- Preparation of Optically Active Cyclic Carbonates and 1,2-Diols via Enantioselective Hydrogenation of α-Methylenedioxolanones Catalyzed by Chiral Ruthenium(II) Complexes
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The enantioselective hydrogenation of α-methylene-1,3-dioxolan-2-ones catalyzed by chiral (diphosphine)ruthenium complexes leads to optically active cyclic carbonates with high enantioselectivities.Their hydrolysis in methanol in the presence of potassium carbonate quantitatively affords optically active 1,2-diols.
- Gendre, Pierre Le,Braun, Thomas,Bruneau, Christian,Dixneuf, Pierre H.
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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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- 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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- Hg(OTf)2-Catalyzed cyclization of alkynyl tert-butylcarbonate leading to cyclic enol carbonate
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Mercuric triflate was shown to be a powerful catalyst for the cyclization of alkynyl tert-butylcarbonates giving rise to cyclic enol carbonates under mild conditions. Internal alkynyl carbonate affords endo cyclization product selectively, while terminal alkynyl carbonate provides only exo cyclization product.
- Yamamoto, Hirofumi,Nishiyama, Mami,Imagawa, Hiroshi,Nishizawa, Mugio
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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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- 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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- Reusable polymer-supported amine-copper catalyst for the formation of α-alkylidene cyclic carbonates in supercritical carbon dioxide
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A green, simple and effective polymer-supported catalytic system has been developed for the cyclization of propargyl alcohols with carbon dioxide (CO 2). α-Alkylidene cyclic carbonates were obtained in satisfactory isolated yields in most cases. The catalyst could be recovered by simple filtration and reused several times without significant loss of activity. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Jiang, Huan-Feng,Wang, A.-Zhong,Liu, Hai-Ling,Qi, Chao-Rong
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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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- 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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p. 889 - 897
(2021/02/09)
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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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- A dual-functional urea-linked conjugated porous polymer anchoring silver nanoparticles for highly efficient CO2conversion under mild conditions
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A dual-functional urea-linked conjugated porous polymer (UCPP) assembled by enol-imine with ordered unit arrays that act as potential anchoring sites in the networks was fabricated, and was further applied as a support for Ag nanoparticles by the coordinate interaction between them. The UCPP not only can well confine the Ag particle size and facilitate high dispersion, but also can afford special CO2-philic moieties to enhance the adsorption properties. The resulting Ag?UCPP as a heterogeneous catalyst exhibited excellent activity for the carboxylative cyclization of propargyl alcohols with CO2 under mild conditions, together with good recyclability, which is probably attributed to the synergistic effect of the UCPP on the adsorption and activation of CO2 and the immobilization of Ag nanoparticles. This work affords possible opportunities for the design and synthesis of a heterogeneous catalyst toward CO2 conversion.
- Li, Lin,Li, Wang,Li, Yuting,Liu, Xiaozhen,Wang, Jianxin,Wang, Liping,Wang, Xiaoji,Zhu, Jie
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p. 13052 - 13059
(2020/10/13)
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- Solvent-Dependent Assembly and Magnetic Relaxation Behaviors of [Cu4I3] Cluster-Based Lanthanide MOFs: Acting as Efficient Catalysts for Carbon Dioxide Conversion with Propargylic Alcohols
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Two structurally similar metal-organic frameworks (MOFs) [Dy2Cu4I3(IN)7(DMF)2]·DMF (1) and [Dy2Cu4I3(IN)7(DMA)2]·DMA (2) (HIN = isonicotinic acid) feathering different coordinated solvent molecules were successfully isolated by tuning the types of solvents in the reaction system. Structural tests indicate that 1 and 2 are both built from 1D Dy(III) chains and copper iodide clusters [Cu4I3], generating into three-dimensional frameworks with an open 1D channel along the a axis. 1 and 2 display extensive and excellent solvent stability. Magnetic studies of 1 and 2 indicate that they exhibit interesting solvent-dependent magnetization dynamics. Importantly, 1 and 2 can act as highly effective catalysts for the carboxylic cyclization of propargyl alcohols with carbon dioxide (CO2) under ambient operating conditions. Additionally, the substrate scope was further explored over compound 1 based on the optimal conditions, and it exhibits efficient cyclic carboxylation of various terminal propargylic alcohols with CO2. This research offers an effective approach for the solvent-guided synthesis of MOFs materials and also presents the great application value of MOFs in CO2 chemical conversion.
- Wu, Zhi-Lei,Gu, Ai-Ling,Gao, Ning,Cui, Hui-Ya,Wang, Wen-Min,Cui, Jian-Zhong
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supporting information
p. 15111 - 15119
(2020/11/02)
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- Tubular metal organic frameworks from the curvature of 2D-honeycombed metal coordination
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A tubular MOF with adequate active sites is prepared by the bending of metal-coordinated honeycombed frameworks via titration and shows fast catalytic kinetics with lower catalytic loading for CO2 conversion. The TON is observed to be 2300 and the corresponding TOF of up to 173 h-1 is achieved for the first time.
- Bao, Junhui,Chen, Yaju,Huang, Liping,Huang, Zhegang,Ji, Hongbing,Kim, Jehan,Wu, Shanshan,Xu, Xin,Zhang, Liwei,Zhou, Xiantai
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supporting information
p. 2403 - 2406
(2020/03/05)
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- Copper(i) iodide cluster-based lanthanide organic frameworks: Synthesis and application as efficient catalysts for carboxylative cyclization of propargyl alcohols with CO2 under mild conditions
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Two metal-organic frameworks (MOFs), namely, [Dy2Cu4I4(NA)6(DMF)2]n (1) and [Gd2Cu2I2(IN)6(DMF)4]·5DMF (2) (HNA = nicotinic acid, HIN = isonicotinic acid), constructed based on lanthanide ions and copper iodide clusters ([Cu4I4] and [Cu2I2]) were successfully synthesized and characterized. Compound 1 has a three-dimensional framework and compound 2 displays a two-dimensional plane with sql topology, respectively. Both of them exhibit high thermostability and solvent stabilities. Additionally, catalytic explorations reveal that 1 displays higher catalytic activity than 2 for the carboxylic cyclization of propargyl alcohols. More importantly, 1 also exhibits excellent catalytic performance in the carboxylation reactions of CO2 and terminal propargylic alcohols with various substituents. To the best of our knowledge, this is the first example of non-noble metal based MOF catalysts for the carboxylative cyclization of propargyl alcohols with CO2 under atmospheric pressure and at room temperature, which provides a highly promising approach for MOFs in the catalytic conversion of CO2 to valuable chemicals.
- Bai, Guoyi,Lan, Xingwang,Li, Meng,Wu, Zhilei,Zhang, Yaxin
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supporting information
p. 11063 - 11069
(2019/08/01)
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- Unusual Missing Linkers in an Organosulfonate-Based Primitive-Cubic (pcu)-Type Metal-Organic Framework for CO2 Capture and Conversion under Ambient Conditions
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A noninterpenetrated organosulfonate-based metal-organic framework (MOF) with a defective primitive-cubic (pcu) topology was successfully synthesized. The unusual missing linkers, along with the highest permanent porosity (~43%) in sulfonate-MOFs, offer a versatile platform for the incorporation of alkynophilic Ag(I) sites. The cyclic carboxylation of alkyne molecules (e.g., propargyl alcohol and propargyl amine) into α-alkylidene cyclic carbonates and oxazolidinones were successfully catalyzed by the use of Ag(I)-embedded sulfonate-MOF under atmospheric pressure of CO2. In all the three catalytic reactions using CO2 as a C1 feedstock, the highly robust sulfonate-based MOF catalyst exhibit at least three-cycle reusability.
- Zhang, Guiyang,Yang, Huimin,Fei, Honghan
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p. 2519 - 2525
(2018/03/13)
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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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- 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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- 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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- AgX@carbon (X = Br and I) as robust and efficient catalysts for the reaction of propargylic alcohols and CO2 to carbonates under ambient conditions
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Development of new efficient catalytic systems for chemical transformation of CO2 is a very attractive topic in green chemistry. In this work, we studied the synthesis of α-alkylidene cyclic carbonates through the coupling reaction between propargylic alcohols and CO2 with new silver catalysts. It was found that activated carbon supported AgX (X = Br and I) was a simple and efficient catalyst for the carboxylative cyclization of propargyl alcohols with CO2 at atmospheric pressure and room temperature. Nearly 99% yield of the desired product was obtained, and the product could be simply separated through solvent extraction. Moreover, the catalyst could be easily recovered and reused at least ten times without a decrease in the catalytic activity and selectivity. These findings are useful for the development of an environmentally friendly chemical process for the production of α-alkylidene cyclic carbonates.
- Qiu, Jikuan,Zhao, Yuling,Wang, Huiyong,Cui, Guokai,Wang, Jianji
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p. 54020 - 54026
(2016/07/06)
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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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- 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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