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NMR detection of isomers arising from restricted rotation of the C-N amide bond of N-formyl-o-toluidine and N,N′-bis-formyl-o-tolidine
Full and unambiguous assignment of all 1H- and 13C-NMR resonances of the isomers due to restricted C-N amide bond rotation of N-formyl-o-toluidine and N,N′-bis-formyl-o-tolidine in DMSO-d6 is reported. The cis-isomer predominates in the equilibrium mixture of both compounds as 1D-NOE difference experiments show.
Quintanilla-Licea, Ramiro,Colunga-Valladares, Juan F.,Caballero-Quintero, Adolfo,Rodriguez-Padilla, Cristina,Tamez-Guerra, Reyes,Gomez-Flores, Ricardo,Waksman, Noemi
p. 662 - 673
(2002)
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Method for synthesizing P-chloroO-toluidine
The invention discloses a method for synthesizing p-chloroo-toluidine, which comprises the following steps: synthesizing o-toluidine and a protective agent in an organic solvent to obtain an amino-protected intermediate. The amino protected intermediate is added into hydrochloric acid, an oxidant is added for chlorination reaction, and a chlorination product is obtained. The chlorinated product is removed and the amino protecting group is removed to give p-chloroo-toluidine. The method for synthesizing p-chloroo-toluidine provided by the invention is high in yield, simple to operate, less in three wastes, high in product content and good in quality, and can be suitable for industrial mass production.
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Paragraph 0094-0095

(2021/10/05)

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)

Copper-Catalyzed Cascade N-Dealkylation/N-Methyl Oxidation of Aromatic Amines by Using TEMPO and Oxygen as Oxidants
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
supporting information
p. 6768 - 6772
(2021/12/31)

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)

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)

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)

Copper promoted aerobic oxidative c(sp3)-c(sp3) bond cleavage of n-(2-(pyridin-2-yl)-ethyl)anilines
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
p. 2725 - 2732
(2020/03/11)

A Practical Approach for the Transamidation of N, N-Dimethyl Amides with Primary Amines Promoted by Sodium tert-Butoxide under Solvent-Free Conditions
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
p. 3286 - 3294
(2020/09/23)

Effective and selective direct aminoformylation of nitroarenes utilizing palladium nanoparticles assisted by fibrous-structured silica nanospheres
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.
(2020/07/09)

Visible-light-induced radical cascade cyclization of oxime esters and aryl isonitriles: Synthesis of cyclopenta[: B] quinoxalines
A visible-light-induced radical cascade cyclization of aryl isonitriles and cyclobutanone oxime esters for the synthesis of cyclopenta[b]quinoxalines has been accomplished for the first time. The key to the success of this process was the integration of the in situ-formed nitrile radical followed by the cascade radical isonitrile/nitrile insertion-cyclization. The easy introduction of substituents for both substrates and the high functional group tolerance of the reaction make it an efficient strategy to give various quinoxaline derivatives in moderate to good yields.
Yuan, Yao,Dong, Wu-Heng,Gao, Xiao-Shuang,Xie, Xiao-Min,Zhang, Zhao-Guo
supporting information
p. 11900 - 11903
(2019/10/11)

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)

Cobalt nanoparticles anchoring on nitrogen doped carbon with excellent performances for transfer hydrogenation of nitrocompounds to primary amines and N-substituted formamides with formic acid
Cobalt nanoparticles anchoring on nitrogen doped carbon derived from pyrolysis of a cobalt complex and chitosan were developed for reduction of nitrocompounds with neat formic acid to their corresponding amines or N-substituted formamides by switch of solvents. Characterization results revealed that most of the nitrogen atoms are present as graphitic N and pyridinic N as anchoring sites, and the cobalt nanoparticles are wrapped by nitrogen doped carbon layers, endowing the catalyst with excellent activity and superior reusability.
Zhang, Yuecheng,Cao, Pengwei,Zhang, Hong-Yu,Yin, Guohui,Zhao, Jiquan
(2019/07/08)

Sustainable Co-Synthesis of Glycolic Acid, Formamides and Formates from 1,3-Dihydroxyacetone by a Cu/Al2O3 Catalyst with a Single Active Sites
Glycolic acid (GA), as important building block of biodegradable polymers, has been synthesized for the first time in excellent yields at room temperature by selective oxidation of 1,3-dihyroxyacetone (DHA) using a cheap supported Cu/Al2O3 catalyst with single active CuII species. By combining EPR spin-trapping and operando ATR-IR experiments, different mechanisms for the co-synthesis of GA, formates, and formamides have been derived, in which .OH radicals formed from H2O2 by a Fenton-like reaction play a key role.
Dai, Xingchao,Adomeit, Sven,Rabeah, Jabor,Kreyenschulte, Carsten,Brückner, Angelika,Wang, Hongli,Shi, Feng
supporting information
p. 5251 - 5255
(2019/03/07)

N,N-coordinated palladium complex with meta-carborane ligand and preparation and application of palladium complex
The invention relates to an N,N-coordinated palladium complex with a meta-carborane ligand and preparation and application of the palladium complex. A preparation method of the palladium complex comprises the following steps that (1) an n-BuLi solution is added into a meta-carborane solution and then a reaction is performed at a room temperature for 30-60 min; (2) 3-chloromethylpyridine is added and reacts at the room temperature for 3-5 h; (3) PdCl2 is added and reacts at the room temperature for 2-5 h, and the palladium complex is obtained through post-treatment; and the palladium complex isused for catalyzing an arylamine formylation reaction to prepare an arylamine formamide compound. Compared with the prior art, the synthesis process of the palladium complex is simple and green, andhas excellent selectivity and a high yield; and the palladium complex has the characteristics such as stable physicochemical properties and thermal stability, and exhibits excellent catalytic activityin the arylamine formylation reaction.
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Paragraph 0045-0048

(2019/11/12)

NH4I-promoted N-acylation of amines via the transamidation of DMF and DMA under metal-free conditions
An unprecedented NH4I-promoted N-formylation and N-acetylization of various amines with dimethylformamide (DMF)and dimethylacetamide (DMA)has been developed. This protocol shows broad substrate scope for aromatic, aliphatic, and heterocyclic amines, which provides a metal-free strategy for N-acylation featuring mild reaction conditions, as well as inexpensive and readily available starting materials.
Chen, Jiahui,Jia, Jing,Guo, Ziyi,Zhang, Jitan,Xie, Meihua
supporting information
p. 1426 - 1429
(2019/05/06)

Mild and facile synthesis of formamide: Reduction and functionalization of CO2 using NaBH(OAc)3 under atmospheric pressure
An approach for N-formylation of amines was developed using NaBH(OAc)3 as a reductant under an atmospheric pressure of CO2 at 50 °C. The corresponding formylated products of various amines, including aliphatic and aromatic amines, amines with reductive-sensitive nitro groups and alkynyl groups and benzamides were obtained in good to excellent yields, and the possible reaction mechanism was also proposed.
Liu, Huan,Nie, Zhuang,Shao, Jiaan,Chen, Wenteng,Yu, Yongping
supporting information
p. 3552 - 3555
(2019/07/09)

Visible-Light-Induced Radical Cascade Cyclization: Synthesis of the ABCD Ring Cores of Camptothecins
A new strategy for constructing indolizino[1,2-b]quinolin-9(11H)-ones (ring cores of camptothecins) from readily available isocyanoarenes and N-(alkyl-2-yn-1-yl)pyridin-2(1H)-ones has been developed through a visible-light-induced radical cascade cyclization process. The reaction proceeds under mild conditions with fair to excellent yields. The easy introduction of substituents for both reactants and the broad functional group tolerance of the reaction make it a straightforward route to the cores of the marketed camptothecins and their derivatives.
Yuan, Yao,Dong, Wuheng,Gao, Xiaoshuang,Gao, Huang,Xie, Xiaomin,Zhang, Zhaoguo
supporting information
p. 2840 - 2846
(2018/03/09)

Method for preparing N-formylated amine compounds
The invention discloses a method for preparation N-formylated amine compounds. In the method, the amine compounds and 1,3-dihydroxy acetone are taken as reaction raw materials reacting in a reactor for 2-48 hours at the reaction temperature of 0-100DEG C in a reaction medium in the presence of composite catalysts and oxidants, and the N-formylated amine compounds are obtained. The method is simpleand moderate in reaction conditions, cost can be reduced, target products can be obtained with high yield, and the catalysts used have high catalytic activity and are easy to be separated from a reaction system and reuses; the method is environment friendly during the whole process, the reaction raw materials are easy to be converted from biodiesel by-product propylene glycol, and use of glycerolis facilitated.
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Paragraph 0040; 0048; 0049

(2018/11/03)

Consecutive Lossen rearrangement/transamidation reaction of hydroxamic acids under catalyst- and additive-free conditions
The Lossen rearrangement is a classic process for transforming activated hydroxamic acids into isocyanate under basic or thermal conditions. In the current report we disclosed a consecutive Lossen rearrangement/transamidation reaction in which unactivated hydroxamic acids were converted into N-substituted formamides in a one-pot manner under catalyst- and additive-free conditions. One feature of this novel transformation is that the formamide plays triple roles in the reaction by acting as a readily available solvent, a promoter for additive-free Lossen rearrangement, and a source of the formyl group in the final products. Acyl groups other than formyl could also be introduced into the product when changing the solvent to other low molecular weight aliphatic amide derivatives. The solvent-promoted Lossen rearrangement was better understood by DFT calculations, and the intermediacy of isocyanate and amine was supported well by experiments, in which the desired products were obtained in excellent yields under similar conditions. Not only monosubstituted formamides were synthesized from hydroxamic acids, but also N,N-disubstituted formamides were obtained when secondary amines were used as precursors.
Jia, Mengmeng,Zhang, Heng,Lin, Yongjia,Chen, Dimei,Chen, Yanmei,Xia, Yuanzhi
p. 3615 - 3624
(2018/05/26)

Supported Palladium Nanoparticles Catalyzed Reductive Carbonylation of Nitroarenes to N-Arylformamides
A facile reductive carbonylation reaction of nitroarenes to N-arylformamide synthesis was investigated under polymer supported palladium (Pd@PS) nanoparticles catalyzed conditions. Dual role of oxalic acid dihydrate ((CO2H)2 ? 2H2O) as H2 source for hydrogenation and CO source for carbonylation reaction for desired products synthesis was critically investigated under favorable DMF solvent conditions. Several cross experiments were performed to establish the best possible hypothesis for the proposed mechanism and understanding about the involvement of CO in the reaction pathway. Further, ortho-substituted nitroarenes were found to be highly specific for facile para-hydroxylation to give corresponding para-hydroxy N-aryl formamides. (Figure presented.).
Thakur, Vandna,Kumar, Ajay,Sharma, Nishtha,Shil, Arun K.,Das, Pralay
supporting information
p. 432 - 437
(2017/12/26)

Copper-(II) Catalyzed N-Formylation and N-Acylation of Aromatic, Aliphatic, and Heterocyclic Amines and a Preventive Study in the C-N Cross Coupling of Amines with Aryl Halides
A Cu-(II) catalyzed N-formylation and N-acylation of amines with moderate to excellent yields, using N, N-dimethyl formamide (DMF) and N, N-dimethyl acetamide (DMA) as a formyl and acylating sources in the presence of 1,2,4-triazole is reported. This novel, highly efficient and simple protocol shows broad substrate scope for aliphatic, aromatic, and heterocyclic amines. In addition, the conditions to prevent N-formylation and N-acylation impurities in the C?N cross coupling of amines and aryl halides are described typically when DMF and DMA are used as solvents, with various catalysts, ligands, and bases.
Sonawane, Rahul B.,Rasal, Nishant K.,Bhange, Dattatraya S.,Jagtap, Sangeeta V.
p. 3907 - 3913
(2018/09/12)

Graphene oxide (GO) catalyzed transamidation of aliphatic amides: An efficient metal-free procedure
Transamidation involves direct interconversion of an amide with amine, and represents an alternative to the common method of amide formation from the reaction of carboxylic acid with an amine. While the carboxamides have huge potential in biological systems and polymer industries, their formation from carboxylic acids requires activation by a suitable catalyst. A metal-free transamidation of aliphatic amide with aromatic amine catalyzed by graphene oxide (GO) has been developed and established as a general, synthetically useful and selective procedure. Graphene oxide bearing several carboxylic acids on the edges and having large surface area acts as an efficient and recyclable catalyst for transamidation.
Bhattacharya, Suchandra,Ghosh, Pranab,Basu, Basudeb
supporting information
p. 899 - 903
(2018/02/09)

A green, efficient, and rapid procedure for the hydrogenation of nitroarenes to formanilides in water
Abstract: A green, efficient, and rapid procedure for the hydrogenation of nitroarenes to formanilides in Pd(TFA)2/HCOOH system in water is described. Under optimized conditions, the reaction of most substrates is complete within 30?min with yields of 30–93%. Furthermore, this procedure is applied successfully for the modification of natural products, such as arctigenin, vindoline, and estrone. Graphical abstract: [Figure not available: see fulltext.].
Wang, Yingying,Zhan, Zhajun,Zhou, Yang,Lei, Min,Hu, Lihong
p. 527 - 533
(2018/01/27)

Diverse catalytic reactivity of a dearomatized PN3P?-nickel hydride pincer complex towards CO2 reduction
A dearomatized PN3P?-nickel hydride complex has been prepared using an oxidative addition process. The first nickel-catalyzed hydrosilylation of CO2 to methanol has been achieved, with unprecedented turnover numbers. Selective methylation and formylation of amines with CO2 were demonstrated by such a PN3P?-nickel hydride complex, highlighting its versatile functions in CO2 reduction.
Li, Huaifeng,Gon?alves, Théo P.,Zhao, Qianyi,Gong, Dirong,Lai, Zhiping,Wang, Zhixiang,Zheng, Junrong,Huang, Kuo-Wei
supporting information
p. 11395 - 11398
(2018/10/20)

Selective Gold-Catalysed Synthesis of Cyanamides and 1-Substituted 1H-Tetrazol-5-Amines from Isocyanides
The newly discovered gold-catalysed reaction of isocyanides with hydrazoic acid generated in situ from trimethylsilyl azide and methanol (or, alternatively, from NaN3/AcOH) produces either cyanamides or 1-substituted 1H-tetrazol-5-amines, depending on the amount of available HN3. The reaction proceeds selectively and in generally high yields of either product, thus providing a particularly convenient access to a wide range of substituted 1H-tetrazol-5-amines that are rather difficult to access otherwise.
?koch, Karel,Císa?ová, Ivana,?těpni?ka, Petr
supporting information
p. 13788 - 13791
(2018/09/14)

One-pot selective N-formylation of nitroarenes to formamides catalyzed by core-shell structured cobalt nanoparticles
One-pot direct N-formylation of readily available nitroarenes with ammonium formate catalyzed by core-shell structured cobalt nanoparticles has been developed. A broad set of nitroarenes was successfully converted to their corresponding formamides in good to high yields with various functional group tolerance. This heterogeneous catalyst can be easily removed from the reaction medium and can be reused several times without a significant loss of reaction efficiency.
Dong, Xiaosu,Wang, Zhaozhan,Duan, Yanan,Yang, Yong
supporting information
p. 8913 - 8916
(2018/08/17)

A fragrant amines for the preparation of compounds (by machine translation)
The invention discloses a fragrant amines preparation method of the compound, the method in a certain amount of supported cobalt-containing catalyst and a certain amount of fragrant nitryl compounds added in the reactor, then adding ammonium formate, and tetrahydrofuran mixed solvent with water, under stirring, the reaction temperature is 80 - 200 °C, reaction 0.5 - 24 h, to get the corresponding sweet-smelling amines compound. According to the preparation method of this invention the use of inexpensive, renewable bamboo shoots as raw materials for preparing carbon precursor, environmental protection, simple and easy to obtain, without adding nitrogen source material; at the same time in order to triphenylphosphine as the phosphorus source, low price. The substituted ammonium hydrogen as the reducing agent, the operation is simple, mild reaction conditions, in particular to an easily reducible functional group containing fragrant nitryl compounds for chemical selectivity can be controlled more easily. (by machine translation)
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Paragraph 0062-0066

(2018/11/10)

Sulfated polyborate-catalyzed N-formylation of amines: a rapid, green and efficient protocol
Abstract: A rapid, green and efficient method for N-formylation reaction of various amines with formic acid in the presence of sulfated polyborate catalyst under solvent-free conditions has been described. The catalyst has the advantage of mild Bronsted as well as Lewis acid character. The catalyst is recyclable with no significant loss in catalytic activity. The present protocol is advantageous due to its solvent-free condition, short reaction time, high yields, easy workup and ability to tolerate a variety of functional groups.
Khatri, Chetan K.,Chaturbhuj, Ganesh U.
p. 2513 - 2519
(2017/11/06)

Co3O4 nanoparticles prepared by oxidative precipitation method: an efficient and reusable heterogeneous catalyst for N-formylation of amines
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
p. 413 - 422
(2017/01/14)

NaY zeolite functionalized by sulfamic acid/Cu(OAc)2 as a new and reusable heterogeneous hybrid catalyst for efficient solvent-free formylation of amines
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
p. 1767 - 1772
(2017/07/27)

Biocatalytic α-Oxidation of Cyclic Amines and N-Methylanilines for the Synthesis of Lactams and Formamides
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
p. 937 - 940
(2017/03/27)

Silver-Catalyzed Chemoselective [4+2] Annulation of Two Isocyanides: A General Route to Pyridone-Fused Carbo- and Heterocycles
A silver-catalyzed chemoselective [4+2] annulation of aryl and heteroaryl isocyanides with α-substituted isocyanoacetamides was developed for the facile and efficient synthesis of 2-aminoquinolones, naphthyridines, and phenanthrolines. A mechanism for this multistep domino reaction is proposed on the basis of a13C-labeling experiment, according to which an unprecedented chemoselective heterodimerization of two different isocyanides generates an α-amidoketenimine intermediate, which undergoes 1,3-amino migration to form an α-imidoylketene, followed by 6 π electrocyclization.
Hu, Zhongyan,Dong, Jinhuan,Men, Yang,Lin, Zhichen,Cai, Jinxiong,Xu, Xianxiu
supporting information
p. 1805 - 1809
(2017/02/05)

Cobalt(II)-Catalyzed Isocyanide Insertion Reaction with Sulfonyl Azides in Alcohols: Synthesis of Sulfonyl Isoureas
A Co(II)-catalyzed isocyanide insertion reaction with sulfonyl azides in alcohols to form sulfonyl isoureas via nitrene intermediate has been developed. This protocol provides a new, environmentally friendly, and simple strategy for the synthesis of sulfonyl isourea derivatives by employing a range of substrates under mild conditions.
Jiang, Tian,Gu, Zheng-Yang,Yin, Ling,Wang, Shun-Yi,Ji, Shun-Jun
supporting information
p. 7913 - 7919
(2017/08/14)

New catalytic performance of immobilized sulfuric acid on activated charcoal for n-formylation of amines with ethyl formate
Summary: Simple and highly efficient procedure for N-formylation of various amines was carried out in the presence of the immobilized sufuric acid on activated charcoal as an efficient promoter system. All reactions were taken place in refluxing ethyl formate (54 °C) under mild reaction conditions. The product formamides were obtained in high to excellent yields (83-95%) within 4-80 min.
Abdollahi, Mohammad,Zeynizadeh, Behzad,Sadighnia, Leila
p. 619 - 627
(2017/11/06)

Acidic ionic liquid immobilized on nanoporous Na+-montmorillonite as an efficient and reusable catalyst for the formylation of amines and alcohols
In this work, nanoporous sodium montmorillonite clay (Na+-MMT) was used as a support for the immobilization of 1-methyl-3-(trimethoxysilylpropyl)-imidazolium hydrogen sulfate. The Na+-MMT chemical modification ([Na+-MMT-[pmim]HSO4) was confirmed by a variety of techniques including Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy and potentiometric titration. The catalytic performance of this immobilized acidic ionic liquid was probed for the N-formylation of a variety of amines using formic acid under solvent-free conditions. This reagent is also useful for the formylation of benzylic alcohols. The procedure gave the products in excellent yields in very short reaction times. Also, this catalyst can be reused ten times without loss of its catalytic activity.
Shirini, Farhad,Mazloumi, Masoumeh,Seddighi, Mohadeseh
p. 1759 - 1776
(2016/03/16)

Supported nano-gold-catalyzed N-formylation of amines with paraformaldehyde in water under ambient conditions
A simple and efficient Au/Al2O3 catalyst was prepared by the co-precipitation method for the oxidative N-formylation of amines with paraformaldehyde. Under the optimized reaction conditions, excellent amine conversion and N-formamide selectivity can be obtained with up to 97% yield with water as the solvent under ambient conditions. This catalyst tolerated a wide range of primary amines and second amines, and it can be reused for at least five runs without obvious deactivation.
Ke, Zhengang,Zhang, Yan,Cui, Xinjiang,Shi, Feng
p. 808 - 816
(2016/02/12)

Covalently bonded zwitterionic sulfamic acid onto the SBA-15 (SBA-15/PrEn-NHSO3H) reveals good Bronsted acidity behavior and catalytic activity in N-formylation of amines
Ethylenediamine-functionalization of SBA-15 with N1-(3-(trimethoxysilyl)propyl)ethane-1,2-diamine (PrEn) was then underwent covalent sulfonation over secondary and primary amine groups (SBA-15/PrEn-NHSO3H) on the surface of the mesoporous SBA-15 pore walls. Scanning electron microscope (SEM), transmission electron microscope (TEM), SEM-energy dispersive X-ray (SEM-EDX), BET surface are analysis, thermal gravimetric (TG), FT-IR spectrums and CHNS were recorded for the characterization of SBA-15/PrEn-NHSO3H. This material was studied as a novel catalyst for N-formylation of amines. Based on the results, SBA-15/PrEn-NHSO3H acted as zwitterionic IL-type heterogeneous catalyst with simple separation feature from the reaction mixture. Moreover, it exhibited excellent recyclability at least for 12 times, and a higher catalytic activity toward N-formylation.
Rostamnia, Sadegh,Doustkhah, Esmail
p. 317 - 324
(2015/11/28)

An efficient method for the synthesis of formamidine and formamide derivatives promoted by sulfonated rice husk ash (RHA-SO3H)
A mild, simple and efficient method has been developed for the promotion of the preparation of N,N′-diphenylformamidines from various aromatic amines and ethyl orthoformate using sulfonated rice husk ash (RHA-SO3H) solid acid catalyst. This reagent has also been used for the N-formylation of a variety of amines using formic acid under solvent-free conditions. The procedures gave the products in very short reaction times and good-to-high yields. Also this catalyst can be reused for five times without loss of its catalytic activity.
Seddighi, Mohadeseh,Shirini, Farhad,Mamaghani, Manouchehr
p. 433 - 439
(2015/02/05)

Preparation and catalytically study of metal-organic frameworks of amine/MIL-53 (Al) as a powerful option in the rapid N-formylation condensation in neat conditions
This paper reports on the preparation and application of amine/MIL-53 (Al) as highly active catalysts for the N-formylation reaction. These Al-MOFs were found to be an efficient, selective and waste-free green solid catalyst for the net condensation of amines and formic acid. The catalyst can be isolated from the reaction mixture and reused at least 6 times.
Rostamnia, Sadegh,Karimi, Ziba
p. 133 - 137
(2015/03/04)

Synthesis of selenazolopyridine derivatives with capability to induce apoptosis in human breast carcinoma MCF-7 cells through scavenge of intracellular ROS
A series of selenazolopyridine derivatives have been synthesized and characterized by X-ray diffraction, high resolution NMR and Mass spectrum. The in vitro anticancer activities of the synthetic compounds were screened against a panel of human cancer cell lines, human breast carcinoma MCF-7 cells, human liver carcinoma HepG2 cells and L02 normal cell line by MTT assay. By analyzing the structure-activity relationship among the synthetic compounds, it was found that 2-(phenylamino) selenazolo [5,4-b] pyridine, (PSeD, 7) had higher growth inhibitory effect on MCF-7 cells. The intracellular mechanism of cell death was evaluated by flow cytometric analysis and ROS assay, which revealed that PSeD could induce MCF-7 cells apoptosis by scavenging intracellular ROS. Taken together, we regard PSeD as an antioxidant which could inhibit cancer cell growth through induction of apoptosis.
Zhou, Meiyun,Ji, Shengbin,Wu, Zhaojun,Li, Yiqun,Zheng, Wenjie,Zhou, Hua,Chen, Tianfeng
p. 92 - 97
(2015/04/22)

The ortho effect on the acidic and alkaline hydrolysis of substituted formanilides
The kinetics of formanilides hydrolysis were determined under first-order conditions in hydrochloric acid (0.01-8 M, 20-60°C) and in hydroxide solutions (0.01-3 M, 25 and 40°C). Under acidic conditions, second-order specific acid catalytic constants were used to construct Hammett plots. The ortho effect was analyzed using the Fujita-Nishioka method. In alkaline solutions, hydrolysis displayed both first- and second-order dependence in the hydroxide concentration. The specific base catalytic constants were used to construct Hammett plots. Ortho effects were evaluated for the first-order dependence on the hydroxide concentration. Formanilide hydrolyzes in acidic solutions by specific acid catalysis, and the kinetic study results were consistent with the AAC2 mechanism. Ortho substitution led to a decrease in the rates of reaction due to steric inhibition of resonance, retardation due to steric bulk, and through space interactions. The primary hydrolytic pathway in alkaline solutions was consistent with a modified BAC2 mechanism. The Hammett plots for hydrolysis of meta- and para-substituted formanilides in 0.10 M sodium hydroxide solutions did not show substituent effects; however, ortho substitution led to a decrease in rate constants proportional to the steric bulk of the substituent.
Desai, Salil Dileep,Kirsch, Lee E.
p. 471 - 488
(2015/06/30)

H-β-zeolite catalyzed transamidation of carboxamides, phthalimide, formamides and thioamides with amines under neat conditions
Efficient transamidation of unactivated carboxamides, phthalimides, formamides and thioamides with amines under solvent-free conditions using H-β-zeolite as a green and recyclable heterogeneous catalyst is described. Easy work up, high purity of the products, recyclability and environmentally-friendly nature of the catalyst are the attractive features of the present methodology. This is the first report for the transamidation of thioamides under heterogeneous conditions.
Rao, Sadu Nageswara,Chandra Mohan, Darapaneni,Adimurthy, Subbarayappa
p. 95313 - 95317
(2015/11/24)

A Catalyst-Free Process for the Direct Oxidative Synthesis of Form-anilides from Arylamines and Aldehydes under Air Atmosphere
An efficient and catalyst-free process for the direct oxidative synthesis of formanilides from primary aromatic amines and aliphatic aldehydes has been developed under mild aerobic oxidation conditions. The isotope-labeling experiments indicated that the oxygen atom of the formanilide originated from dioxygen.
Qin, Yuancheng,Cheng, Yuanyuan,Luo, Xubiao,Li, Mingjun,Xie, Yu,Gao, Yunhua
supporting information
p. 1900 - 1904
(2015/08/06)

Gold-Catalyzed Reductive Transformation of Nitro Compounds Using Formic Acid: Mild, Efficient, and Versatile
Developing new efficient catalytic systems to convert abundant and renewable feedstocks into valuable products in a compact, flexible, and target-specific manner is of high importance in modern synthetic chemistry. Here, we describe a versatile set of mild catalytic conditions utilizing a single gold-based solid catalyst that enables the direct and additive-free preparation of four distinct and important amine derivatives (amines, formamides, benzimidazoles, and dimethlyated amines) from readily available formic acid (FA) and nitro starting materials with high level of chemoselectivity. By controlling the stoichiometry of the employed FA, which has attracted considerable interest in the area of sustainable chemistry because of its potential as an entirely renewable hydrogen carrier and as a versatile C1 source, a facile atom- and step-efficient transformation of nitro compounds can be realized in a modular fashion. Renewable formic acid as a flexible feedstock: A versatile heterogeneous gold-based catalytic system has been developed for the controlled, flexible, and target-specific reductive transformation of nitro compounds using stoichiometric equivalents of formic acid as a key starting material under mild and convenient conditions. The overall operational simplicity, high chemoselectivity, functional-group tolerance, and reusability of the catalyst make this approach an attractive and reliable tool for organic and process chemists.
Yu, Lei,Zhang, Qi,Li, Shu-Shuang,Huang, Jun,Liu, Yong-Mei,He, He-Yong,Cao, Yong
p. 3029 - 3035
(2015/09/28)

Effective Formylation of Amines with Carbon Dioxide and Diphenylsilane Catalyzed by Chelating bis(tzNHC) Rhodium Complexes
The reductive formylation of amines using CO2 and hydrosilanes is an attractive method for incorporating CO2 into valuable organic compounds. However, previous systems required either high catalyst loadings or high temperatures to achieve high efficiency, and the substrate scope was mostly limited to simple amines. To address these problems, a series of alkyl bridged chelating bis(NHC) rhodium complexes (NHC=N-heterocyclic carbene) have been synthesized and applied to the reductive formylation of amines using CO2 and Ph2SiH2. A rhodium-based bis(tzNHC) complex (tz=1,2,3-triazol-5-ylidene) was identified to be highly effective at a low catalyst loading and ambient temperature, and a wide substrate scope, including amines with reducible functional groups, were compatible. Beyond the norm: Rhodium complexes bearing a strong electron-donating bis(1,2,3-triazol-5-ylidene) ligand were found to be excellent catalysts for the reductive formylation of amines with CO2 and Ph2SiH2 at ambient temperature. The catalyst system possesses a broad substrate scope which tolerates a variety of reducible functional groups and is suitable for the synthesis of bioactive compounds. Tf=trifuoromethanesulfonyl.
Nguyen, Thanh V. Q.,Yoo, Woo-Jin,Kobayashi
supporting information
p. 9209 - 9212
(2015/08/06)

Br?nsted acidic ionic liquid supported on rice husk ash (RHA-[pmim]HSO4): A highly efficient and reusable catalyst for the formylation of amines and alcohols
In this work, rice husk ash (RHA), as a natural source of amorphous silica, was used as a support for the immobilization of 1-methyl-3-(trimethoxysilylpropyl)-imidazolium hydrogen sulfate. The immobilized acidic ionic liquid was characterized with a variety of techniques including infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and pH analysis. The catalytic performance of this heterogeneous ionic liquid was probed for the N-formylation of a variety of amines using formic acid under solvent free conditions. It is also useful for the formylation of benzylic alcohols. The procedure gave the products in excellent yields in very short reaction times. Also this catalyst can be reused ten times without loss of its catalytic activity.
Shirini, Farhad,Seddighi, Mohadeseh,Mamaghani, Manouchehr
p. 50631 - 50638
(2014/12/10)

Palladium-catalyzed C(sp2)-H arylation using formamide as a transformable directing group
A new process for the ortho arylation of formanilides through palladium-catalyzed C-H activation is described. Formamide is reported as a transformable directing group in the transition-metal-catalyzed C-H functionalization reaction. The resulting biarylformanilide products can be readily transformed to the corresponding biarylisocyanides or N-heterocycles.
Wan, Congqing,Zhao, Jiaji,Xu, Mingfang,Huang, Jinbo
p. 4751 - 4756
(2014/06/09)

Highly efficient N-formylation of amines with ammonium formate catalyzed by nano-Fe3O4 in PEG-400
A simple and efficient protocol for the formylation of amines with ammonium formate with excellent yields catalyzed by Fe3O4 nanoparticles in PEG-400 is described. Notably, this method shows excellent activity and chemoselectivity for the formylation of primary and secondary arylamines. Moreover, the nano-Fe3O4 catalyst and PEG-400 could be easily recovered and reused.
Wang, Zhao-Gang,Lu, Ming
p. 1234 - 1240
(2014/01/06)

A green protocol for the N-formylation of amines using molybdate sulfuric acid as a reusable solid catalyst
A novel and efficient method for the N-formylation of amines via the reaction of orthoformates and amines is developed. The reactions are mediated by a catalytic amount of molybdate sulfuric acid as a heterogeneous solid acid.
Karami, Bahador,Farahi, Mahnaz,Pam, Fariba
p. 6292 - 6296
(2015/02/19)

Synthesis and characterization of copper nanoparticles supported on reduced graphene oxide as a highly active and recyclable catalyst for the synthesis of formamides and primary amines
We report here the synthesis of reduced graphene oxide supported copper nanoparticles (rGO/Cu NPs) from copper (II) sulfate pentahydrate and graphite precursors using a simple protocol. The catalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) and energy dispersive X-ray spectroscopy (EDS). The rGO/Cu NPs is proved to be a useful heterogeneous catalyst in Cu-catalyzed formamidation and amination of arylboronic acids. The catalyst can be recovered by simple filtration from the reaction mixture and reused several times without significant loss of catalytic activity.
Fakhri, Parisa,Jaleh, Babak,Nasrollahzadeh, Mahmoud
p. 17 - 22
(2014/01/06)