- Metalized Carbon Nitrides for Efficient Catalytic Functionalization of CO2
-
As an effective approach toward sustainability and global carbon balance, the reductive conversion of CO2 into value-added chemicals is of considerable significance. Here, by simply calcining the mixture of NH4SCN and KCl in an air atmosphere, potassium dopants and negatively charged electron-rich centers are simultaneously introduced into carbon nitride materials via a metalation engineering strategy. The resultant metalized catalysts with deprotonated imide sites and doped potassium ions demonstrate much-enhanced activity for catalyzing CO2 reductive hydrosilylation with excellent conversion and >90% selectivity, whereas the pristine carbon nitride catalyst shows only negligible activity. Both experimental and theoretical results reveal the crucial role of the negatively charged electron-rich centers and potassium dopants in tailoring the energy band positions and electronic structure for the efficient donor-acceptor interaction and much increased driving force for CO2 reduction. The present work offers molecular-level insights into the boosted CO2 reduction activity via engineering the electronic structure of the metalized carbon nitride catalyst and reducing the energy offset between frontier molecular orbitals of CO2 and the catalyst, which can provide a conceptual guide for further development of efficient catalytic CO2 reduction systems.
- Cheng, Jiajia,Hou, Yuchen,Lian, Kangkang,Xiao, Hongxiang,Lin, Sen,Wang, Xinchen
-
p. 1797 - 1808
(2022/02/07)
-
- Additive-free selective methylation of secondary amines with formic acid over a Pd/In2O3 catalyst
-
Formic acid is used as the sole carbon and hydrogen source in the methylation of aromatic and aliphatic amines to methylamines. The reaction proceeds via a formylation/transfer hydrogenation pathway over a solid Pd/In2O3 catalyst without the need for any additive.
- Benaissa, Idir,Cantat, Thibault,Genre, Caroline,Godou, Timothé,Pinault, Mathieu
-
-
- 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.
- -
-
Paragraph 0032
(2021/06/09)
-
- Preparation method of formamide compound
-
The invention belongs to CO. 2 The invention relates to the technical field of activation conversion and related chemistry, and provides a preparation method of a formamide compound, which uses carbon dioxide. The amide compound and phenylsilane are used as raw materials, and the formamide compound is synthesized under the action of the nano porous palladium catalyst. The invention mainly provides a novel simple catalytic system and utilizes CO. 2 C1 The catalytic system has the advantages of mild reaction conditions, simple experiment operation, good functional group compatibility and the like. Because carbon dioxide is abundant, cheap and easily available and renewable C1 , The invention has great application value and social economic benefits.
- -
-
Paragraph 0039-0042
(2021/10/27)
-
- Catalyst freeN-formylation of aromatic and aliphatic amines exploiting reductive formylation of CO2using NaBH4
-
Herein, we report a sustainable approach forN-formylation of aromatic as well as aliphatic amines using sodium borohydride and carbon dioxide gas. The developed approach is catalyst free, and does not need pressure or a specialized reaction assembly. The reductive formylation of CO2with sodium borohydride generates formoxy borohydride speciesin situ, as confirmed by1H and11B NMR spectroscopy. Thein situformation of formoxy borohydride species is prominent in formamide based solvents and is critical for the success of theN-formylation reactions. The formoxy borohydride is also found to promote transamidation reactions as a competitive pathway along with reductive functionalization of CO2with amine leading toN-formylation of amines.
- Kumar, Arun,Kumar, Yashwant,Mahajan, Dinesh,Sharma, Nidhi,Sharma, Pankaj
-
p. 25777 - 25787
(2021/08/05)
-
- Recyclable Oxofluorovanadate-Catalyzed Formylation of Amines by Reductive Functionalization of CO2 with Hydrosilanes
-
An efficient method has been developed for the reductive amination of CO2 by using readily available and recyclable oxofluorovanadates as catalysts. Various amines are transformed into the desired N-formylated products in moderate to excellent yields at room temperature in the presence of phenylsilane. Mechanistic studies based on in situ infrared spectroscopy suggest a reaction pathway initiated through F?Si interactions. The activated phenylsilane allows for CO2 insertion to produce phenylsilyl formate, which undergoes attack by the amine to generate the target product.
- Wu, Shanxuan,Huang, Zijun,Jiang, Xiaolin,Yan, Fachao,Li, Yuehui,Du, Chen-Xia
-
p. 1763 - 1766
(2021/03/01)
-
- Immobilized Zn(OAc)2on bipyridine-based periodic mesoporous organosilica for N -formylation of amines with CO2and hydrosilanes
-
Zinc acetate (Zn(OAc)2) was successfully immobilized on a bipyridine-based periodic mesoporous organosilica (BPy-PMO-TMS), as confirmed by solid-state NMR and energy-dispersive X-ray spectroscopies, X-ray diffractometry, and nitrogen adsorption/desorption isotherm analyses. The immobilized Zn complex, Zn(OAc)2(BPy-PMO-TMS), exhibited good catalytic activity during the N-formylations of amines and amides with CO2 and PhSiH3 to produce the corresponding formamides. Zn(OAc)2(BPy-PMO-TMS) with a lower Zn loading was found to exhibit higher catalytic activity.
- Lin, Xiao-Tao,Matsumoto, Kazuhiro,Maegawa, Yoshifumi,Takeuchi, Katsuhiko,Fukaya, Norihisa,Sato, Kazuhiko,Inagaki, Shinji,Choi, Jun-Chul
-
supporting information
p. 9501 - 9505
(2021/06/14)
-
- Borane-Trimethylamine Complex as a Reducing Agent for Selective Methylation and Formylation of Amines with CO2
-
We report herein that a borane-trimethylamine complex worked as an efficient reducing agent for the selective methylation and formylation of amines with 1 atm CO2 under metal-free conditions. 6-Amino-2-picoline serves as a highly efficient catalyst for the methylation of various secondary amines, whereas in its absence, the formylation of primary and secondary amines was achieved in high yield with high chemoselectivity. Mechanistic studies suggest that the 6-amino-2-picoline-borane catalytic system operates like an intramolecular frustrated Lewis pair to activate CO2.
- Zhang, Yanmeng,Zhang, He,Gao, Ke
-
supporting information
p. 8282 - 8286
(2021/10/25)
-
- Ionization of Porous Hypercrosslinked Polymers for Catalyzing Room-Temperature CO2 Reduction via Formamides Synthesis
-
Porous materials with heterogeneous nature occupy a pivotal position in the chemical industry. This work described a facile pre- and post-synthetic approach to modify porous hypercrosslinked polymer with quaternary ammonium bromide, rendering it as efficient catalyst for CO2 conversion. The as-prepared porous ionic polymer (PiP@QA) displayed an improved specific surface area of 301 m2·g?1 with hierarchically porous structure, good selective adsorption of CO2, as well as high ion density. Accordingly, PiP@QA catalyst exhibited excellent catalytic performances for the solvent-free synthesis of various formamides from CO2, amines and phenylsilane under 35?°C and 0.5?MPa. We speculated that the superior catalytic efficiency and broad substrate scope of this catalyst could be resulted from the synergistic effect of flexible ionic sites with unique nanoporous channel that might increase the collision probability of reactants and active sites as well as enhance the diffusion of reactants and products during the reaction process. With the good reusability, PiP@QA was also available for the efficient conversion of simulated flue gas (15% CO2 in N2, v/v) into target formamides with quantitative selectivity at room temperature, which further highlighted its industrial application potential in chemical recycling the real-word CO2 to valuable products. Graphic Abstract: [Figure not available: see fulltext.].
- Ren, Qinggang,Chen, Yaju,Qiu, Yongjian,Tao, Leiming,Ji, Hongbing
-
p. 2919 - 2927
(2021/02/01)
-
- Study on the mild, rapid and selective difluorocarbene-mediated triclassification of iododifluoroacetophenone with secondary amines and tree model for product classification
-
Difluorocarbene is a very active and widely used intermediate in organic synthesis. In this work, a room temperature difluorocarbene-mediated triclassification reaction of iododifluoroacetophenone (2) and secondary amines with mild condition, short reaction time (only 10 min) and high selectivity had been studied, which produced one of the following three substances: N-CF2H derivatives (up to 87% yield), formamides (82–89% yield) or the recycled starting secondary amines. This phenomenon was related to the structural stability of the corresponding products. If unstable, it would be hydrolyzed to formamides first, and then further hydrolyzed to starting amines. Based on the geometric structure of the raw materials, the corresponding prediction tree model was established, which provided guidance for the further application of difluoromethylation of Vemurafenib (1ee) and AZD9291 (1ff).
- Chen, Xiu-Ping,Han, Jie,Hu, Yin-Jie,Li, Yun-Fang,Wang, Xiang-Cong,Ran, Jian-Xiong,Wang, Zhong-Hua,Wu, Fan-Hong
-
-
- 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)
-
- Zinc Powder Catalysed Formylation and Urealation of Amines Using CO2 as a C1 Building Block?
-
Transformation of CO2 into valuable organic compounds catalysed by cheap and biocompatible metal catalysts is one of important topics of current organic synthesis and catalysis. Herein, we report the zinc powder catalysed formylation and urealation of amines with CO2 and (EtO)3SiH under solvent free condition. Using 2 molpercent zinc powder as the catalyst, a series of secondary amines, both the aromatic ones and the aliphatic ones, can be formylated into formamides. When primary aromatic amines were used as the substrates, the reactions produce urea derivatives. The electronic and steric effects from the substrates on the formylation and urealation reactions were observed and discussed. The recovery and reusability of zinc powder were investigated, showing the zinc powder can be reused in the formylation reaction without loss of catalytic activity. The analysis on the reactants/products mixture after filtering out the zinc powder showed the zinc concentration in the mixture is low to 1 ppm. The pathways for the formylation and urealation of amines with this catalytic system were also investigated, and related to the different substrates.
- Du, Chongyang,Chen, Yaofeng
-
p. 1057 - 1064
(2020/06/30)
-
- Catalyst-free selective: N -formylation and N -methylation of amines using CO2 as a sustainable C1 source
-
We herein describe catalyst-free selective N-formylation and N-methylation of amines using CO2 as a sustainable C1 source. By tuning the reaction solvent and temperature, the selective synthesis of formamides and methylamines is achieved in good to excellent yields using sodium borohydride (NaBH4) as a sustainable reductant.
- Zou, Qizhuang,Long, Guangcai,Zhao, Tianxiang,Hu, Xingbang
-
supporting information
p. 1134 - 1138
(2020/03/11)
-
- Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
-
We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.
- Du, Chen-Xia,Huang, Zijun,Jiang, Xiaolin,Li, Yuehui,Makha, Mohamed,Wang, Fang,Zhao, Dongmei
-
supporting information
p. 5317 - 5324
(2020/09/17)
-
- Selective: N-formylation/N-methylation of amines and N-formylation of amides and carbamates with carbon dioxide and hydrosilanes: Promotion of the basic counter anions of the zinc catalyst
-
A catalyst composed of commercially available Zn(OAc)2 and 1,10-phenanthroline (phen) was effective in the N-formylation/N-methylation of amines using CO2 as the C1 source in the presence of hydrosilanes. An equimolar reaction of N-methylaniline with PhSiH3 under a CO2 atmosphere yielded the N-formylation product in 92% yield at 25 °C. Scale-up of the reaction using 10 mmol substrate was also successful in affording the desired product in 83% yield (1.1 g). This catalyst exhibits a high thermal stability and a turnover number (TON) of 385000 at 150 °C. In addition, the reaction of N-methylaniline in the presence of excess Ph2SiH2 produced N,N-dimethylaniline. Furthermore, our catalytic protocol was developed for the N-formylation of amides and carbamates, which have smaller pKa values and lower reactivities than the corresponding amines. The present Zn(OAc)2/phen catalyst was found to show versatility in the conversion of CO2 and amines into several functionalized organic chemicals under mild conditions. We propose that the basic counter anion (i.e., the acetate) of the catalyst activates both the Si-H and N-H bonds.
- Zhang, Qiao,Lin, Xiao-Tao,Fukaya, Norihisa,Fujitani, Tadahiro,Sato, Kazuhiko,Choi, Jun-Chul
-
supporting information
p. 8414 - 8422
(2020/12/29)
-
- 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)
-
- Synthesis of silyl formates, formamides, and aldehydesviasolvent-free organocatalytic hydrosilylation of CO2
-
Carbon dioxide (CO2) was used as a C1 source to prepare silyl formates, formamides, and aldehydes. Tetrabutylammonium acetate (TBAA) catalyzed the solvent-freeN-formylation of amines with CO2and hydrosilane to give formamides including Weinreb formamide, Me(MeO)NCHO, which was successively converted into aldehydes by one-pot reactions with Grignard reagents.
- Ema, Tadashi,Hasegawa, Jun-Ya,Hiyoshi, Mahoko,Murata, Takumi,Ratanasak, Manussada
-
supporting information
p. 5783 - 5786
(2020/06/03)
-
- Alkyl-substituted ethyl acetate-based guanidine ionic liquid as well as preparation and application thereof
-
The invention discloses alkyl-substituted ethyl acetate-based guanidine ionic liquid as well as preparation and application thereof, which are characterized in that tetramethylguanidine and 2-bromo ester are ionized to obtain alkyl-substituted ethyl acetate-based guanidine ionic liquid, and the alkyl-substituted ethyl acetate-based guanidine ionic liquid is applied as a catalyst to formylation and methylation reactions of carbon dioxide, N-methylaniline and derivatives of the N-methylaniline to selectively generate N-methylformylaniline or N, N-dimethylaniline and derivatives thereof. Compared with the prior art, the alkyl-substituted ethyl acetate-based guanidine ionic liquid has the advantages of good catalytic performance, mild reaction conditions, simple post-treatment, simple synthesis, low cost, greenness and high efficiency, avoids the use of a large amount of organic solvents when being used as a solvent and a catalyst at the same time, and has important meanings in the research of medicinal chemistry and medical intermediate compounds.
- -
-
Paragraph 0042-0045
(2020/07/21)
-
- Highly Efficient Binuclear Copper-catalyzed Oxidation of N,N-Dimethylanilines with O2
-
A binuclear copper-salicylate complex, [Cu(Sal)2(NCMe)]2 (Sal=salicylate), was found to be an active catalyst for the oxidation of N,N-dimethylanilines by O2, affording the corresponding N-methyl-N-phenylformamides as major products. The reactions were carried out with a O2 balloon and the S/C (substrate/catalyst ratio) of the model reaction could be up to 1×105, providing a practical and highly efficient catalytic protocol for accessing N-methyl-N-phenylformamides.
- Liu, Yuxia,Yan, Yonggang,Xue, Dong,Wang, Zhongfu,Xiao, Jianliang,Wang, Chao
-
p. 2221 - 2225
(2020/03/23)
-
- Ligand-protected Au4Ru2and Au5Ru2nanoclusters: Distinct structures and implications for site-cooperation catalysis
-
We report two ligand-protected Au4Ru2 and Au5Ru2 nanoclusters with distinct atomic-packing modes and electronic structures, both of which act as ideal model catalysts for identifying the catalytically active sites of catalysts on the nanoclusters. Au5Ru2 exhibits superior catalytic performances to Au4Ru2 for N-methylation of N-methylaniline to N-methylformanili, which is likely due to the site-cooperation catalysis of Au5Ru2. This journal is
- Sun, Yongnan,Yang, Dan,Zhang, Yuying,Hu, Weigang,Cheng, Xinglian,Liu, Xu,Chen, Mingyang,Zhu, Yan
-
supporting information
p. 12833 - 12836
(2020/11/02)
-
- Iron-Catalyzed Selective N-Methylation and N-Formylation of Amines with CO2
-
We herein describe an efficient iron-catalyzed selective N-methylation and N-formylation of amines with CO2 and silane using mono-phosphine as ligand. With commercially available [CpFe(CO)2]2 as catalyst, Fe-catalyzed methylation of amines was achieved with triphenylphosphine as a ligand. Using tributylphosphine as a ligand, Fe-catalyzed formylation of amines was realized at a lower temperature. The method was successfully applied in the late-stage methylation and formylation of drug molecules containing amine moiety. (Figure presented.).
- Li, Wen-Duo,Zhu, Dao-Yong,Li, Gang,Chen, Jie,Xia, Ji-Bao
-
supporting information
p. 5098 - 5104
(2019/11/03)
-
- Mn-Catalyzed Selective Double and Mono-N-Formylation and N-Methylation of Amines by using CO2
-
Functionalization of amines by using CO2 is of fundamental importance considering the abundance of amines and CO2. In this context, the catalytic formylation and methylation of amines represent convenient and successful protocols for selective CO2 utilization as a C1 building block. This study represents the first example of selective catalytic double N-formylation of aryl amines by using a dinuclear Mn complex in the presence of phenylsilane. This robust system also allows for selective formylation and methylation of amines under a range of conditions.
- Huang, Zijun,Jiang, Xiaolin,Zhou, Shaofang,Yang, Peiju,Du, Chen-Xia,Li, Yuehui
-
p. 3054 - 3059
(2019/04/10)
-
- 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)
-
- Unexpected Macrocyclic Multinuclear Zinc and Nickel Complexes that Function as Multitasking Catalysts for CO2 Fixations
-
Unique self-assembled macrocyclic multinuclear ZnII and NiII complexes with binaphthyl-bipyridyl ligands (L) were synthesized. X-ray analysis revealed that these complexes consisted of an outer ring (Zn3L3 or Ni3L3) and an inner core (Zn2 or Ni). In the ZnII complex, the inner Zn2 part rotated rapidly inside the outer ring in solution on an NMR timescale. These complexes exhibited dual catalytic activities for CO2 fixations: synthesis of cyclic carbonates from epoxides and CO2 and temperature-switched N-formylation/N-methylation of amines with CO2 and hydrosilane.
- Takaishi, Kazuto,Nath, Bikash Dev,Yamada, Yuya,Kosugi, Hiroyasu,Ema, Tadashi
-
supporting information
p. 9984 - 9988
(2019/06/24)
-
- Air-tolerant direct reductive N-methylation of amines using formic acid via simple inorganic base catalysis
-
The construction of N-methyl amine moieties is an important reaction that has found numerous applications. Development of new methylation agents that are more environmentally benign than classical agents, such as iodomethane and methyl sulfate, is still highly desirable. Herein, we report a convenient protocol for direct reductive N-methylation of amines using formic acid as the methylation agent via simple inorganic base catalysis. The present protocol operates under transition-metal-free and air-tolerant conditions. Both the catalyst, K2HPO4, and the reductant, polymethylhydrosiloxane (PMHS), are cheap and easily separable from the crude reaction product mixture. Mechanistic investigations suggest that the reaction occur through the formation of an acetal intermediate followed by the C–N bond formation.
- Huang, Yan,Deng, Wei,Lin, Bo-Lin
-
supporting information
(2019/05/29)
-
- Biomass-derived N-doped porous carbon: An efficient metal-free catalyst for methylation of amines with CO2
-
Developing green, efficient, and low-cost catalysts for methylation of N-H by using CO2 as the C1 resource is highly desired yet remains a significant challenge. Herein, N-doped porous carbons (NPCs) were designed, synthesized, and proved to be an excellent metal-free catalyst for CO2-participated methylation conversion. NPCs were prepared via the pyrolysis of a mixture of tannic acid and urea. Both theoretical calculation and experiment demonstrate that the N species especially pyridinic N and pyrrolic N within NPCs can work as Lewis basic sites for attacking CO2 to weaken the CO bonds and lower the molecule conversion barrier, facilitating the subsequent methylation of N-H to produce, for example, N,N-dimethylaniline. Besides, the unique porous structure can enrich CO2 and accelerate mass transfer, synergistically promoting the conversion of CO2. The optimized NPC(1/5) catalyst, integrating the porous structure and strong Lewis basicity, exhibits excellent catalytic activity for CO2-based methylation reaction under mild conditions (1 bar CO2, 75 °C). Our work, for the first time, demonstrates the feasibility of using NPCs to catalyze the methylation of amino compounds to produce N,N-dimethylamine by exploiting CO2 as the C1 resource.
- Tang, Feiying,Wang, Liqiang,Liu, You-Nian
-
supporting information
p. 6252 - 6257
(2019/12/03)
-
- 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)
-
- An efficient method for the N-formylation of amines under catalyst- and additive-free conditions
-
A simple catalyst- and additive-free method for the N-formylation of amines has been developed. The advantages of this protocol include a wide range of functional group tolerance, high efficiency and a lack of required extra promoters under mild conditions. This convenient strategy will provide a facile synthesis towards N-formamide natural products and pharmaceutical derivatives. A mechanism that involves difluorocarbene is proposed for this reaction.
- Xu, Zhuo-Wei,Xu, Wen-Yi,Pei, Xiao-Jun,Tang, Fei,Feng, Yi-Si
-
supporting information
p. 1254 - 1258
(2019/04/10)
-
- Function-oriented ionic polymers having high-density active sites for sustainable carbon dioxide conversion
-
On the basis of the development of function-oriented synthesis (FOS), we presented for the first time an efficient and one-pot construction of functional ionic polymers (FIPs) through the phenol-formaldehyde condensation process (pre-synthetic approach); FIPs had high density of Br?nsted acidic and ionic sites. Considering the electrophilic-nucleophilic dual activation of phenolic hydroxyl groups and bromide anions, the imidazolium-based FIP-Im exhibited high activity for metal-, solvent- and additive-free synthesis of cyclic carbonates from CO2 and epoxides under mild conditions. Then, to obtain higher ionic density and a more flexible skeleton, FIP-Im@QA was also prepared by implanting quaternary ammonium (QA) in the framework of FIP-IMvia the Williamson ether synthesis (post-synthetic modification), which demonstrated high efficiency in the N-formylation reaction of multitudinous secondary amines with CO2 and PhSiH3 at ambient temperature. More interestingly, these function-oriented catalysts were compatible with the target transformation under low CO2 concentration (15% in 85% N2, v/v) and were also reused for more than six times without a significant loss of activity and selectivity. Therefore, this study could not only facilitate the design and construction of FIPs, but also provide sustainable protocols for efficient production of value-added chemicals from CO2 under mild conditions.
- Chen, Yaju,Luo, Rongchang,Bao, Junhui,Xu, Qihang,Jiang, Jun,Zhou, Xiantai,Ji, Hongbing
-
supporting information
p. 9172 - 9182
(2018/05/28)
-
- Copper catalysis: Ligand-controlled selective: N -methylation or N -formylation of amines with CO2 and phenylsilane
-
Cupric subcarbonate (Cu2(OH)2CO3) was found to be effective for the reductive functionalization of CO2 to produce formamides and methylamines with phenylsilane as reductant. Interestingly, N-formylation and N-methylation were switched on/off by subtly choosing the ligand: DPPB (1,4-bis(diphenylphosphino)butane) promoted N-methylation whereas Ph2CyP (diphenylcyclohexylphosphine) favored for N-formylation.
- Li, Xue-Dong,Xia, Shu-Mei,Chen, Kai-Hong,Liu, Xiao-Fang,Li, Hong-Ru,He, Liang-Nian
-
supporting information
p. 4853 - 4858
(2018/11/21)
-
- 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)
-
- 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)
-
- Tungstate catalysis: Pressure-switched 2- and 6-electron reductive functionalization of CO2 with amines and phenylsilane
-
An efficient and environmentally benign tungstate catalyst for reductive functionalization of CO2 with amines and phenylsilane was developed. By simply varying the pressure, 2-electron or 6-electron reduction of CO2 was successfully achieved with simultaneous C-N bond formation, thus leading to the formation of formamides and methylamines, respectively. That is, secondary and primary amines furnished the corresponding methylamines or dimethylamines in excellent yields under atmospheric pressure of CO2, while various formamides were formed in yields ranging from 52% to 98% when increasing the CO2 pressure to 2 MPa. 1H NMR studies and control experiments demonstrate that N-formylation proceeds through the formation of silyl formate, while N-methylation proceeds through an aminal intermediate generated by 4-electron reduction of CO2.
- Wang, Mei-Yan,Wang, Ning,Liu, Xiao-Fang,Qiao, Chang,He, Liang-Nian
-
supporting information
p. 1564 - 1570
(2018/04/12)
-
- Method for preparing formamide and N-methylamines by carrying out selective reduction on carbon dioxide and amines regulated by ligand
-
The invention relates to a method for preparing formamide and N-methylamines by carrying out selective reduction on carbon dioxide and amines regulated by a ligand. According to the method, copper salt is used as a catalyst, organic amine or organic phosphorus is used as the ligand, CO2 and a hydrosilane are respectively used as a C1 resource and a reducing agent, and amines are used as a nucleophilic reagent; a reaction is carried out in an organic solvent, the consumption of the catalyst is 1-5mol%, and the consumption of the ligand is 1-20 mol%, the reaction temperature is 20-80 DEG C, theCO2 pressure is 0.1-8.0 MPa, the reaction time is 10-48h, the highest yield of the formamide is up to 98%, and the highest yield of the N-methylamine is up to 95%. The method provided by the inventionhas the advantages that the ligand is used for a regulation method for selective reduction preparation of the formamide and the N-methylamines for the first time; the catalyst is low in price, easy to obtain and simple in composition; the renewable CO2 is used as a raw material, so that the use of the traditional toxic formylation and methylation reagents is avoided; the substrate is wide in application scope and is suitable for a variety of secondary amines.
- -
-
Paragraph 0127-0134
(2019/01/14)
-
- N-aryl formamide prepared by using ethyl bromodifluoroacetate as formylating reagent
-
The invention discloses a compound of N-aryl formamide prepared by using ethyl bromodifluoroacetate as a formylating reagent. The compound is prepared by using N-alkyl arylamine as a raw material, ethyl bromodifluoroacetate as a formylating reagent and copper as a catalyst, adding different ligands, bases, etc., performing reaction under stirring in a reaction solvent at 100-120 DEG C for 10-14 hours; then filtering the reaction solution to obtain filtrate after reaction ending; concentrating the filtrate, removing the solvent by using a rotary evaporator to obtain a residue, treating the residue by silica gel column chromatography, eluting with an eluent, collecting the effluent according to the actual gradient; combining the effluent containing the product, concentrating the combined effluent to remove the solvent, and performing vacuum drying to obtain the target product. The compound has the advantages of simple and easily obtained raw materials, simple preparation process, less pollution, low energy consumption and high yield.
- -
-
Paragraph 0024
(2018/12/02)
-
- Copper-Catalyzed N-Formylation of Amines through Tandem Amination/Hydrolysis/Decarboxylation Reaction of Ethyl Bromodifluoroacetate
-
Ethyl bromodifluoroacetate (BrCF2COOEt) was first used as the N-formylating reagent in the copper-catalyzed N-formylation of amines. A range of primary, secondary, cyclic arylamines, and aliphatic amines underwent the N-formylation smoothly to furnish the N-formamides in moderate-to-excellent yields.
- Li, Xiao-Fang,Zhang, Xing-Guo,Chen, Fan,Zhang, Xiao-Hong
-
p. 12815 - 12821
(2018/10/20)
-
- Method for synthesizing N-aryl formamide compound
-
A method for synthesizing an N-aryl formamide compound comprises the following steps: putting an N, N-dimethylaniline compound, cuprous chloride, sodium tetrafluoroborate and salicylic acid in an organic solvent in an oxygen atmosphere, reacting for 0.5-4
- -
-
Paragraph 0082; 0086
(2018/12/02)
-
- 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)
-
- Catalyst-free: N -formylation of amines using BH3NH3 and CO2 under mild conditions
-
The catalyst-free N-formylation of amines using CO2 as the C1 source and BH3NH3 as the reductant has been developed for the first time. The corresponding formylated products of both primary and secondary amines are obtained in good to excellent yields (up to 96% of isolated yield) under mild conditions.
- Zhao, Tian-Xiang,Zhai, Gao-Wen,Liang, Jian,Li, Ping,Hu, Xing-Bang,Wu, You-Ting
-
supporting information
p. 8046 - 8049
(2017/07/22)
-
- 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)
-
- Electrostatic Catalyst Generated from Diazadiborinine for Carbonyl Reduction
-
Since the seminal discovery by van der Waals in the late 19th century that weak attractive forces exist between even electrically neutral atoms or molecules, a number of noncovalent interactions have been recognized. Among them, electrostatic interactions such as hydrogen bonds play pivotal roles in countless chemical processes and biochemical living systems. By mimicking biocatalysis, various organocatalysts equipped with hydrogen-bond functionality have been developed; however, a challenge has persisted in designing catalysts exploiting other types of noncovalent interactions. Here, we report metal-free hydroboration reactions of carbonyl compounds and CO2 catalyzed by aromatic diazadiborinine. A joint experimental and computational study on the reaction mechanism suggests that adducts of diazadiborinine with carbonyl and CO2 formed at the initial stage of the reactions serve as actual catalysts. The former stabilizes the transition state by using the electrostatic interaction between the hydride of borane and the polar, hole-shaped structure of the adduct.
- Wu, Di,Wang, Ruixing,Li, Yongxin,Ganguly, Rakesh,Hirao, Hajime,Kinjo, Rei
-
supporting information
p. 134 - 151
(2017/07/17)
-
- Immobilization of ionic liquids to covalent organic frameworks for catalyzing the formylation of amines with CO2 and phenylsilane
-
We presented the immobilization of ionic liquids on the channel walls of COFs using a post-synthetic strategy. The ionic [Et4NBr]50%-Py-COF afforded a high CO2 adsorption capacity of 164.6 mg g-1 (1 bar, 273 K) and was developed as an effective heterogeneous catalyst for the transformation of CO2 into value-added formamides under ambient conditions.
- Dong, Bin,Wang, Liangying,Zhao, Shang,Ge, Rile,Song, Xuedan,Wang, Yu,Gao, Yanan
-
supporting information
p. 7082 - 7085
(2016/06/09)
-
- Biomass-derived γ-valerolactone as an efficient solvent and catalyst for the transformation of CO2 to formamides
-
Efficient conversion of carbon dioxide (CO2) into valuable chemicals is a very attractive topic. Herein, we conducted the first work on the utilization of biomass-derived γ-valerolactone (GVL) as the solvent and catalyst for transformation of CO2 with various primary and secondary amines in the presence of phenylsilane (PhSiH3), and the corresponding desired formamides were produced with high yields without any additional catalyst. Systematic studies indicated that the lactone structure of GVL played a key role in the formation of the active silyl formates and the activation of N-H bonds in amines, thus leading to the excellent performance of GVL for the catalytic reactions.
- Song, Jinliang,Zhou, Baowen,Liu, Huizhen,Xie, Chao,Meng, Qinglei,Zhang, Zhanrong,Han, Buxing
-
supporting information
p. 3956 - 3961
(2016/07/21)
-
- 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)
-
- Reactions of Tertiary Allylic Amines and Dichlorocarbenes
-
In this article, a study on reactions of tertiary allylic amines and dichlorocarbenes had been described. Tertiary allylic amines could result from an interesting de-N-allylation/formylation reaction under the treatment of dichlorocarbenes. Notably, amines containing steric substituents or electron-deficient aromatic substituents on the nitrogen will go through cyclopropanations of the carbon-carbon double bond.
- Wang, Meili,Xiao, Fenfen,Bai, Yinjuan,Hu, Xiangdong
-
p. 2259 - 2265
(2015/09/22)
-
- Hydrophosphination of CO2 and Subsequent Formate Transfer in the 1,3,2-Diazaphospholene-Catalyzed N-Formylation of Amines
-
Hydrophosphination of CO2 with 1,3,2-Diazaphospholene (NHP-H; 1) afforded phosphorus formate (NHP-OCOH; 2) through the formation of a bond between the electrophilic phosphorus atom in 1 and the oxygen atom from CO2, along with hydride transfer to the carbon atom of CO2. Transfer of the formate from 2 to Ph2SiH2 produced Ph2Si(OCHO)2 (3) in a reaction that could be carried out in a catalytic manner by using 5 mol % of 1. These elementary reactions were applied to the metal-free catalytic N-formylation of amine derivatives with CO2 in one pot under ambient conditions.
- Chong, Che Chang,Kinjo, Rei
-
supporting information
p. 12116 - 12120
(2015/10/12)
-
- Imidazolium-Based Ionic Liquids Catalyzed Formylation of Amines Using Carbon Dioxide and Phenylsilane at Room Temperature
-
The CO2-involved synthesis of chemicals is of significance. In this work, we found that 1-alkyl-3-methylimidazolium ionic liquids (ILs) had high efficiency for catalyzing the formylation of amines using CO2 and phenylsilane at room temperature, producing the corresponding formylated products in excellent yields under the metal-free condition. The ILs acted as bifunctional catalysts, which activated the Si-H bond of phenylsilane to react with CO2 to form the formoxysilane intermediate and simultaneously activated the amine substrate through the hydrogen bond. Moreover, the imidazolium cation and the anions of the ILs showed an excellent synergistic effect on catalyzing the formylation of amines.
- Hao, Leiduan,Zhao, Yanfei,Yu, Bo,Yang, Zhenzhen,Zhang, Hongye,Han, Buxing,Gao, Xiang,Liu, Zhimin
-
p. 4989 - 4993
(2015/09/15)
-
- Copper/N,N-dimethylglycine catalyzed Goldberg reactions between aryl bromides and amides, aryl iodides and secondary acyclic amides
-
An efficient and general copper-catalyzed Goldberg reaction at 90-110 °C between aryl bromides and amides providing the desired products in good to excellent yields has been developed using N,N-dimethylglycine as the ligand. The reaction is tolerant toward a wide range of amides and a variety of functional group substituted aryl bromides. In addition, hindered, unreactive aromatic and aliphatic secondary acyclic amides, known to be poor nucleophiles, are efficiently coupled with aryl iodides through this simple and cheap copper/N,N-dimethylglycine catalytic system.
- Jiang, Liqin
-
supporting information
p. 13448 - 13460
(2015/02/19)
-
- Catalysed anti-Markovnikov oxidation of terminal aryl alkenes to aldehydes and transformation of methyl aryl tertiary amines to formamides with H2O2 as a terminal oxidant
-
Anti-Markovnikov oxidation of terminal aryl alkenes to aldehydes and transformation of N-methyl aryl tertiary amines to formamides with H2O2 as a terminal oxidant under mild conditions have been achieved with moderate to good product yields using [FeIII(TF4DMAP)OTf] as catalyst. This journal is
- Du, Yi-Dan,Tse, Chun-Wai,Xu, Zhen-Jiang,Liu, Yungen,Che, Chi-Ming
-
supporting information
p. 12669 - 12672
(2015/05/20)
-