- Copper-catalysed synthesis of α-alkylidene cyclic carbonates from propargylic alcohols and CO2
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We report a N-heterocyclic carbene copper(i) complex-catalysed formal cycloaddition between readily available propargylic alcohols and carbon dioxide at room temperature. By using the combination of a sterically demandingBPDPrCuCl complex (BPDPr = 1,3-bis(2,6-diisopropylphenyl)-1,3-diazonine-2-ylidene) and CsF, as catalytic system, primary propargylic alcohols are efficiently converted to the corresponding α-alkylidene cyclic carbonates. Gram scale (up to 89% yield) and reusability experiments (74% global yield, turnover number value = 103) showcase the robustness of the catalytic system. This practically simple protocol also tolerates secondary and tertiary propargylic alcohols under CO2at atmospheric pressure, enabling the direct synthesis of substituted and unsubstituted α-alkylidene cyclic carbonates at room temperature.
- Cervantes-Reyes, Alejandro,Farshadfar, Kaveh,Rudolph, Matthias,Rominger, Frank,Schaub, Thomas,Ariafard, Alireza,Hashmi
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supporting information
p. 889 - 897
(2021/02/09)
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- Highly efficient synthesis of alkylidene cyclic carbonates from low concentration CO2using hydroxyl and azolate dual functionalized ionic liquids
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A highly efficient catalytic system was developed for the reaction between CO2 and propargylic alcohols for alkylidene cyclic carbonates. Ionic liquids (ILs) with different anions and cations were designed as cocatalysts, in order to find out the effect of the cation and the anion on this reaction. The results indicated that the effect of the cation was significant, especially the hydroxyl group on the cation played an important role due to the presence of a hydrogen bond. It was also found that the basicity of the anion was important for its catalytic activity, where the anion with moderate basicity gave the best activity. Moreover, this hydroxyl and azolate dual functionalized catalytic system showed excellent reusability and generality. It is worth mentioning that at a low concentration of CO2, this dual functionalized catalytic system showed excellent catalytic activity even in a gram-scale reaction, indicating its potential in carbon capture and utilization processes.
- Shi, Guiling,Zhai, Ran,Li, Haoran,Wang, Congmin
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p. 592 - 596
(2021/01/28)
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- Synthesis of α-alkylidene cyclic carbonatesviaCO2fixation under ambient conditions promoted by an easily available silver carbamate
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The simple and cost-effective compound [Ag(O2CNEt2)], in combination with PPh3, works as an effective catalytic precursor in the carboxylation of propargyl alcohols at ambient temperature and atmospheric CO2pressure, and in most cases under solventless conditions. The silver carbamate revealed a better performance than commercial silver oxide, Ag2O, and allowed to obtain a series of α-alkylidene cyclic carbonates in high yields.
- Bresciani, Giulio,Bortoluzzi, Marco,Ghelarducci, Claudia,Marchetti, Fabio,Pampaloni, Guido
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p. 4340 - 4346
(2021/03/15)
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- Noble metal-free Cu(i)-anchored NHC-based MOF for highly recyclable fixation of CO2under RT and atmospheric pressure conditions
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The utilization of CO2as a C1 feedstock for the synthesis of high-value chemicals and fuels is an important step towards mitigating the increasing concentration of atmospheric carbon dioxide as well as the production of value-added chemicals. Herein, we demonstrate the development of an efficient recyclable catalyst for the conversion of CO2into oxazolidinones, which are important commodity chemicals for antibiotics, by utilizing an N-heterocyclic carbene (NHC)-based metal-organic framework (MOF). The NHC-centers lined in the pore walls of the MOF were utilized to anchor catalytically active Cu(i) ions by post-synthetic modification (PSM). The Cu(i)-embedded MOF showed highly recyclable and selective CO2uptake properties with a high heat of interaction energy of 43 kJ mol?1. The presence of a high density of CO2-philic NHC and catalytic Cu(i) sites in the 1D channels of the MOF render highly efficient catalytic activity for fixation of CO2into α-alkylidene cyclic carbonates and oxazolidinones at RT and atmospheric pressure conditions. Notably, Cu(i)@NHC-MOF showed excellent recyclability for up to 10 cycles of regeneration with retention of catalytic activity as well as chemical stability. To the best of our knowledge, Cu(i)@NHC-MOF is the first example of a noble metal-free MOF-based heterogeneous catalyst for the utilization of CO2to synthesize important value-added chemicals under mild conditions.
- Das, Rajesh,Nagaraja, C. M.
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supporting information
p. 5195 - 5204
(2021/07/29)
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- 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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p. 4825 - 4830
(2020/08/10)
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- Highly Efficient Fixation of Carbon Dioxide at RT and Atmospheric Pressure Conditions: Influence of Polar Functionality on Selective Capture and Conversion of CO2
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The rapid increase in the concentration of atmospheric carbon dioxide (CO2) has resulted in undesirable environmental issues. Hence, selective CO2 capture and utilization as C1 feedstock for the preparation of high-value chemicals and fuels has been considered as a promising step toward mitigating the growing concentration of atmospheric CO2. In this direction, herein we report rational construction of a Ag(I)-anchored sulfonate-functionalized UiO-66 MOF named as MOF-SO3Ag composed of CO2-philic sulfonate functionality and catalytically active alkynophilic Ag(I) sites for chemical fixation of carbon dioxide. The MOF-SO3Ag exhibits selective as well as recyclable adsorption of CO2 with a high heat of adsorption energy (Qst) of 37.8 kJ/mol. On the other hand, the analogous MOF, UiO-66 doped with Ag(I), showed a lower Qst value of 30 kJ/mol, highlighting the importance of the sulfonate group for stronger interaction with CO2. Furthermore, the MOF-SO3Ag acts as an efficient heterogeneous catalyst for cyclic carboxylation of propargylic alcohols to generate α-alkylidene cyclic carbonates in >99percent yield at mild conditions of RT and 1 bar CO2. More importantly, one-pot synthesis of oxazolidinones by a three-component reaction between CO2, propargylic alcohol, and primary amine has also been achieved using MOF-SO3Ag catalyst under the mild conditions. The MOF is highly recyclable and retains its superior catalytic activity even after several cycles. To the best of our knowledge, MOF-SO3Ag is the first example of MOF reported for RT chemical fixation of CO2 to oxazolidinones by aminolysis of α-alkylidene cyclic carbonates under the environment-friendly mild conditions.
- Das, Rajesh,Nagaraja, C. M.
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supporting information
(2020/07/21)
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- A highly stable polyoxovanadate-based Cu(i)-MOF for the carboxylative cyclization of CO2with propargylic alcohols at room temperature
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A novel polyoxovanadate-based copper(i)-organic framework, [CuI(bib)]4{VV4O12} (V-Cu-MOF, bib = 1,4-bis(1H-imidazoly-1-yl)benzene), is facilely synthesized under mild hydrothermal conditions. The structure of the V-Cu-MOF is constructed from a cyclic {V4O12}4- polyanion cluster and a 1D chain Cu(i)-MOF ([CuI(bib)]+). The presence of the {V4O12}4- cluster stabilizes the Cu(i)-MOF with Cu(i) as the center, thereby improving the stability of the V-Cu-MOF and enabling it to stably exist in various solvents and pH = 2-12 solutions. Additionally, the V-Cu-MOF as a heterogeneous catalyst can catalyze the carboxylative cyclization of CO2 and propargylic alcohols to high value-added α-alkylidene cyclic carbonates at room temperature, and the conversion and selectivity are almost 100%. More importantly, no obvious decrease in the yield of the α-alkylidene cyclic carbonate is observed after ten cycles. These results indicate the excellent catalytic activity and sustainability of the V-Cu-MOF. Research on the mechanism of the catalytic reaction suggests that the high-density Cu(i) sites in the V-Cu-MOF are the catalytically active centers for activating the CC bonds of propargylic alcohols. To the best of our knowledge, this is the first example of polyoxometalate-based metal-organic framework catalyst for catalyzing the conversion of CO2 to value-added α-alkylidene cyclic carbonates at room temperature. This journal is
- Dang, Tian-Yi,Li, Zhuo,Liu, Shu-Mei,Liu, Shu-Xia,Lu, Ying,Tian, Hong-Rui,Zhang, Zhong
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p. 7513 - 7520
(2020/11/23)
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- Isolable CO2 Adducts of Polarized Alkenes: High Thermal Stability and Catalytic Activity for CO2 Chemical Transformation
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Various CO2 adducts of tetra-hydropyrimidin-2-ylidene (THPE) derived from the commercially available 1, 5-diazabicyclo[4.3.0]non-5-ene (DBN) were firstly synthesized. X-ray single crystal analysis revealed the bent geometry of the binding CO2 having an O?C?O angle of 127.50~129.51° for THPE?CO2 adducts. In situ FTIR experiments demonstrated that THPE?CO2 adducts had unprecedented thermal stability in DMSO, even at 100 °C without decomposition. It was found that the THPE?CO2 adducts were highly active in catalyzing the carboxylative cyclization of CO2 with propargylic alcohols under mild conditions, significantly higher than the previously reported organocatalysts. Various internal and terminal functionalized propargylic alcohols were tolerated in these processes to afford the corresponding α-alkylidene cyclic carbonates in moderate to good yields with complete (Z)-stereoselectivity. Isotope labeling, in combination with in-situ FTIR and stoichiometric experiments, reveal that the catalytic reaction tends to proceed via the THPE?CO2-mediated basic ionic pair mechanism. (Figure presented.).
- Zhou, Hui,Zhang, Rui,Lu, Xiao-Bing
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supporting information
p. 326 - 334
(2019/01/04)
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- A Noble-Metal-Free Metal–Organic Framework (MOF) Catalyst for the Highly Efficient Conversion of CO2 with Propargylic Alcohols
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Cyclization of propargylic alcohols with CO2 is an important reaction in industry, and noble-metal catalysts are often employed to ensure the high product yields under environmentally friendly conditions. Herein a porous noble-metal-free framework 1 with large 1D channels of 1.66 nm diameter was synthesized for this reaction. Compound 1 exhibits excellent acid/base stability, and is even stable in corrosive triethylamine for one month. Catalytic studies indicate that 1 is an effective catalyst for the cyclization of propargylic alcohols and CO2 without any solvents under mild conditions, and the turnover number (TON) can reach to a record value of 14 400. Furthermore, this MOF catalyst also has rarely seen catalytic activity when the biological macromolecule ethisterone was used as a substrate. Mechanistic studies reveal that the synergistic catalytic effect between CuI and InIII plays a key role in the conversion of CO2.
- Hou, Sheng-Li,Dong, Jie,Jiang, Xiao-Lei,Jiao, Zhuo-Hao,Zhao, Bin
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supporting information
p. 577 - 581
(2018/12/11)
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- CO2 transformation under mild conditions using tripolyphosphate-grafted KCC-1-NH2
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Fibrous nanosilica (KCC-1) as a catalyst support was investigated in terms of stability, recycling, and reusability. For the first time, CO2 transformation was performed via the synthesis and application of KCC-1 together with sodium tripolyphosphate (STPP) and 3-aminopropyltriethoxysilane (APTES) as its functionalized derivative. To this goal, KCC-1/STPP NPs were applied to act as a nanocatalyst with excellent catalytic activities under green reaction conditions.
- Sadeghzadeh, Seyed Mohsen,Zhiani, Rahele,Moradi, Marjan
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p. 535 - 544
(2018/04/26)
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- Naturally occurring gallic acid derived multifunctional porous polymers for highly efficient CO2 conversion and I2 capture
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Assembly of naturally occurring building blocks into functional materials is of great importance. Herein, we utilized plant-derived polyphenols as building blocks to prepare porous organic polymers (POPs) with multifunctional sites, and a typical POP (denoted as GA-azo-POP) could be achieved from gallic acid through an azo-coupling strategy. As a superior support, GA-azo-POP supported Ag nanoparticles could efficiently catalyze the carboxylative cyclization of propargyl alcohols with CO2 with a very low usage of Ag (0.14 mol%). Meanwhile, the GA-azo-POP showed a high capacity for I2 adsorption (up to 287 mg g-1), which was higher than that of the reported solid materials at a similar I2 concentration. More interestingly, after adsorbing I2, the GA-azo-POP could efficiently catalyze the formation of cyclic carbonates from CO2. The excellent performance of the GA-azo-POP resulted from the co-existence of aromatic, azo, and phenolic OH functional groups and its porous structure.
- Xie, Chao,Song, Jinliang,Wu, Haoran,Hu, Yue,Liu, Huizhen,Yang, Youdi,Zhang, Zhanrong,Chen, Bingfeng,Han, Buxing
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p. 4655 - 4661
(2018/10/23)
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- Boosting the Catalytic Performance of Organic Salts for the Fast and Selective Synthesis of α-Alkylidene Cyclic Carbonates from Carbon Dioxide and Propargylic Alcohols
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The synthesis of α-alkylidene cyclic carbonates (αCCs) by the carboxylative coupling of CO2 with propargylic alcohols is receiving increasing interest but requires the use of catalysts that are most often added in large quantities and/or lack selectivity. Herein, we describe the fine-tuning of the structure of organocatalysts of the ammonium-type that enables us to identify the important structural parameters that dictate their catalytic performance. Tetrabutylammonium oxalate was revealed to be one of the most attractive organocatalysts with a remarkably fast, complete and selective production of αCCs at a low catalyst loading (2.5 mol %) under solvent-free conditions. This study opens new avenues for the facile and selective synthesis of libraries of αCCs from CO2 and propargylic alcohol by using simple organocatalysts.
- Grignard, Bruno,Ngassamtounzoua, Charlène,Gennen, Sandro,Gilbert, Bernard,Méreau, Rapha?l,Jerome, Christine,Tassaing, Thierry,Detrembleur, Christophe
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p. 2584 - 2592
(2018/06/27)
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- A simple and robust AgI/KOAc catalytic system for the carboxylative assembly of propargyl alcohols and carbon dioxide at atmospheric pressure
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A simple and robust AgI/KOAc system was developed for the cyclization of propargyl alcohols and carbon dioxide under mild conditions, and was identified to have excellent activities for numerous substrates, especially sterically hindered terminal alkynes and internal alkynes. Notably, the Ag loading involved was an unprecedentedly low level of 0.05 mol%.
- Yuan, Ye,Xie, Yu,Zeng, Cheng,Song, Dandan,Chaemchuen, Somboon,Chen, Cheng,Verpoort, Francis
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p. 2933 - 2939
(2017/08/14)
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- A recyclable AgI/OAc- catalytic system for the efficient synthesis of α-alkylidene cyclic carbonates: Carbon dioxide conversion at atmospheric pressure
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The cyclization of carbon dioxide and propargylic alcohols, especially challenging substrates, were efficiently catalyzed by a green and recyclable AgI/OAc- system under atmospheric pressure, which is shown to be the most recyclable system with 20 recycle rounds and has the lowest loading among all the reported recyclable systems that work under atmospheric pressure.
- Yuan, Ye,Xie, Yu,Zeng, Cheng,Song, Dandan,Chaemchuen, Somboon,Chen, Cheng,Verpoort, Francis
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supporting information
p. 2936 - 2940
(2017/07/24)
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- One-pot carboxylative cyclization of propargylic alcohols and CO2 catalysed by N-heterocyclic carbene/Ag systems
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A series of N-heterocyclic carbene (NHC)/Ag systems were developed for the carboxylative assembly of propargylic alcohols and carbon dioxide (CO2). With the catalysis of these catalytic systems, a variety of target α-alkylidene cyclic carbonates could be obtained smoothly under atmospheric CO2 pressure in straightforward one-pot processes. Particularly, these reactions could be performed without any stoichiometric addition of bases or additives. Further mechanistic investigation reveals that the excellent activities are attributed to the effective activations of CO2 accomplished by the NHCs via the formation of the NHC-CO2 adducts.
- Yuan, Ye,Xie, Yu,Song, Dandan,Zeng, Cheng,Chaemchuen, Somboon,Chen, Cheng,Verpoort, Francis
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- Tetrabutylphosphonium-Based Ionic Liquid Catalyzed CO2 Transformation at Ambient Conditions: A Case of Synthesis of α-Alkylidene Cyclic Carbonates
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A series of tetrabutylphosphonium ([Bu4P]+)-based ionic liquids (ILs) with multiple-site for CO2 capture and activation in their anions, which could efficiently catalyze the cyclization reaction of propargylic alcohols with CO2 at ambient conditions, are reported. Especially, the IL, [Bu4P]3[2,4-OPym-5-Ac], which has three interaction sites for attracting CO2 together with a pKa1 value of 9.13, exhibited the best performance, affording a series of α-alkylidene cyclic carbonates in moderate to good yields. The mechanism exploration demonstrated that IL served as a bifunctional catalyst with anion simultaneously activating CO2 via multiple-site cooperative interactions and the C≡C triple bond in propargylic alcohol via inductive effect, thus resulting in the production of α-alkylidene cyclic carbonates. (Chemical Equation Presented).
- Wu, Yunyan,Zhao, Yanfei,Li, Ruipeng,Yu, Bo,Chen, Yu,Liu, Xinwei,Wu, Cailing,Luo, Xiaoying,Liu, Zhimin
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p. 6251 - 6255
(2017/09/15)
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- Metalated Mesoporous Poly(triphenylphosphine) with Azo Functionality: Efficient Catalysts for CO2 Conversion
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Mesoporous poly(triphenylphosphine) with azo functionality (poly(PPh3)-azo) is reported, which was synthesized via oxidative polymerization of P(m-NH2Ph)3 at ambient conditions. This kind of polymer could strongly coordinate with metal ions (e.g., Ru3+) and could reduce Ag+ in situ to metallic form. The resultant metalated poly(PPh3)-azo (e.g., poly(PPh3)-azo-Ag or -Ru) were discovered to be highly efficient catalysts for CO2 transformation. Poly(PPh3)-azo-Ag showed more than 400 times higher site-time-yield (STY) for the carboxylative cyclization of propargylic alcohols with CO2 at room temperature compared with the best heterogeneous catalyst reported. Poly(PPh3)-azo-Ru also exhibited good activity for the methylation of amines with CO2. It was demonstrated that the high performances of the catalysts originated from the cooperative effects between the polymer and the metal species. In addition, both catalysts showed good stability and easy recyclability, thus demonstrating promising potential for practical utilization for the conversion of CO2 into value-added chemicals.
- Yang, Zhenzhen,Yu, Bo,Zhang, Hongye,Zhao, Yanfei,Chen, Yu,Ma, Zhishuang,Ji, Guipeng,Gao, Xiang,Han, Buxing,Liu, Zhimin
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p. 1268 - 1273
(2016/02/18)
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- Azole-Anion-Based Aprotic Ionic Liquids: Functional Solvents for Atmospheric CO2 Transformation into Various Heterocyclic Compounds
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The chemical transformation of atmospheric CO2 is of great significance yet still poses a great challenge. Herein, azole-anion-based aprotic ionic liquids (ILs) were synthesized by the deprotonation of weak proton donors (e.g., 2-methylimidazole, 4-methylimidazole, and 2,4-dimethylimidazole) with tetrabutylphosphonium hydroxide, [Bu4P][OH]. We found that these ILs, such as [Bu4P][2-MIm], could activate atmospheric CO2 through the formation of carbamates. The resultant carbamate intermediates could further react with various types of substrate, including propargylic alcohols, 2-aminobenzonitriles, ortho-phenylenediamines, and 2-aminothiophenol, thereby producing α-alkylidene cyclic carbonates, quinazoline-2,4(1 H,3 H)-diones, benzimidazolones, and benzothiazoline, respectively, in moderate-to-good yields. Thus, we have achieved the transformation of CO2 at atmospheric pressure, and we expect this method to open up new routes for the synthesis of various oxygen-containing heterocyclic compounds under metal-free conditions.
- Zhao, Yanfei,Wu, Yunyan,Yuan, Guangfeng,Hao, Leiduan,Gao, Xiang,Yang, Zhenzhen,Yu, Bo,Zhang, Hongye,Liu, Zhimin
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p. 2735 - 2740
(2016/10/11)
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- Robust Silver(I) Catalyst for the Carboxylative Cyclization of Propargylic Alcohols with Carbon Dioxide under Ambient Conditions
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Inspired by the bulkier bis(triphenylphosphine)-silver cation-induced mechanism of propargylic alcohols and carbon dioxide through the alkyl carbonate intermediate, a robust dual-component catalytic system consisting of silver acetate and tetraheptylammonium bromide was rationally developed for the synthesis of α-methylene cyclic carbonates under ambient conditions without employing any additional organic base and ligand. This is one of the most effective catalysts reported to date for this conversion, with a very high turnover number of up to 6024, probably due to the synergistic effect of Lewis basic and Lewis acidic species for the activation of both propargylic alcohol and carbon dioxide by the formation of the alkyl carbonate with a bulkier counterion. Notably, this catalyst also worked well for the carboxylative cyclization of propargylic amines with carbon dioxide with the highest turnover number of 544.
- Song, Qing-Wen,He, Liang-Nian
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supporting information
p. 1251 - 1258
(2016/04/26)
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- Tuning the basicity of ionic liquids for efficient synthesis of alkylidene carbonates from CO2 at atmospheric pressure
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A strategy to achieve the efficient synthesis of alkylidene carbonates from CO2 at atmospheric pressure by tuning the basicity of ionic liquids was developed. Excellent yields were obtained due to basic ionic liquids' dual roles both as absorbents and as activators. The reaction mechanism was investigated through a combination of NMR spectroscopy, controlled experiments and quantum calculations, indicating the importance of a moderate basicity.
- Chen, Kaihong,Shi, Guiling,Dao, Rina,Mei, Ke,Zhou, Xiuyuan,Li, Haoran,Wang, Congmin
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supporting information
p. 7830 - 7833
(2016/07/06)
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- Bifunctional silver(I) complex-catalyzed CO2 conversion at ambient conditions: Synthesis of α-methylene cyclic carbonates and derivatives
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Abstract The chemical conversion of CO2 at atmospheric pressure and room temperature remains a great challenge. The triphenylphosphine complex of silver(I) carbonate was proved to be a robust bifunctional catalyst for the carboxylative cyclization of propargylic alcohols and CO2 at ambient conditions leading to the formation of α-methylene cyclic carbonates in excellent yields. The unprecedented performance of [(PPh3)2Ag]2CO3 is presumably attributed to the simultaneous activation of CO2 and propargylic alcohol. Moreover, the highly compatible basicity of the catalytic species allows propargylic alcohol to react with CO2 leading to key silver alkylcarbonate intermediates: the bulkier [(Ph3P)2AgI]+ effectively activates the carbon-carbon triple bond and enhances O-nucleophilicity of the alkylcarbonic anion, thereby greatly promoting the intramolecular nucleophilic cyclization. Notably, this catalytic protocol also worked well for the reaction of propargylic alcohols, secondary amines, and CO2 (at atmospheric pressure) to afford β-oxopropylcarbamates.
- Song, Qing-Wen,Chen, Wei-Qiang,Ma, Ran,Yu, Ao,Li, Qiu-Yue,Chang, Yao,He, Liang-Nian
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p. 821 - 827
(2015/06/02)
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- Fluorinated microporous organic polymers: Design and applications in CO2adsorption and conversion
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Fluorinated microporous organic polymers (F-MOPs) were designed, showing twice higher CO2adsorption capacity than corresponding non-fluorous MOPs. The incorporation of phenanthroline moieties into F-MOPs afforded them the ability to coordinate with Ag(I), and the resultant F-MOP-Ag(I) displayed high efficiency for the reaction of CO2with propargyl alcohols to form a-alkylidene cyclic carbonates at 25°C.
- Yang, Zhen-Zhen,Zhao, Yanfei,Zhang, Hongye,Yu, Bo,Ma, Zhishuang,Ji, Guipeng,Liu, Zhimin
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supporting information
p. 13910 - 13913
(2015/02/19)
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- Efficient chemical fixation of CO2 promoted by a bifunctional Ag2WO4/Ph3P system
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An efficient heterogeneous silver-catalyzed reaction for construction of the α-methylene cyclic carbonate motif was developed through carboxylative assembly of propargyl alcohols and CO2. Such a CO2 fixation protocol proceeded smoothly with only 1 mol% of Ag2WO 4 and 2 mol% of PPh3 as well as atmospheric CO2 at room temperature under solvent-free conditions, in an environmentally benign and low energy manner along with an easy operating procedure. Notably, up to 98% isolated yields of carbonates could be attained with exclusive chemo-selectivity. In addition, the dual activation capacity of Ag 2WO4 towards both the propargylic substrate and CO 2 is based on which cooperative catalytic mechanism by the silver cation and the tungstate anion is proposed. Recycling trials on carboxylative cyclization of propargyl alcohols and CO2 illustrate that the catalyst can be reused at least 4 times with retention of high catalytic activity and selectivity. Especially, it allows the direct and effective application in the one-pot synthesis of various oxazolidinones bearing exocyclic alkenes and carbamates in moderate to high yields upon the alternative introduction of primary or secondary amines.
- Song, Qing-Wen,Yu, Bing,Li, Xue-Dong,Ma, Ran,Diao, Zhen-Feng,Li, Rong-Guan,Li, Wei,He, Liang-Nian
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supporting information
p. 1633 - 1638
(2014/03/21)
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- Alkoxide-functionalized imidazolium betaines for CO2 activation and catalytic transformation
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Alkoxide-functionalized imidazolium betaines (AFIBs), including an alkoxide anion and an imidazolium cation, were synthesized by treating potassium tert-butoxide with 1-(2-hydroxyethyl)-2,3-disubstituted imidazolium bromide. The novel betaines were able to quickly capture CO2, affording carboxylate zwitterions (AFIB-CO2 adducts). In the presence of adventitious water, the transformation of the AFIB-CO2 adducts into the corresponding bicarbonate salts was observed by 1H and 13C NMR spectroscopy. The structures of the AFIB bicarbonate salts were solved using single crystal X-ray crystallography. Furthermore, the dithiocarboxylate zwitterions (AFIB-CS2 adducts), which are more stable to moisture in comparison with their CO2 adducts, were prepared by reacting CS2 with the corresponding betaines. X-Ray single crystal analysis revealed the bent geometry of the binding CS2 in the dithiocarboxylate zwitterions with a S-C-S angle of 126.6-126.9°, which indirectly confirms the structures of the AFIB-CO2 adducts in hand. These AFIB-CO2 adducts were found to function as organocatalysts for the coupling reaction of propargylic alcohols with CO 2 for selectively producing valuable cyclic carbonates under mild and solvent-free reaction conditions. the Partner Organisations 2014.
- Wang, Yan-Bo,Sun, Dong-Sheng,Zhou, Hui,Zhang, Wen-Zhen,Lu, Xiao-Bing
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p. 2266 - 2272
(2014/04/17)
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- Polystyrene-supported N-heterocyclic carbene-silver complexes as robust and efficient catalysts for the reaction of carbon dioxide and propargylic alcohols
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Three polystyrene-supported N-heterocyclic carbene-silver complexes [PS-NHC-Ag(I)] and a polystyrene-supported N-heterocyclic carbene-copper complex [PS-NHC-Cu(I)] catalyst were synthesized and characterized by elemental analysis, Fourier transform infrared spectroscopy, inductively coupled plasma-atom emission spectrometer, thermogravimetric analysis and scanning electron micrographs. The catalytic activity of the supported catalysts was investigated for the reaction of propargylic alcohols and carbon dioxide. PS-NHC-Cu(I) showed no catalytic activity to the reaction, while PS-NHC-Ag(I) showed a considerable high activity and selectivity for the reaction, yielding the corresponding α-alkylidene cyclic carbonates in high to excellent yields under mild conditions. Most importantly, the supported catalysts could be separated easily from the products and reused up to 15 times without loss of their high catalytic activity, showing excellent stability. The effect of various reaction parameters such as carbon dioxide pressure, temperature, time, and catalyst loading on the reaction was also investigated. Copyright
- Tang, Xiaodong,Qi, Chaorong,He, Haitao,Jiang, Huanfeng,Ren, Yanwei,Yuan, Gaoqing
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supporting information
p. 2019 - 2028
(2013/08/23)
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- Fast CO2 sequestration, activation, and catalytic transformation using N -heterocyclic olefins
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N-Heterocyclic Olefin (NHO) with high electronegativity at the terminal carbon atom was found to show a strong tendency for CO2 sequestration, affording a CO2 adduct (NHO-CO2). X-ray single crystal analysis revealed the bent geometry of the binding CO2 in the NHO-CO2 adducts with an O-C-O angle of 127.7-129.9, dependent on the substitute groups of N-heterocyclic ring. The length of the C carboxylate-CNHO bond is in the range of 1.55-1.57 A, significantly longer than that of the Ccarboxylate-C NHC bond (1.52-1.53 A) of the previously reported NHC-CO 2 adducts. The FTIR study by monitoring the ν(CO2) region of transmittance change demonstrated that the decarboxylation of NHO-CO2 adducts is easier than that of the corresponding NHC-CO 2 adducts. Notably, the NHO-CO2 adducts were found to be highly active in catalyzing the carboxylative cyclization of CO2 and propargylic alcohols at mild conditions (even at ambient temperature and 0.1 MPa CO2 pressure), selectively giving α-alkylidene cyclic carbonates in good yields. The catalytic activity is about 10-200 times that of the corresponding NHC-CO2 adducts at the same conditions. Two reaction paths regarding the hydrogen at the alkenyl position of cyclic carbonates coming from substrate (path A) or both substrate and catalyst (path B) were proposed on the basis of deuterium labeling experiments. The high activity of NHO-CO2 adduct was tentatively ascribed to its low stability for easily releasing the CO2 moiety and/or the desired product, a possible rate-limiting step in the catalytic cycle.
- Wang, Yan-Bo,Wang, Yi-Ming,Zhang, Wen-Zhen,Lu, Xiao-Bing
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supporting information
p. 11996 - 12003
(2013/09/02)
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- Effective guanidine-catalyzed synthesis of carbonate and carbamate derivatives from propargyl alcohols in supercritical carbon dioxide
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The reactions of propargyl alcohols with carbon dioxide in supercritical carbon dioxide or in acetonitrile with gaseous carbon dioxide in the presence of organic bases as catalysts have been examined. Bicyclic guanidines are effective catalysts for the formation of α-methylene cyclic carbonates under mild reaction conditions. Oxoalkyl carbonates, oxoalkyl carbamates or α-methyleneoxazolidinones are obtained in high yields and good selectivities in one-step starting from propargyl alcohols and an external nucleophile (alcohols or amines) using bicyclic guanidines as catalysts in supercritical carbon dioxide. Propargylic diols under the same reaction conditions underwent a rearrangement process instead of carbon dioxide insertion whereas in the presence of an external nucleophile the formation of oxocarbonates, oxocarbamates or cyclic carbamates was achieved in satisfactory yields.
- Ca', Nicola Della,Gabriele, Bartolo,Ruffolo, Giuseppe,Veltri, Lucia,Zanetta, Tito,Costa, Mirco
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supporting information; experimental part
p. 133 - 146
(2011/04/18)
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- Silver-catalyzed carbon dioxide incorporation and rearrangement on propargylic derivatives
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A silver/DBU catalyst system was developed for the effective synthesis of cyclic carbonate and oxazolidinone from the reaction of CO2 with propargylic alcohols and propargylic amines, respectively, in high yields under mild conditions. It was f
- Kikuchi, Satoshi,Yoshida, Shunsuke,Sugawara, Yuudai,Yamada, Wataru,Cheng, Hau-Man,Sekine, Kohei,Iwakura, Izumi,Ikeno, Taketo,Yamada, Tohru
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experimental part
p. 698 - 717
(2011/09/14)
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- Electrochemically catalyzed synthesis of cyclic carbonates from CO 2 and propargyl alcohols
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A convenient and efficient electrochemical method has been developed for the synthesis of the α-alkylidene cyclic carbonates from carbon dioxide (CO2) and propargyl alcohols at room temperature. The electrosynthesis was successfully carried out with a copper anode and a nickel cathode in an undivided cell containing n-Bu4NBr-MeCN electrolyte with a constant current under 3 MPa pressure of CO2, and the α-alkylidene cyclic carbonates were obtained in good to excellent isolated yields in the secondary and tertiary terminal propargylic alcohols cases. The experimental results show that the electrogenerated Cu+ ions and strong bases in situ could efficiently catalyze or promote the coupling reaction under the cooperation of electrolytic medium MeCN and supporting electrolyte n-Bu4NBr. The plausible mechanism of the coupling reaction was also discussed briefly.
- Yuan, Gao-Qing,Zhu, Guo-Jun,Chang, Xiao-Ying,Qi, Chao-Rong,Jiang, Huan-Feng
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experimental part
p. 9981 - 9985
(2011/02/22)
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- Gold-catalyzed rearrangement of propargylic tert-butyl carbonates
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Diversely substituted 4-alkylidene-1,3-dioxolan-2-ones are efficiently synthesized by a gold(I)-catalyzed rearrangement of propargylic tert-butyl carbonates. The substrates are readily accessible and the transformation, which is performed under mild react
- Buzas, Andrea K.,Istrate, Florin M.,Gagosz, Fabien
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experimental part
p. 1889 - 1901
(2009/06/20)
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- 1,3-Dialkylimidazolium-2-carboxylates as versatile N-heterocyclic carbene-CO2 adducts employed in the synthesis of carboxylates and α-alkylidene cyclic carbonates
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1,3-Dialkylimidazolium-2-carboxylate compounds of formulas 1a, 2, and 4 have been synthesized and fully characterized by X-ray spectroscopy quite recently. Up today, these compounds have found some interesting applications as precursors of N-heterocyclic carbenes (NHCs) used as ligands for metal-complexes or in the synthesis of organic compounds and ionic liquids. We have recently reported the use of 1-butyl, 3-methylimidazolium-2-carboxylate and 1,3-dimethylimidazolium-2-carboxylate in a CO2-transfer reaction to CH3OH and acetophenone for the synthesis of methylcarbonate and benzoylacetate. The scope of this CO2-transfer reaction has been expanded to several organic compounds with active hydrogen (acetone, cyclohexanone, and benzylcyanide) for the synthesis of carboxylates of pharmaceutical interest, and to propargyl alcohols for the synthesis of α-alkylidene cyclic carbonates.
- Tommasi, Immacolata,Sorrentino, Fabiana
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body text
p. 104 - 107
(2009/04/14)
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- Silver-catalyzed incorporation of carbon dioxide into propargylic alcohols
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The combined use of a catalytic amount of silver acetate and a stoichiometric amount of DBU efficiently catalyzed the incorporation of CO 2 under mild reaction conditions into a wide range of propargylic alcohols bearing a terminal or an intern
- Yamada, Wataru,Sugawara, Yudai,Hau, Man Cheng,Ikeno, Taketo,Yamada, Tohru
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p. 2604 - 2607
(2008/02/06)
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- Gold(I)-catalyzed formation of 4-alkylidene-1,3-dioxolan-2-ones from propargylic tert-butyl carbonates
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A study concerning the gold(I)-catalyzed rearrangement of propargylic tert-butyl carbonates into 4-alkylidene-1,3-dioxolan-2-ones is described. The mild reaction conditions employed allow the efficient synthesis of a variety of cyclic carbonates that would be less conveniently obtained using reported methods. Variability in the structure of the final product has been observed and is significantly dependent on the nature of the substituent attached to the alkyne moiety.
- Buzas, Andrea,Gagosz, Fabien
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p. 515 - 518
(2007/10/03)
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- Ionic Liquid as an Efficient Promoting Medium for Fixation of CO 2: Clean Synthesis of α-Methylene Cyclic Carbonates from CO2 and Propargyl Alcohols Catalyzed by Metal Salts under Mild Conditions
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Reactions of propargylic alcohols with CO2 in a [BMIm][PhSO 3]/CuCl catalytic system to produce the corresponding α-methylene cyclic carbonates were conducted with high yields. Mild reaction conditions, enhanced rates, improved yields, and recyclable ionic liquid catalyst systems are the remarkable features exhibited in this process. Furthermore, the use of large amounts of tertiary amines as well as nitrogen-containing organic solvent as employed in previously studies was avoided.
- Gu, Yanlong,Shi, Feng,Deng, Youquan
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p. 391 - 394
(2007/10/03)
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- Catalytic formation of carbamates and cyclic carbonates by copper complex of 2,5,19,22-tetraaza[6,6](1,1′)ferrocenophane-1,5-diene X-ray crystal structure of [Cu(1)]PF6
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The reaction of [Cu(MeCN)4]PF6 with a ferrocene-containing tetraazamacrocycle 2,5,19,22-tetraaza[6,6](1,1)ferrocenophane-1,5-diene (1) gives the copper(I) complex of the type [Cu(1)]PF6 (2) which crystallizes in the orthorhombic system: P212121 (#19); a = 7.597(2) A, b = 14.805(5) A, c = 24.194(4) A; Z = 4; R = 0.080; Rw = 0,083. The geometry around the central metal is a distorted tetrahedron with two pairs of differing Cu-N bond length. This complex has demonstrated the excellent catalytic activity toward the formation of cyclic carbonates and carbamates in the presence of CO2, giving almost quantitative product yields in most reactions that have been employed.
- Kim, Hak-Soo,Kim, Jeong-Won,Kwon, Soon-Chul,Shim, Sang-Chul,Kim, Tae-Jeong
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p. 337 - 344
(2007/10/03)
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- Functional Carbonates: Cyclic α-Methylene and β-Oxopropyl Carbonates from Prop-2-ynyl Derivatives and CO2
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The phosphine-catalysed synthesis of cyclic α-methylene carbonates 2 directly from prop-2-ynyl alcohol derivatives and CO2 is described.These cyclic carbonates 2 are key intermediates for the selective access to β-oxopropyl carbonates 3 by reaction with alcohols under mild conditions, but in the presence of Et3N or KCN as catalyst.
- Joumier, Jean Marc,Fournier, Jean,Bruneau, Christian,Dixneuf, Pierre H.
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p. 3271 - 3274
(2007/10/02)
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- PHOSPHINE CATALYSED SYNTHESIS OF UNSATURATED CYCLIC CARBONATES FROM CARBON DIOXIDE AND PROPARGYLIC ALCOHOLS
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A new route to α-methylene cyclic carbonates is reported, by direct reaction of carbon dioxide with α-ethynyl alcohols in the presence of a catalytic amount of a phosphine.
- Furnier, Jean,Bruneau, Christian,Dixneuf, Pierre H.
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p. 3981 - 3982
(2007/10/02)
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