184007-11-2Relevant articles and documents
Preparation of Optically Active Cyclic Carbonates and 1,2-Diols via Enantioselective Hydrogenation of α-Methylenedioxolanones Catalyzed by Chiral Ruthenium(II) Complexes
Gendre, Pierre Le,Braun, Thomas,Bruneau, Christian,Dixneuf, Pierre H.
, p. 8453 - 8455 (1996)
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.
Electrochemically catalyzed synthesis of cyclic carbonates from CO 2 and propargyl alcohols
Yuan, Gao-Qing,Zhu, Guo-Jun,Chang, Xiao-Ying,Qi, Chao-Rong,Jiang, Huan-Feng
, p. 9981 - 9985 (2010)
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.
Bifunctional silver(I) complex-catalyzed CO2 conversion at ambient conditions: Synthesis of α-methylene cyclic carbonates and derivatives
Song, Qing-Wen,Chen, Wei-Qiang,Ma, Ran,Yu, Ao,Li, Qiu-Yue,Chang, Yao,He, Liang-Nian
, p. 821 - 827 (2015)
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.
Hg(OTf)2-Catalyzed cyclization of alkynyl tert-butylcarbonate leading to cyclic enol carbonate
Yamamoto, Hirofumi,Nishiyama, Mami,Imagawa, Hiroshi,Nishizawa, Mugio
, p. 8369 - 8373 (2006)
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.
Highly efficient synthesis of alkylidene cyclic carbonates from low concentration CO2using hydroxyl and azolate dual functionalized ionic liquids
Shi, Guiling,Zhai, Ran,Li, Haoran,Wang, Congmin
, p. 592 - 596 (2021)
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.
A highly stable polyoxovanadate-based Cu(i)-MOF for the carboxylative cyclization of CO2with propargylic alcohols at room temperature
Dang, Tian-Yi,Li, Zhuo,Liu, Shu-Mei,Liu, Shu-Xia,Lu, Ying,Tian, Hong-Rui,Zhang, Zhong
, p. 7513 - 7520 (2020)
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
Reusable polymer-supported amine-copper catalyst for the formation of α-alkylidene cyclic carbonates in supercritical carbon dioxide
Jiang, Huan-Feng,Wang, A.-Zhong,Liu, Hai-Ling,Qi, Chao-Rong
, p. 2309 - 2312 (2008)
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.
Tuning the basicity of ionic liquids for efficient synthesis of alkylidene carbonates from CO2 at atmospheric pressure
Chen, Kaihong,Shi, Guiling,Dao, Rina,Mei, Ke,Zhou, Xiuyuan,Li, Haoran,Wang, Congmin
, p. 7830 - 7833 (2016)
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.
Copper-catalysed synthesis of α-alkylidene cyclic carbonates from propargylic alcohols and CO2
Cervantes-Reyes, Alejandro,Farshadfar, Kaveh,Rudolph, Matthias,Rominger, Frank,Schaub, Thomas,Ariafard, Alireza,Hashmi
supporting information, p. 889 - 897 (2021/02/09)
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.
Synthesis of α-alkylidene cyclic carbonatesviaCO2fixation under ambient conditions promoted by an easily available silver carbamate
Bresciani, Giulio,Bortoluzzi, Marco,Ghelarducci, Claudia,Marchetti, Fabio,Pampaloni, Guido
, p. 4340 - 4346 (2021/03/15)
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.
