- Reduced Graphene Oxide Supported Ag Nanoparticles: An Efficient Catalyst for CO2 Conversion at Ambient Conditions
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A highly efficient carboxylative cyclization of propargylic alcohols with CO2 under atmospheric pressure catalyzed by silver (0) nanoparticles decorated reduced graphene oxide (Ag-rGO) is reported. Ag-rGO was fully characterized by scanning electron microscope spectra (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectra, Raman spectra and X-ray photoelectron spectroscopy (XPS). Notably, Ag-rGO can be also applied to the construction of other value-added chemicals (β-oxopropylcarbamates and 2-oxazolidinones) from CO2 at ambient conditions. In addition, Ag-rGO is stable and reusable, which shows the potential for the practical application for CO2 capture and utilization (CCU).
- Zhang, Xiao,Chen, Kai-Hong,Zhou, Zhi-Hua,He, Liang-Nian
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- Green Conversion of CO2 and Propargylamines Triggered by Triply Synergistic Catalytic Effects in Metal–Organic Frameworks
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Cyclization of propargylamines with CO2 to obtain 2-oxazolidone heterocyclic compounds is an essential reaction in industry but it is usually catalyzed by noble-metal catalysts with organic bases as co-catalysts under harsh conditions. We have synthesized a unique CuI/CuII mixed valence copper-based framework {[(CuI6I5)Cu3IIL6(DMA)3](NO3)?9DMA}n (1) with good solvent and thermal stability, as well as a high density of uncoordinated amino groups evenly distributed in the large nanoscopic channels. Catalytic experiments show that 1 can effectively catalyze the reaction of propargylamines with CO2, and the yield can reach 99 %. The turnover frequency (TOF) reaches a record value of 230 h?1, which is much higher than that of reported noble-metal catalysts. Importantly, this is the first report of heterogeneously catalyzed green conversion of propargylamines with CO2 without solvents and co-catalysts under low temperature and atmospheric pressure. A mechanistic study reveals that a triply synergistic catalytic effect between CuI/CuII and uncoordinated amino groups promotes highly efficient and green conversion of CO2. Furthermore, 1 directly catalyzes this reaction with high efficiency when using simulated flue gas as a CO2 source.
- Geng, Liang-Chen,Hou, Sheng-Li,Jiang, Xiao-Lei,Jiao, Yue-E,Wang, Hao-Zhe,Zhao, Bin
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- Ambient Chemical Fixation of CO2 Using a Robust Ag27 Cluster-Based Two-Dimensional Metal–Organic Framework
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Unprecedented double S2? templated Ag27 clusters have been stabilized by 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP-H2) ligands to afford a robust 2D metal–organic framework (Ag27-MOF). This silver cluster-assembled materi
- Cui, Ping,Fu, Qiang,Guo, Rui,Huang, Shan,Li, Weifeng,Sun, Di,Tung, Chen-Ho,Wang, Fenglong,Yao, Qingxia,Zhao, Meihua
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- Non-Noble-Metal Metal-Organic-Framework-Catalyzed Carboxylative Cyclization of Propargylic Amines with Atmospheric Carbon Dioxide under Ambient Conditions
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The coupling reaction of propargylic amines and carbon dioxide (CO2) to synthesize 2-oxazolidinones is an important reaction in industrial production, and yet harsh reaction conditions and noble-metal catalysts are often required to achieve high product yields. Herein, one novel noble-metal-free three-dimensional framework, [Mg3Cu2I2(IN)4(HCOO)2(DEF)4]n (1), assembled by magnesium and copper clusters was synthesized and applied to this reaction. Compound 1 displays excellent solvent stability. Importantly, 1, acting as heterogeneous catalyst, can highly catalyze the cyclization of propargylic amines with CO2 under atmospheric pressure at room temperature, which can be recycled at least five times without an obvious decrease of the catalytic activity. NMR spectroscopy, coupled with 13C-isotope- and deuterium-labeling experiments, clearly clarifies the mechanism of this catalytic system: CO2 was successfully captured and converted to the product of 2-oxazolidinones, the CC bond of propargylic amines can be effectively activated by 1, and proton transfer was involved in the reaction process. Density functional theory calculations are further conducted to uncover the reaction path and the crucial role of compound 1 during the reaction.
- Gu, Ai-Ling,Wang, Wan-Ting,Cheng, Xin-Yu,Hu, Tian-Ding,Wu, Zhi-Lei
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p. 13425 - 13433
(2021/08/30)
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- Expanded Ring NHC Silver Carboxylate Complexes as Efficient and Reusable Catalysts for the Carboxylative Cyclization of Unsubstituted Propargylic Derivatives
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Stabilized by a bulky N-heterocyclic carbene [BPDPr, 1,3-bis(2,6-diisopropylphenyl)-1,3-diazonine-2-ylidene] ligand, new silver carboxylate complexes of the form BPDPrAgO2C-R (R=Me, Ph) have been synthesized and fully char
- Cervantes-Reyes, Alejandro,Saxl, Tobias,Stein, Philipp M.,Rudolph, Matthias,Rominger, Frank,Asiri, Abdullah M.,Hashmi, A. Stephen K.
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p. 2367 - 2374
(2021/04/21)
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- Highly Efficient Conversion of Propargylic Amines and CO2 Catalyzed by Noble-Metal-Free [Zn116] Nanocages
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The reaction of propargylic amines and CO2 can provide high-value-added chemical products. However, most of catalysts in such reactions employ noble metals to obtain high yield, and it is important to seek eco-friendly noble-metal-free MOFs catalysts. Here, a giant and lantern-like [Zn116] nanocage in zinc-tetrazole 3D framework [Zn22(Trz)8(OH)12(H2O)9?8 H2O]n Trz=(C4N12O)4? (1) was obtained and structurally characterized. It consists of six [Zn14O21] clusters and eight [Zn4O4] clusters. To our knowledge, this is the highest-nuclearity nanocages constructed by Zn-clusters as building blocks to date. Importantly, catalytic investigations reveal that 1 can efficiently catalyze the cycloaddition of propargylic amines with CO2, exclusively affording various 2-oxazolidinones under mild conditions. It is the first eco-friendly noble-metal-free MOFs catalyst for the cyclization of propargylic amines with CO2. DFT calculations uncover that ZnII ions can efficiently activate both C≡C bonds of propargylic amines and CO2 by coordination interaction. NMR and FTIR spectroscopy further prove that Zn-clusters play an important role in activating C≡C bonds of propargylic amines. Furthermore, the electronic properties of related reactants, intermediates and products can help to understand the basic reaction mechanism and crucial role of catalyst 1.
- Cao, Chun-Shuai,Cheng, Peng,He, Liang-Nian,Shi, Ying,Song, Zhen-Jun,Xia, Shu-Mei,Xu, Hang,Zhao, Bin
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p. 8586 - 8593
(2020/03/26)
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- Binuclear Tridentate Hemilabile Copper(I) Catalysts for Utilization of CO2into Oxazolidinones from Propargylic Amines
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Four binuclear tridentate copper(I) complexes were synthesized based on the trans effect of the hybrid ligands. The catalytic performance and behavior of the prepared copper(I) complexes were evaluated in the carboxylative cyclization of propargylic amine
- Chen, Fei,Tao, Sheng,Deng, Qian-Qian,Wei, Donghui,Liu, Ning,Dai, Bin
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p. 15197 - 15212
(2020/11/30)
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- Efficient and Recyclable Cobalt(II)/Ionic Liquid Catalytic System for CO2 Conversion to Prepare 2-Oxazolinones at Atmospheric Pressure
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Converting CO2 into value-added chemicals represents a promising way to alleviate the CO2 derived environmental issues, for which the development of catalysts with high efficiency and recyclability is very desirable. Herein, the catalytic system by combining cobalt source and ionic liquid (IL) has been developed as the efficacious and recyclable catalyst for the carboxylative cyclization of propargylic amine and CO2 to prepare 2-oxazolinones. In this protocol, various propargylic amines were successfully transformed into the corresponding 2-oxazolinones with CoBr2 and diethylimidazolium acetate ([EEIM][OAc]) as the catalyst under atmospheric CO2 pressure. It is worth noting that the turnover number (TON) of this transformation can be up to 1740, presumably being attributed to the cooperative effect of the cobalt and IL. Furthermore, the existence of IL enables the catalytic system to be easily recycled to 10 times without losing its activity.
- Zhou, Zhi-Hua,Chen, Kai-Hong,He, Liang-Nian
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p. 1223 - 1228
(2019/11/21)
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- In Situ Generated Zinc(II) Catalyst for Incorporation of CO2 into 2-Oxazolidinones with Propargylic Amines at Atmospheric Pressure
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Incorporation of CO2 into heterocyclic compounds (i.e., 2-oxazolidinones) under mild conditions, especially at atmospheric pressure still remains challenging. The mononuclear ZnII complex ZnCl2(TBD)2, where TBD=
- Liu, Xi,Wang, Mei-Yan,Wang, Si-Yuan,Wang, Qi,He, Liang-Nian
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p. 1210 - 1216
(2017/03/29)
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- Copper-catalyzed cascade reactions of N-(2-bromoallyl)amines with KHCO 3 as the C1 source: An efficient process for the synthesis of oxazolidin-2-ones
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A novel synthesis of oxazolidin-2-ones by carbamic acid formation and a subsequent copper-catalyzed intramolecular vinylation from N-(2-bromoallyl) amines and KHCO3 was developed. KHCO3 was used as a C1 source and base in this effici
- Jin, Hongwei,Yang, Yukun,Jia, Jianhong,Yue, Binjie,Lang, Bo,Weng, Jianquan
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p. 26990 - 26992
(2014/07/21)
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- Regiospecific Introduction of Amino-alkene Functionality into 1,2,3-Triols, 1,3-Dihalogenopropan-2-ols, and 2,3-Dihalogenopropanols promoted by Fluoride Anion
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Regiospecific transformations of 1,2,3-triol, 1,3-dihalogenopropan-2-ol, and 2,3-dihalogenopropanol derivatives into oxazolidin-2-ones and/or oxazol-2(3H)-ones promoted by fluoride anion are described.
- Shimizu, Makoto,Yoshioka, Hirosuke
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p. 689 - 690
(2007/10/02)
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