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Method for preparing formamide compound by using MCOF to catalyze CO2 as carbon source at normal temperature and pressure
The invention provides a method for preparing a formamide compound by using MCOF to catalyze CO2 as a carbon source at normal temperature and pressure, and belongs to the technical field of chemistry and chemical engineering. Under the conditions of normal temperature and normal pressure, CO2 is used as a carbon source to realize N-formylation reaction of various amine substrates. The method has the advantages that the reaction system uses the metal ion-doped two-dimensional covalent organic framework MCOF as the catalyst, CO2 is reduced at normal temperature and normal pressure to provide acyl, high-pressure hydrogen and toxic CO are prevented from being used, and the reaction conditions are mild (normal temperature and normal pressure). According to the method for preparing the formamide, the greenhouse gas carbon dioxide serves as a carbon source, the cost is low, operation is easy, reaction conditions are mild (normal temperature and normal pressure), the yield of the prepared formamide product is excellent (99%), and a green synthesis method is provided for N-acylation reaction.
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Paragraph 0034

(2021/06/09)

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

Highly Efficient and Selective N-Formylation of Amines with CO2 and H2 Catalyzed by Porous Organometallic Polymers
The valorization of carbon dioxide (CO2) to fine chemicals is one of the most promising approaches for CO2 capture and utilization. Herein we demonstrated a series of porous organometallic polymers could be employed as highly efficient and recyclable catalysts for this purpose. Synergetic effects of specific surface area, iridium content, and CO2 adsorption capability are crucial to achieve excellent selectivity and yields towards N-formylation of diverse amines with CO2 and H2 under mild reaction conditions even at 20 ppm catalyst loading. Density functional theory calculations revealed not only a redox-neutral catalytic pathway but also a new plausible mechanism with the incorporation of the key intermediate formic acid via a proton-relay process. Remarkably, a record turnover number (TON=1.58×106) was achieved in the synthesis of N,N-dimethylformamide (DMF), and the solid catalysts can be reused up to 12 runs, highlighting their practical potential in industry.
Shen, Yajing,Zheng, Qingshu,Chen, Zhe-Ning,Wen, Daheng,Clark, James H.,Xu, Xin,Tu, Tao
supporting information
p. 4125 - 4132
(2021/01/12)

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

One-Pot Synthesis of Tertiary Amides from Organic Trichlorides through Oxygen Atom Incorporation from Air by Convergent Paired Electrolysis
A convergent paired electrolysis catalyzed by a B12 complex for the one-pot synthesis of a tertiary amide from organic trichlorides (R-CCl3) has been developed. Various readily available organic trichlorides, such as benzotrichloride and its derivatives, chloroform, dichlorodiphenyltrichloroethane (DDT), trichloro-2,2,2-trifluoroethane (CFC-113a), and trichloroacetonitrile (CNCCl3), were converted to amides in the presence of tertiary amines through oxygen incorporation from air at room temperature. The amide formation mechanism in the paired electrolysis, which was mediated by a cobalt complex, was proposed.
Luo, Zhongli,Imamura, Kenji,Shiota, Yoshihito,Yoshizawa, Kazunari,Hisaeda, Yoshio,Shimakoshi, Hisashi
p. 5983 - 5990
(2021/05/04)

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

Olefin functionalized IPr.HCl monomer as well as preparation method and application thereof
The invention relates to an olefin functionalized IPr.HCl monomer, a preparation method thereof, a method for preparing an N-heterocyclic carbene functionalized organic polymer (PS-IPr-x) by using the olefin functionalized IPr.HCl monomer, and application of the N-heterocyclic carbene functionalized organic polymer as a heterogeneous catalyst for catalyzing reduction N-formylation of carbon dioxide and amine. A heterogeneous catalyst is prepared by using cheap and easily available DVB as a polymerization cross-linking agent through an AIBN-initiated olefin polymerization method, and has the advantages of low preparation cost and simple preparation method. Meanwhile, the catalytic activity of the catalyst is obviously higher than that of reported catalysts, and the catalyst has a wide practical application prospect.
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(2021/06/21)

Method for preparing formamide compound by catalyzing carbon dioxide hydrogenation with porous material
The invention belongs to the technical field of organic synthesis and heterogeneous catalysis, and particularly relates to a method for preparing a formamide compound by catalyzing carbon dioxide hydrogenation through a porous material. The method comprises the following steps: by taking a porous organic metal polymer as a catalyst, reacting an amine compound with carbon dioxide and hydrogen in anair atmosphere to prepare the formamide compound. The method has the advantages of high reaction efficiency, good selectivity, mild conditions, economy, environmental protection, simple operation andthe like; wherein a solid metal polymer material with large specific surface area, strong carbon dioxide adsorption, hierarchical pore channel distribution and highly dispersed metal centers is designed and synthesized as a reaction catalyst by changing a cross-linked copolymer proportion; the catalyst is especially used for catalytic synthesis of fine chemical N, N-dimethylformamide (DMF), doesnot need any additional solvent, alkali or other additives, and is convenient for separation and purification of DMF. The catalyst can be recycled; no special equipment is needed in the reaction, thereaction operation is simple, and further industrial application is facilitated.
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Paragraph 0136-0139

(2020/06/16)

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

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

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

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

Copper catalyzed: N-formylation of α-silyl-substituted tertiary N-alkylamines by air
A site-selective method to prepare N-formyl amines efficiently that relies on the copper(i)-catalyzed oxidation of α-silyl-substituted tertiary N-alkylamines by air at room temperature is described. The oxidative protocol was shown to exhibit excellent functional group tolerance as it was applicable to a wide variety of amine substrates and a number of bioactive molecules and natural products. Moreover, it delinates a ligand-and additive-free amine oxidation process mediated by a low-cost metal salt with oxygen from air taking on the role of both the terminal oxidant and as part of the formylation reagent, which is unprecedented in copper catalysis. It also offers the first synthetic method that can selectively generate α-amino radical species as reactive intermediates from α-silylamines under non-photochemical reaction conditions.
Bruce, Lachlan David,Chan, Philip Wai Hong,Jin, Jianwen,Xia, Bo,Zhao, Yichao
supporting information
p. 5296 - 5302
(2020/09/17)

Process for Productions of Formamides and Acrylamides
This invention relates to performance chemicals field, it discloses a novel and green process for simultaneous productions of formamides as well as mono- and multi-functional acrylamides under very mild conditions and with high efficiency. These substances are widely useful as industrial solvents or raw materials, in particular acrylamides are important olefinically-unsaturated polymerizable monomers in photo-curing materials.
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(2020/02/27)

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

The synthesis of cyanoformamides via a CsF-promoted decyanation/oxidation cascade of 2-dialkylamino-malononitriles
A mild and efficient method for the synthesis of cyanoformamides from N,N-disubstituted aminomalononitriles with CsF as the promoter has been developed. This method features a wide substrate scope and high reaction efficiency, and will facilitate corresponding cyanoformamide-based biological studies and synthetic methodology development.
Lei, Lin-Sheng,Xue, Cao-Gen,Xu, Xue-Tao,Jin, Da-Ping,Wang, Shao-Hua,Bao, Wen,Liang, Huan,Zhang, Kun,Asiri, Abdullah M.
supporting information
p. 3723 - 3726
(2019/04/17)

Novel clamp metal complex and application thereof
The invention discloses a method for preparing a novel clamp-shaped complex and application of the novel clamp-shaped complex in the reaction of catalytic hydrogenation of carboxylic acid ester compounds to produce corresponding alcohols and reaction of carbon dioxide catalytic hydrogenation to form formamide compounds. Carboxylic acid esters and hydrogen as raw materials or carbon dioxide, hydrogen and amine compounds as raw materials are reacted in an organic solvent condition or a solvent-free condition in the presence of a transition metal complex as a catalyst to respectively form the corresponding alcohol compounds and/or corresponding formamide compounds. The method has the advantages of being high in reaction efficiency, good in selectivity, mild in conditions, economical, environmentally-friendly, and simple in operation, and has good promotion and application prospects.
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Paragraph 0250-0253

(2019/04/26)

Eco-friendly acetylcholine-carboxylate bio-ionic liquids for controllable: N-methylation and N-formylation using ambient CO2 at low temperatures
Catalytic fixation of CO2 to produce valuable fine chemicals is of great significance to develop a green and sustainable circulation of excessive carbon in the environment. Herein, a series of non-toxic, biodegradable and recyclable acetylcholine-carboxylate bio-ionic liquids with different cations and anions were simply synthesized for producing formamides and methylamines using atmospheric CO2 as a carbon source, and phenylsilane as a hydrogen donor. The selectivity toward products was tuned by altering the reaction temperature under solvent or solvent-free conditions. N-Methylamines (ca. 96% yield) were obtained in acetonitrile at 50 °C, while N-formamides (ca. 99% yield) were attained without a solvent at 30 °C. The established bio-ionic liquid catalytic system found a wide range of applicability in substrates and possessed a high potentiality in scale-up to gram-grade production. The developed catalytic system was fairly stable, which could be easily reused without an apparent loss of reactivity, possibly due to the strong electrostatic interactions between the cation and anion. The combination of experimental and computational results explicitly elucidated the reaction mechanism: PhSiH3 activated by a bio-IL was favorable for the formation of silyl formate from hydrosilylation of CO2, followed by a reaction with an amine to give an N-formamide, while an N-methylamine was formed by further hydrosilylation of the N-formamide.
Zhao, Wenfeng,Chi, Xiaoping,Li, Hu,He, Jian,Long, Jingxuan,Xu, Yufei,Yang, Song
supporting information
p. 567 - 577
(2019/02/14)

Ozone and ozone/vacuum-UV degradation of diethyl dithiocarbamate collector: Kinetics, mineralization, byproducts and pathways
The diethyl dithiocarbamate (DDC) collector, a precursor of toxic N-nitrosamines, is detected in flotation wastewaters usually at the ppm level. In this study, the O3 and O3/Vacuum-UV (O3/VUV) processes were compared to investigate the efficient removal of DDC with a low risk of N-nitrosamine formation. The results showed that 99.55% of DDC was removed at 20 min by O3/VUV, and the degradation rate constant was 3.99 times higher than that using O3-alone. The C, S and N mineralization extents of DDC using O3/VUV reached 36.36%, 62.69% and 79.76% at 90 min, respectively. O3/VUV achieved a much higher mineralization extent of DDC than O3-alone. After 90 min of degradation, O3/VUV achieved lower residual concentrations of CS2 and H2S, and released lower amounts of gaseous sulfur byproducts compared to O3-alone. The solid phase extraction and gas chromatography-mass spectrometry (SPE/GC-MS) analysis indicated that the main byproducts in O3/VUV degradation of DDC were amide compounds without the detection of N-nitrosamines. The avoidance of N-nitrosamine formation might be attributed to exposure of UV irradiation and enhanced formation of OH radicals in the O3/VUV system. The degradation pathways of DDC were proposed. This work indicated that O3/VUV was an efficient alternative treatment technique for the removal of DDC flotation collector with low risk of N-nitrosamine formation.
Fu, Pingfeng,Ma, Yanhong,Yang, Huifen,Li, Gen,Lin, Xiaofeng
p. 23579 - 23588
(2019/08/12)

Electrocatalytic Reduction of CO2 to Methanol by Iron Tetradentate Phosphine Complex Through Amidation Strategy
The iron complex of tetradentate tris[2-(diphenylphosphino) ethyl]phosphine (PP3), [Fe(PP3)(MeCN)2](BF4)2, was able to electrocatalytically reduce CO2 to formate with a Faradaic efficiency (FE) of approximately 97.3 % in acetonitrile. Upon addition of diethylamine as a cocatalyst, electrocatalytic reduction to methanol was achieved with an FE of 68.5 %, and other products were formamide and formate. A mechanistic study suggested that the [FeH(PP3)](BF4) hydride complex was the active species in the electrocatalysis. Added amine as cocatalyst could react with CO2 to form carbamate, which could then be reduced to formamide and further to methanol. By contrast, free CO2 could only be reduced to formate as the end-product.
Bi, Jiaojiao,Hou, Pengfei,Liu, Fang-Wei,Kang, Peng
p. 2195 - 2201
(2019/05/15)

Practical Catalytic Cleavage of C(sp3)?C(sp3) Bonds in Amines
The selective cleavage of thermodynamically stable C(sp3)?C(sp3) single bonds is rare compared to their ubiquitous formation. Herein, we describe a general methodology for such transformations using homogeneous copper-based catalysts in the presence of air. The utility of this novel methodology is demonstrated for Cα?Cβ bond scission in >70 amines with excellent functional group tolerance. This transformation establishes tertiary amines as a general synthon for amides and provides valuable possibilities for their scalable functionalization in, for example, natural products and bioactive molecules.
Li, Wu,Liu, Weiping,Leonard, David K.,Rabeah, Jabor,Junge, Kathrin,Brückner, Angelika,Beller, Matthias
supporting information
p. 10693 - 10697
(2019/07/09)

Polymer Meets Frustrated Lewis Pair: Second-Generation CO2-Responsive Nanosystem for Sustainable CO2 Conversion
Frustrated Lewis pairs (FLP), a couple comprising a sterically encumbered Lewis acid and Lewis base, can offer latent reactivity for activating inert gas molecules. However, their use as a platform for fabricating gas-responsive materials has not yet developed. Merging the FLP concept with polymers, we report a new generation CO2-responsive system, differing from the first-generation ones based on an acid–base equilibrium mechanism. Two complementary Lewis acidic and basic block copolymers, installing bulky borane- and phosphine-containing blocks, were built as the macromolecular FLP. They can bind CO2 to drive micellar formation, in which CO2 as a cross-linker bridges the block chains. This dative bonding endows the assembly with ultrafast response (2 can function as nanocatalysts for recyclable C1 catalysis, opening a new direction of sustainable CO2 conversion.
Chen, Liang,Liu, Renjie,Yan, Qiang
supporting information
p. 9336 - 9340
(2018/07/25)

Ru@PsIL-Catalyzed Synthesis of N-Formamides and Benzimidazole by using Carbon Dioxide and Dimethylamine Borane
This work reports the synthesis and characterization of ruthenium nanoparticles (Ru NPs) supported on polymeric ionic liquids (PILs). This catalyst shows high catalytic activity towards the N-formylation of amines and synthesis of benzimidazoles from 1,2-diamines and carbon dioxide (CO2) by reductive dehydrogenation of dimethylamine borane. This methodology shows excellent functional group tolerance with broad substrate scope towards the synthesis of N-formamides and benzimidazoles. Interestingly, this protocol also provides the tandem reduction of 2-nitroamines and CO2 to synthesize benzimidazoles. It was proposed that the ionic liquid phase of the polymer plays pivotal roles such as assisting the stabilization of nanoparticles electrostatically, providing an ionic environment, and controlling the easy access of the substrates/reagents to the active sites. The developed methodology utilizes CO2 as a C1 source and water/ethanol as a green solvent system. Additionally, the catalyst was found to be recyclable in nature and shows five consecutive recycling runs without significant loss in its activity.
Saptal, Vitthal B.,Sasaki, Takehiko,Bhanage, Bhalchandra M.
p. 2593 - 2600
(2018/04/30)

N-Formylation of Amines with CO2 and H2 by Using NHC–Iridium Coordination Assemblies as Solid Molecular Catalysts
One of the NHC–iridium coordination assemblies containing 1,5-cyclooctadiene (COD) and iodide ion has been demonstrated as robust, efficient, recyclable solid molecular catalyst for N-formylation of diverse primary and secondary amines with CO2 and H2 under mild reaction conditions. Remarkably, in the case of N,N-dimethylformamide production, even at 0.1 mol % catalyst loading under solvent-free conditions, the solid catalyst can be readily recovered by simply filtration and reused more than 10 runs without noticeable loss of activity.
Zhang, Yang,Wang, Jiaquan,Zhu, Haibo,Tu, Tao
supporting information
p. 3018 - 3021
(2018/09/06)

Synthesis of New Class of Copper(II) Complex-Based FeNi3/KCC-1 for the N-Formylation of Amines Using Dihydrogen and Carbon Dioxide
This study investigated the potential application of an efficient, easily recoverable, and reusable copper(II)-based catalyst bearing polyvinyl alcohol (PVA) immobilized on FeNi3/KCC-1/APTPOSS [FeNi3/KCC-1/APTPOSS/TCT/PVA/Cu(II)] magnetic nano-particles (MNPs) for the N-formylation of amines via CO2 hydrogenation. FeNi3/KCC-1/TCT/PVA/Cu(II) MNPs were thoroughly characterized by transmission electron microscopy, field emission-scanning electron microscopy, vibrating sample magnetometry, thermo-gravimetric analysis, inductively coupled plasma-mass spectrometry (ICP-MS), and the Brunauer, Emmett, and Teller method. After the reaction, only minor changes to the morphology of the catalyst recycled by the ICP-MS were evidenced, thus corroborating its robustness. Graphical Abstract: [Figure not available: see fulltext.]
Zhiani, Rahele,Saadati, Seyed Mahdi,Zahedifar, Mahboobeh,Sadeghzadeh, Seyed Mohsen
p. 2487 - 2500
(2018/07/05)

METHOD FOR PREPARING FORMAMIDE COMPOUND
Disclosed is a method for preparing a formamide compound, the method uses carbon dioxide, hydrogen and an amine compound as raw materials and a transition metal complex as a catalyst, and the reaction is carried out in an organic solvent or in the absence of a solvent to form a formamide compound. The method of the present invention is an effective method of chemical utilization of carbon dioxide, which has the advantages of high reaction efficiency, a good selectivity, mild conditions, economic and environmental protection, being simple and convenient to operate and the like, and has a good popularization and application prospect.
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Paragraph 0189-0190

(2018/02/28)

B(C6F5)3: a robust catalyst for the activation of CO2 and dimethylamine borane for the N-formylation reactions
In this work, B(C6F5)3 is utilized as an organocatalyst for the transition-metal-free N-formylation of amines using carbon dioxide (CO2) as a C1 source and dimethylamine borane (Me2NH·BH3) as a green hydrogen transfer source at 80 °C. Most reported works utilize silane and hydrogen for the N-formylation reactions using CO2 which have thus far been limited by low atom economy, high cost or the use of harsh reaction conditions. This catalytic protocol affords a broad range of formylated products in moderate to excellent yields under mild reaction conditions with a high TON and TOF. The bulky boron (B(C6F5)3) catalyst reacts with amines and forms a Frustrated Lewis Pair (FLP) and activates CO2 and Me2NH·BH3 molecules. Additionally, this boron catalyst shows high catalytic activity for the cyclization of o-phenylenediamines using CO2 and Me2NH·BH3 to synthesize benzimidazoles.
Saptal, Vitthal B.,Juneja, Gaurav,Bhanage, Bhalchandra M.
supporting information
p. 15847 - 15851
(2018/10/04)

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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(2018/11/03)

DBU-Catalyzed Selective N-Methylation and N-Formylation of Amines with CO2 and Polymethylhydrosiloxane
We describe herein an efficient organocatalytic system for the selective N-methylation and N-formylation of amines with carbon dioxide (CO2) as a sustainable C1 feedstock and polymethylhydrosiloxane (PMHS) as a cost-effectvie reducing reagent. High-yielding N-methylation products are obtained with low catalyst loading (1%) of DBU. Selective N-formylation of amines is achieved using the same catalytic system at a lower reaction temperature. (Figure presented.).
Li, Gang,Chen, Jie,Zhu, Dao-Yong,Chen, Ye,Xia, Ji-Bao
supporting information
p. 2364 - 2369
(2018/05/07)

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)

Preparation method of N,N-diethyl formamide
The invention discloses a preparation method of N,N-diethyl formamide. The N,N-diethyl formamide with the purity being more than 99.9 percent is obtained by taking formic acid and diethylamine as raw materials according to the molar ratio of the formic acid to the diethylamine being 1:1, using a Al2O3/VB1 composite catalyst system, removing excessive formic acid and catalyst and a trace amount of diethylamine from a liquid phase mixture after reaction, and performing reduced-pressure rectification in a rectification tower. According to the preparation method, a normal-pressure reactor, a distillation device and a rectification device are adopted and microwave heating is adopted, so that the reaction time is shortened, the diethylamine conversion rate is increased, the product purity is high, the production cost is low, operation is facilitated, and high-quality N,N-diethyl formamide can be synthesized quickly.
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Paragraph 0018-0023

(2017/11/04)

Preparation method of formamide compound
The invention provides a preparation method of a formamide compound. A preparation process of the preparation method comprises the following steps: uniformly mixing formic acid and an amine compound raw material selected from primary amine or secondary amine to prepare a homogeneous reaction system; raising the temperature of the homogeneous reaction system to 160 DEG C to 230 DEG C; decomposing the homogeneous reaction system to obtain carbon monoxide and enabling the carbon monoxide to participate in reaction; collecting a reaction product to obtain the formamide compound. The invention provides a novel technology for synthesizing the formamide compound through a heterogeneous method; a catalyst does not need to be used in a reaction process and an operation process is simple and controllable; the selectivity of the amine compound raw material is high.
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Paragraph 0048-0054

(2018/03/24)

Cooperative Catalytic Activation of Si?H Bonds: CO2-Based Synthesis of Formamides from Amines and Hydrosilanes under Mild Conditions
A simple cooperative catalytic system was successfully developed for the solvent-free N-formylation of amines with CO2 and hydrosilanes under ambient conditions, which was composed of a Zn(salen) catalyst and quaternary ammonium salt. These commercially available binary components activated the Si?H bonds effectively, owing to the intermolecular synergistic effect between Lewis base and transition metal center (LB–TM), and subsequently facilitated the insertion of CO2 to form the active silyl formats, thereby leading to excellent catalytic performance at a low catalyst loading. Furthermore, the bifunctional Zn(salen) complexes, with two imidazolium-based ionic-liquid (IL) units at the 3,3′-position of salen ligand, acted as intramolecularly cooperative catalysts, and the solvent-regulated separation resulted in facile catalyst recycling and reuse.
Luo, Rongchang,Lin, Xiaowei,Chen, Yaju,Zhang, Wuying,Zhou, Xiantai,Ji, Hongbing
p. 1224 - 1232
(2017/03/29)

Transformation of carbon dioxide into valuable chemicals over bifunctional metallosalen catalysts bearing quaternary phosphonium salts
The chemical transformation of CO2 under mild conditions remains a great challenge because of its exceptional kinetic and thermodynamic stability. Two important reactions in the transformation of CO2 are the N-formylation reaction of amines using hydrosilanes and CO2, and the cycloaddition of CO2 to epoxides. Here, we report the high efficiency of bifunctional metallosalen complexes bearing quaternary phosphonium salts in catalyzing both of these reactions under solvent-free, mild conditions without the need for co-catalysts. The catalysts' bifunctionality is attributed to an intramolecular cooperative process between the metal center and the halogen anion. Depending on the reaction, this activates CO2 by permitting either the synergistic activation of Si–H bond via metal–hydrogen coordinative bond (M–H) or the dual activation of epoxide via metal–oxygen coordinative bond (M–O). The one-component catalysts are also shown to be easily recovered and reused five times without significant loss of activity or selectivity. The current results are combined with previous work in the area to propose the relevant reaction mechanisms.
Zhang, Wuying,Luo, Rongchang,Xu, Qihang,Chen, Yaju,Lin, Xiaowei,Zhou, Xiantai,Ji, Hongbing
p. 736 - 744
(2017/04/24)

Bio-Inspired Mn(I) Complexes for the Hydrogenation of CO2 to Formate and Formamide
Developing new, efficient catalysts that contain Earth-abundant metals and simple, robust ligands for CO2 hydrogenation is important to create cost-effective processes of CO2 utilization. Inspired by nature, which utilizes an ortho-OH-substituted pyridine motif in Fe-containing hydrogenases, we developed a Mn complex with a simple N-donor ligand, 6,6′-dihydroxy-2,2′-bipyridine, that acts as an efficient catalyst for CO2 hydrogenation. Turnover numbers of 6250 for hydrogenation of CO2 to formate in the presence of DBU were achieved. Moreover, hydrogenation of CO2 to formamide was achieved in the presence of a secondary amine.
Dubey, Abhishek,Nencini, Luca,Fayzullin, Robert R.,Nervi, Carlo,Khusnutdinova, Julia R.
p. 3864 - 3868
(2017/06/23)

Metallosalen-Based Ionic Porous Polymers as Bifunctional Catalysts for the Conversion of CO2 into Valuable Chemicals
A series of new metallosalen-based ionic porous organic polymers (POPs) were synthesized for the first time using a simple unique strategy based on the free-radical copolymerization reaction. Various techniques were used to characterize the physicochemical properties of these catalysts. These well-designed materials endowed high surface area, hierarchical porous structures, and enhanced CO2/N2 adsorptive selectivity. Moreover, these POPs having both metal centers (Lewis acid) and ionic units (nucleophile) could serve as bifunctional catalysts in the catalytic conversion of CO2 into high value-added chemicals without any additional co-catalyst under mild and solvent-free conditions, for example, CO2/epoxides cycloaddition and Nformylation of amines from CO2 and hydrosilanes. The results demonstrated that the irregular porous structure was very favorable for the diffusion of substrates and products, and the microporous structural property resulted in the enrichment of CO2 near the catalytic centers in the CO2-involved transformations. Additionally, the superhydrophobic property could not only enhance the chemoselectivity of products but also promote the stability and recyclability of catalysts.
Luo, Rongchang,Chen, Yaju,He, Qian,Lin, Xiaowei,Xu, Qihang,He, Xiaohui,Zhang, Wuying,Zhou, Xiantai,Ji, Hongbing
p. 1526 - 1533
(2017/04/14)

Betaine Catalysis for Hierarchical Reduction of CO2 with Amines and Hydrosilane To Form Formamides, Aminals, and Methylamines
An efficient, sustainable organocatalyst, glycine betaine, was developed for the reductive functionalization of CO2 with amines and diphenylsilane. Methylamines and formamides were obtained in high yield by tuning the CO2 pressure and reaction temperature. Based on identification of the key intermediate, that is, the aminal, an alternative mechanism for methylation involving the C0 silyl acetal and aminal is proposed. Furthermore, reducing the CO2 amount afforded aminals with high yield and selectivity. Therefore, betaine catalysis affords products with a diversified energy content that is, formamides, aminals and methylamines, by hierarchical two-, four- and six-electron reduction, respectively, of CO2 coupled with C?N bond formation.
Liu, Xiao-Fang,Li, Xiao-Ya,Qiao, Chang,Fu, Hong-Chen,He, Liang-Nian
supporting information
p. 7425 - 7429
(2017/06/13)

Highly productive CO2 hydrogenation to methanol-a tandem catalytic approach: Via amide intermediates
A new system for CO2 reduction to methanol has been demonstrated using homogeneous ruthenium catalysts with a range of amine auxiliaries. Modification of this amine has a profound effect on the yield and selectivity of the reaction. A TON of 8900 and TOF of 4500 h-1 is achieved using a [RuCl2(Ph2PCH2CH2NHMe)2] catalyst with a diisopropylamine auxiliary.
Everett,Wass
supporting information
p. 9502 - 9504
(2017/09/01)

Ru/ceria-catalyzed direct formylation of amines and CO to produce formamides
We herein report a new strategy of directly converting amines and CO to formamides with 100% atom utilization efficiency. It is suitable for up to 25 amine substrates with no additives. Ru/ceria is found to be an excellent catalyst for this reaction due the efficient co-activation of CO and amine on Ru species.
Wang, Yehong,Zhang, Jian,Chen, Haijun,Zhang, Zhixin,Zhang, Chaofeng,Li, Mingrun,Wang, Feng
p. 88 - 92
(2017/01/24)

Preparation method for methanamide
The invention relates to a method for preparing methanamide compounds through carbonylation of amine. The method employs primary amine or secondary amine and carbon monoxide (CO) as reactants and prepares the methanamide compounds through a CO-inserted carbonylation reaction under the catalysis of ruthenium-loaded hydroxyapatite (Ru/HAP). Reaction conditions are that the reaction is carried out in a tank reactor under stirring; CO pouring pressure is 0.5 to 5.0 MPa; and reaction temperature is 100 to 200 DEG C. The method has the characteristics that (1) the reaction has 100% atom economy and is free of generation of any by-product; (2) the ruthenium-loaded hydroxyapatite is used as a catalyst, the catalyst is simple to prepare and efficiently catalyzes the reaction, and the yield of the methanamide compounds can reach 80% or above; and (3) the catalyst has good stability and can be cyclically used four times or more.
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Paragraph 0029; 0030

(2017/05/26)

Method for preparing methallyl alcohol and amide simultaneously
A method for preparing methallyl alcohol and amide simultaneously is characterized in that methylallyl carboxylate taken as a raw material and an amine compound taken as an ammonolysis agent react under the action of a catalyst to produce methallyl alcohol and an amide compound. The methylallyl carboxylate and the amine compound taken as the ammonolysis agent are firstly adopted, and the methallyl alcohol and the amide compound are obtained under the action of the catalyst. The reaction process is a bulk reaction, no solvents are added, almost no wastewater or salt are produced, and byproduct methyl allyl ether is not produced; the defect that a large number of wastewater is produced through hydrolysis is overcome due to adoption of ammonolysis, the methallyl alcohol and the amide compound are coproduced directly by use of ammonoysis, coupling production is realized, and the cost is reduced.
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Paragraph 0032-0033

(2017/11/29)

Cu-Catalyzed Synthesis of 3-Formyl Imidazo[1,2-a]pyridines and Imidazo[1,2-a]pyrimidines by Employing Ethyl Tertiary Amines as Carbon Sources
A highly efficient synthesis of 3-formyl imidazo[1,2-a]pyridine and imidazo[1,2-a]pyrimidine, under Cu-catalyzed aerobic oxidative conditions and by utilizing ethyl tertiary amines as carbon sources, is disclosed. A novel activation mode of ethyl tertiary amines in which simultaneous selective cleavage of C-C bond and C-N bond of ethyl group with molecular oxygen as terminal oxidant in this one-pot protocol is reported for the first time. This reaction features broad substrate scope, good functional group tolerance, as well as diversified and valuable products.
Rao, Changqing,Mai, Shaoyu,Song, Qiuling
supporting information
p. 4726 - 4729
(2017/09/22)

Iron-Catalyzed Amide Formation from the Dehydrogenative Coupling of Alcohols and Secondary Amines
The five-coordinate iron(II) hydride complex (iPrPNP)Fe(H)(CO) (iPrPNP = N[CH2CH2(PiPr2)]2) selectively catalyzes the dehydrogenative intermolecular coupling of alcohols and secondary amines to form tertiary amides. This is the most productive base-metal catalyst for dehydrogenative amidation reported to date, in some cases achieving up to 600 turnovers. The catalyst works well for sterically undemanding amines and alcohols or cyclic substrates and is particularly effective in the synthesis of formamides from methanol. However, the catalyst performance declines rapidly with the incorporation of large substituents on the amine or alcohol substrate. Variable-temperature NMR spectroscopic studies suggest that the catalyst resting state is an off-cycle iron(II) methoxide species, (iPrPN(H)P)Fe(H)(OCH3)(CO), resulting from addition of methanol across the Fe-N bond of (iPrPNP)Fe(H)(CO). This reversibly formed iron(II) methoxide complex is favored at mild temperatures but eliminates methanol upon heating.
Lane, Elizabeth M.,Uttley, Katherine B.,Hazari, Nilay,Bernskoetter, Wesley
supporting information
p. 2020 - 2025
(2017/06/13)

A tertiary amine oxidation cracking method of preparing carboxamide
The invention provides a method for preparing formamide through tertiary amine oxicracking. According to the method, tertiary amine serves as a substrate, air or oxygen serves as an oxygen source, and oxicracking occurs on the tertiary amine under the action of a catalyst to generate the formamide. The method is high in oxidation efficiency and product yield and economical and environmentally friendly by taking the air or oxygen as the oxygen source and has a very good application prospect.
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Paragraph 0014; 0023

(2017/08/26)

Photocatalytic N-formylation of amines via a reductive quenching cycle in the presence of air
Photochemical N-formylation of amines was performed under simple and mild reaction conditions. Amines are common electron donors in reductive photocatalysis, which then typically decompose after donating an electron to the photocatalyst. We have found that these oxidized amines can be utilized to give N-formamides in the presence of air without additional formylating agents. The reaction proceeds via the in situ formation of enamines. Oxygen (air) is necessary for the reaction to occur as it regenerates the photocatalyst forming superoxide radical anions as crucial intermediates involved in the reaction.
Ghosh, Tamal,Das, Amrita,K?nig, Burkhard
supporting information
p. 2536 - 2540
(2017/04/03)

Preparation method of N-formamide compound
The invention discloses a preparation method of an N-formamide compound. The preparation method includes the steps that carbon dioxide and organic amine serve as raw materials, hydrogen-containing silane is added to serve as a reducing agent, a 0.1-1.0mol% salen type metal complex serve as a catalyst, and an N-formamide organic compound is synthesized at the pressure of 0.1-5.0 MPa and the temperature of 25-100 DEG C with a cocatalyst added or not; after the reaction is finished, an organic solvent is added, centrifugation is carried out, the catalyst is separated out, the solvent is removed from supernatant liquid through rotary evaporation, and then the N-formamide compound is obtained. The preparation method has the advantages that the reaction conditions are mild, it is unnecessary to add any organic solvent, operation is easy, catalytic activity is high, and substrate compatibility is good, and the preparation method accords with the environment-friendly synthesis process and is suitable for industrial production. Besides, the catalytic system can be conveniently separated from the reaction system by adding the solvent, and the catalyst can be recycled.
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Paragraph 0050; 0051; 0052; 0053

(2017/04/28)

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
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.
p. 4872 - 4881
(2016/07/07)

An Efficient Protocol for Formylation of Amines Using Carbon Dioxide and PMHS under Transition-Metal-Free Conditions
A highly efficient, green and simple base catalytic system was investigated for the formylation of amines using CO2 and PMHS [poly(methylhydrosiloxane)] under mild reaction conditions. This reaction proceeds smoothly without additives and furnishes the corresponding N-formylated products from both the 1° and the 2° aliphatic as well as aromatic amines in good to excellent yields.
Nale, Deepak B.,Bhanage, Bhalchandra M.
p. 1413 - 1417
(2016/05/24)

Fluoride-Catalyzed Methylation of Amines by Reductive Functionalization of CO2with Hydrosilanes
An effective and inexpensive organocatalyst tetrabutylammonium fluoride (TBAF) was developed for the reductive functionalization of CO2with amines to selectively afford formamides or methylamines by employing hydrosilanes. Hydrosilanes with different substituents show discriminatory reducing activity. Thus, the formation of formamides and further reduction products, that is, methylamines could be controlled by elegantly tuning hydrosilane types. Formamides were obtained exclusively under an atmospheric pressure of CO2with triethoxysilane. Using phenylsilane as a reductant, methylamines were attained with up to 99 % yield at 50 °C coupled to a complete deoxygenation of CO2. The crucial intermediate silyl formate in the formylation step was identified and thereby a tentative mechanism involving the fluoride-promoted hydride transfer from the hydrosilane to CO2/formamide was proposed. Striking features of this metal-free protocol are formylation and methylation of amines by reductive functionalization of CO2with hydrosilanes and mild reaction conditions.
Liu, Xiao-Fang,Ma, Ran,Qiao, Chang,Cao, Han,He, Liang-Nian
p. 16489 - 16493
(2016/11/09)

Solid poly-N-heterocyclic carbene catalyzed CO2 reduction with hydrosilanes
The utility of solid poly-N-heterocyclic carbene (poly-NHC) materials as organocatalysts for carbon dioxide reduction was studied. These poly-NHC particles were demonstrated to be useful as heterogeneous organocatalysts for the reduction of carbon dioxide to methanol and for the formylation of N–H bonds with hydrosilanes as a hydride donor. These solid catalysts could potentially be useful in large-scale syntheses due to the ease of catalyst recycle and reuse, providing cost savings and environmental sustainability in the long run.
Riduan, Siti Nurhanna,Ying, Jackie Y.,Zhang, Yugen
p. 46 - 51
(2016/11/11)