Molecular Catalysis
·
2022
·
IF 5.089
Xiao-Chao Chen,Lin Guo,Guang-Hui Shi,Kai-Chun Zhao,Yong Lu,Ye Liu
Carbon dioxide (CO 2 ) was found to serve as a novel and green catalyst for the first time in N -formylation of amines with N, N -dimethylformamide (DMF), wherein only the aliphatic amines were applicable to afford the formamides in the yield of 71∼95%. The isotope labeling experiment with DMF- d 7 indicated that the N -formyl group in the formylated product was originated from DMF rather than CO 2 . The control experiments and the in situ high-pressure FT-IR spectra demonstrated that the formation of the carbamate salt of cyclohexylammonium cyclohexylcarbamate ( A ) derived from the reaction of CO 2 with cyclohexylamine was the driving force for this reaction. Accordingly, the mechanism of CO 2 -catalyed N -formylation of aliphatic amines with DMF was proposed, involving the formation of carbamate salt intermediate with enhanced nucleophilicity in anion in favor of the attack on carbonyl-group of DMF.
研究领域:
有机化学
·
绿色化学
✓ 已验证
DOI
高影响因子
C-Journal of Carbon Research
·
2024
·Vol. 10
·期 3
·62
·
IF 3.9
Xuexin Yuan,Qiqi Zhou,Yu Chen,Hai-Jian Yang,Qingqing Jiang,Juncheng Hu,Cun-Yue Guo
In the present work, inexpensive and commercially available diethyltriamine pentaacetic acid (DTPA) was used as an initiator to catalyze the N-formylation reaction of CO2with amines via the construction of C-N bonds in the presence of xanthone as the photosensitizer and PhSiH3as the reducing agent. After a systematic study of various factors, the optimal conditions for the photocatalytic reaction were obtained: 2.5 mmol of amine, 2.5 mmol of PhSiH3, 10 mol% of DTPA, 20 mol% of xanthone, 1 mL of dimethylsulfoxide (DMSO), atmospheric pressure, and 35 W UV lamp irradiation for 48 h. Under the optimal conditions, the catalyst system afforded high performance for the N-formylation of amines (primary and secondary amines) and CO2, and the yields of the N-formylated products of dialkylamines were above 70%. Further studies exhibit that the catalytic system has a wide scope of substrate applications. For various alicyclic secondary amines, heterocyclic secondary amines, aliphatic primary amines, and aromatic primary amines, the corresponding N-formylation products can be obtained efficiently. In addition, the catalyst can be recycled by simple precipitation and filtration. After five cycles of recycling, there was no significant change in the catalytic and structural properties of DTPA. Finally, a possible reaction mechanism is proposed.
研究领域:
化学
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环境科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS TODAY
·
2024
·
IF 5.2
Peng Bai,Yicheng Zhao,Yongdan Li
Photocatalytic N -formylation of amines with CO 2 is a promising strategy to convert CO 2 into value-added chemicals sustainably. In this work, Pd-Bi bimetallic modified ZnO enriched in oxygen vacancies is constructed for photocatalytic CO 2 formylation of benzylamine at room temperature without any reductants. The Pd and Bi sites reduce the band gap energy of ZnO, promote the separation of the photogenerated charge carriers and enhance the adsorption capacity of CO 2 . The yield of N -benzylformamide reaches 31.7 mmol g −1 with a selectivity of 85.3 % after 3-hour radiation in N , N -dimethylformamide (DMF) solvent. The aldehyde group involved in the formylation of benzylamine is derived from the decomposition of DMF, which is regenerated with the aldehyde group coming from the reduction of CO 2 . The decomposition-regeneration cycle of DMF solvent enlarges the reaction region, which is beneficial to the activity and selectivity of the formylation process. The synergistic photocatalytic system shows a good universality. This study provides a new approach to high-efficiency CO 2 utilization and formamide production.
研究领域:
材料科学
·
环境科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2024
·
IF 3.9
Yuhao Yang,Minghui Tan,Hailun Geng,Xiujuan Gao,Yisheng Tan,Qingde Zhang
Oriented designing the microenvironment of catalytic sites is essential for understanding catalytic processes. In this work, EDTA was first grafted in UiO-66 and then chelated Rh to obtain an efficient catalyst for 1-hexene hydroformylation reaction. EDTA not only served as a chelation site for Rh immobilization in UiO-66, but also markedly influenced the structure and properties of Rh/UiO-66. The incorporation of EDTA reduced the micropore content and suppressed the formation of heavy products. Moreover, the grafted EDTA regulated the electronic state of Rh effectively to improve the CO and propene adsorption, thus constructing an appropriate microenvironment for hydroformylation. Therefore, EDTA-modified Rh/U-E catalyst exhibited higher aldehydes yield, TOF and stability than Rh/U without EDTA. The dual role of EDTA in anchoring Rh sites and modulating the microenvironment for hydroformylation provides more prospects for designing customized MOFs-based catalysts.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2024
·
IF 15.7
Zhounan Yu,Leilei Zhang,Yuanlong Tan,Rizheng Jing,Hongchen Cao,Caiyi Lou,Rile Ge,Junhu Wang,Aiqin Wang,Tao Zhang
Rh-P complexes have been widely used as catalysts for hydroformylation reactions. The extremely high price of Rh and its scarce reserves have prompted the exploration of the alternatives. In this study, we reported that Pt/PS-PPh 2 single-atom catalysts promoted by SnCl 2 were highly efficient and selective for the hydroformylation of higher α-alkenes. A broad scope of substrates (i.e., C 6 –C 12 ) were smoothly converted to the corresponding linear aldehydes with high yields under reaction conditions of 90–120 °C and 4–6 MPa syngas . The turnover frequency (TOF) was comparable to homogeneous Pt-Sn catalysts, and the linear/branched ratio reached as high as > 20. In addition, the catalyst could be reused with the extra addition of SnCl 2 . The promotional role of SnCl 2 was elucidated by quasi- in situ X-ray adsorption fine structure, Fourier transform infrared, and Mössbauer spectroscopy . It was discovered that SnCl 2 was transformed into Sn(dioxane)Cl 3 − species coordinated to Pt as a moderately electron-donating ligand, which, together with the phosphine group, stabilized mononuclear Pt (I) species against reduction and aggregation.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2024
·
IF 2.7
Yufen Wang,Yantao Wang,Yongqing Ma,Asma Mohmmad Elsharif,Chen Zhang,Weiran Yang,Christophe Len
A new transition-metal-free catalytic system which uses sodium iodide as the catalyst with formic acid as the hydrogen donor in a biphasic medium was reported for the reduction of the hydroxyl group and various unsaturated groups such as CC, CC, CN and CO. Using the same catalytic system, reductive N-formylation of nitroarenes with formic acid was explored to produce the corresponding amide in high selectivity. Moreover, the catalyst stability was evaluated and reaction mechanisms were studied and proposed for the three model reactions.
研究领域:
有机化学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
ChemSusChem
·
2015
·Vol. 8
·期 12
·2066-2072
·
IF 7.657
Yehong Wang,Jian Zhang,Jing Liu,Chaofeng Zhang,Zhixin Zhang,Jie Xu,Shutao Xu,Fangjun Wang,Feng Wang
Graphical CO 2 -mediated reactions: CO 2 -mediated metathesis reactions between amines and DMF to synthesize formamides are described. The N -formylation of amines to formamides is achieved by activating amines, not DMF, via a C N and N H bond metathesis reaction. Using this method, primary, secondary, aromatic, and heterocyclic amines as well as diamines can be obtained with good to excellent formamide yields. Herein, we report CO 2 -mediated metathesis reactions between amines and DMF to synthesize formamides. More than 20 amines, including primary, secondary, aromatic, and heterocyclic amines, diamines, and amino acids, are converted to the corresponding formamides with good-to-excellent conversions and selectivities under mild conditions. This strategy employs CO 2 as a mediator to activate the amine under metal-free conditions. The experimental data and in situ NMR and attenuated total reflectance IR spectroscopy measurements support the formation of the N -carbamic acid as an intermediate through the weak acid–base interaction between CO 2 and the amine. The metathesis reaction is driven by the formation of a stable carbamate, and a reaction mechanism is proposed.
研究领域:
有机化学
·
绿色化学
✓ 已验证
DOI
PubMed
高影响因子
Molecular Catalysis
·
2024
·
IF 3.9
Yifei Chen,Xinnan Zhao,Chen Xin,Xiuqin Dong,Hao Gong
This work explored the role of defective sites on the hydroformylation of n-butene through ligand regulation. The investigation examined the effect of modulator properties on defect sites and rhodium loading, and optimized the H 2 BDC/modulator ratio to improve catalyst activity. Atomically dispersed Rh is anchored to these highly dispersed defect sites, effectively preventing aggregation and thereby enhancing hydrogenation ability. Under optimal conditions, the catalyst achieved a conversion of 96.9 %, with an overall aldehyde selectivity of 90 %. DRIFTS analysis provided compelling evidence that Rh(CO) 2 and HRhCO species were formed on 1Rh/MOF-5-HBC, improving CO insertion capability. This study highlights the significance of MOFs as catalyst supports in enhancing performance through defect engineering. The ability of the modulator to induce defect formation was measured by p K a. Meanwhile, it has been discovered that the length differences between the modulator and the MOF organic ligand can have a significant impact on the stability of defective MOFs.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CHEMISTRY
·
2020
·Vol. 38
·期 10
·1057-1064
·
IF 3.826
Chongyang Du,Yaofeng Chen
Summary of main observation and conclusion Transformation of CO 2 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 CO 2 and (EtO) 3 SiH under solvent free condition. Using 2 mol% 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.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2017
·
IF 4.339
Yuqing Wang,Li Yan,Cunyao Li,Miao Jiang,Wenlong Wang,Yunjie Ding
Porous organic copolymer (denoted as CPOL-BP&P) was afforded through the copolymerization of vinyl biphephos and tris (4-vinylphenyl)phosphine monomers under solvothermal conditions, and followed with impregnation method provided a highly efficient Rh/CPOL-BP&P catalyst with high activity (TOF = 11,200 h −1 ) and regioselectivity (the ratio of linear to branched aldehydes, l:b = 62.2) for heterogeneous hydroformylation of 1-butene. High regioselectivity was also obtained in the hydroformylation of butene mixture (2-butene: l:b = 55.8, isomeric mixture of butenes: l:b = 56.0). The Rh/CPOL-BP&P catalysts were thoroughly characterized by means of nitrogen sorption isotherms, in situ FT-IR, XPS, solid-state 31 P MAS NMR, HAADF-STEM, SEM and TEM. The formation of unique coordination bonds with Rh species in the polymer skeleton was determined. Heterogeneous hydroformylation of butenes was effectively realized due to a synergetic effect between PPh 3 moiety and biphephos moiety.
研究领域:
材料化学
·
催化化学
✓ 已验证
DOI
高影响因子
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
·
2015
·
IF 3.615
Miao Jiang,Li Yan,Yunjie Ding,Qi Sun,Jia Liu,Hejun Zhu,Ronghe Lin,Fengshou Xiao,Zheng Jiang,Jingyue Liu
The heterogenization of homogeneous catalysts is of critical importance for both fundamental research and practical applications. The key obstacle to industrial applications of heterogenized homogeneous catalysts is the long-term stability of the immobilized molecular complexes. We unambiguously demonstrate in this report that the vinyl-functionalized PPh 3 polymers supported single Rh sites (Rh/POL–PPh 3 ) catalyst provided not only excellent catalytic activity but also ultrahigh stability for fixed-bed olefins hydroformylation , which is one of the most important industrial homogeneous catalytic processes for the synthesis of aldehydes and alcohols. HAADF-STEM and EXAFS results indicated that the Rh atoms were present in single Rh sites which were strongly coordinated with the exposed phosphorous atoms of the POL–PPh 3 support. The Rh/POL-PPh 3 catalyst provided high activity and selectivity because it maintained the catalytic functionalities similar to the homogeneous HRh(CO)(PPh 3 ) 3 complex, as demonstrated both by 31 P MAS NMR and in situ FT-IR experiments. Thus a reaction mechanism, similar to that over the homogeneous HRh(CO)(PPh 3 ) 3 complex, was proposed for olefin hydroformylation over the novel Rh/POL–PPh 3 catalyst.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2021
·
IF 8.198
Jian Fang,Zhi-Qiang Wang,Xinjia Wei,Yuan Ma,Honghui Gong,Xue-Qing Gong,Zhenshan Hou
The N-formylation reaction of various amines with CO2 is a promising method to utilize CO2 for the production of high value-added chemicals. Herein, an efficient Ru catalyst system consisting of Ru complex ([PPN][Ru(CO)3Cl3]) and the ionic liquid 1-butyl-3-methylimidazolium hydrogen phosphate ([Bmim]2[HPO4]), has been developed for the N-formylation reaction. Activity evaluation demonstrated that the catalyst system exhibited good to excellent yields of formamides under very mild conditions with the assistance of ionic liquids (ILs). Furthermore, the catalyst system could be reused at least five times with a slight loss of activity in N-formylmorpholine production. Further characterization by 1H nuclear magnetic resonance (NMR), 13C NMR, and density functional theory (DFT) calculations showed that the ILs ([Bmim]2[HPO4]) could facilitate the adsorption of CO2 by a concerted action of both cations and anions of the ILs to form phosphorus carbonate intermediate, thus effectively promoting the reaction. DFT calculations demonstrated that the formation of Ru–H was the first step, and then the CO2 absorbed by [Bmim]2[HPO4] inserted directly into Ru–H by cooperating with the Ru sites to form HCOO– species. After that, formate species dissociated from Ru catalysts and dehydrated to form formamides by the catalytic action of Ru complex and the basic IL.
研究领域:
化学工程
·
催化化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）