitriles
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Pathway selective aryne-based novel multicomponent coupling reactions with isonitriles and nitriles are described. Crucial to these reactions is the formation of a silver-aryne complex, which shows differential reactivity toward isonitriles and nitriles to form two different forms of ortho-nitrilium organosilver arene species. Interception of the nitrilium of an aryne-isonitrile adduct with another isonitrile leads to the formation of benzocyclobutene-1,2-diimines, whereas the nitrilium of an aryne-nitrile adduct renders selective formation of 3H-indol-3-imines or 3-iminoindolin-2-ol depending on the structure of the nitrile employed.
- Ghorai, Sourav,Lin, Yongjia,Xia, Yuanzhi,Wink, Donald J.,Lee, Daesung
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supporting information
p. 642 - 647
(2020/01/31)
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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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- Silver-Catalyzed, N-Formylation of Amines Using Glycol Ethers
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A silver-catalyzed protocol was found to afford the N-formylation of amines in moderate-to-good yields. Ethylene glycol-derived, oligomeric ethers were found to function as the formylating agent, with 1,4-dioxane affording the best results. This reaction does not require the use of stoichiometric activating reagents, and avoids the use of explosive reagents or toxic gases, such as CO, as the C1 synthon. Mechanistic studies indicate a single-electron transfer-based pathway. This work highlights the ability of silver to participate in unexpected reaction pathways.
- King, Bradley H.,Wang, Michelle L.,Jesse, Kate A.,Kaur, Guneet,Tran, Brianna,Walser-Kuntz, Ryan,Iafe, Robert G.,Wenzel, Anna G.
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p. 13256 - 13263
(2020/11/26)
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- METHOD OF CARBON MONOXIDE FIXATION AND METHOD OF AMINE FORMYLATION
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The present invention relates to a method for fixing carbon monoxide in a metal-free condition and a method for formating amine using the same.
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Paragraph 0078; 0081-0085; 0100-0102
(2021/02/19)
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- Tracing and elucidating visible-light mediated oxidation and C-H functionalization of amines using mass spectrometry
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The co-existing mechanism of visible light mediated direct oxidation and C-H functionalization of amines was investigated by capturing all the intermediates using online mass spectrometry. The two-step dehydrogenation of amine involving a proton coupled electron transfer (PCET) process was revealed for the first time.
- Ai, Wanpeng,Gao, Yunpeng,Xue, Jinjuan,Liu, Xiaoyun,Liu, Huwei,Wang, Jianbo,Bai, Yu
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supporting information
p. 2163 - 2166
(2020/02/26)
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- Catalytic Activity of a Zr MOF Containing POCOP-Pd Pincer Complexes
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A metal-organic framework assembled from POCOP-Pd pincer complex metallolinkers (1-PdBF4, Zr6O4(OH)4(L-PdMeCN)3(BF4)3, L = (2,6-(OPAr2)2C6H3, Ar = p-C6H4CO2-) has been generated via postsynthetic oxidative I-/BF4- ligand exchange with NOBF4. 1-PdBF4 catalyzes a range of organic transformations, including transfer hydrogenation of unsaturated organic substrates, terminal alkyne hydration, and intramolecular hydroarylation of alkynes. The homogeneous analogue, tBu4POCOP-PdBF4, shows poor catalytic activity for transfer hydrogenation and alkyne hydration and decomposes under the catalytic reaction conditions. Solubility limitations and catalyst deactivation pathways observed for the homogeneous pincer complex propound the advantages of using porous solid supports to immobilize organometallic species.
- Kassie, Abebu A.,Wade, Casey R.
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p. 2214 - 2221
(2020/07/06)
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