Cycloaddition Of Epoxides Research Articles

Synthesis of Cyclic Carbonates from Alkenyl and Alkynyl Substrates

AbstractAs an extensively used chemical product, cyclic carbonate was generally synthesized by transesterification, or the cycloaddition of epoxides, diols with CO2. To reduce the production costs and expand the raw materials, alkenyl and alkynyl substrates have caused much attention in the synthesis of cyclic carbonates, such as olefins, allyl alcohols and propargylic alcohols. Based on the alkenyl substrate, the synthetic process involves a continuous reaction of oxidative carboxylation, with epoxide or halohydrin as an intermediate usually. Therefore, peroxides and nucleophiles (halogens or organic bases) are often necessary in the conversion. Using propargylic alcohols to produce α‐alkylidene cyclic carbonates, noble metal catalysts play crucial roles in alkynyl activation, and organic bases are considered to assist the intramolecular and intermolecular proton transfer and combine CO2 molecular. As the carboxyl sources in products, inorganic carbonates and organic carboxylic acids also have some applications instead of CO2. In this review, we summarized the synthetic routes of cyclic carbonates from alkenyl and alkynyl substrates in the aspect of catalyst, mechanism and the development tendency.

Multifunctional Mesoporous Ionic Gels and Scaffolds Derived from Polyhedral Oligomeric Silsesquioxanes.

A new methodology for fabrication of inorganic-organic hybrid ionogels and scaffolds is developed through facile cross-linking and solution extraction of a newly developed ionic polyhedral oligomeric silsesquioxane with inorganic core. Through design of various cationic tertiary amines, as well as cross-linkable functional groups on each arm of the inorganic core, high-performance ionogels are fabricated with excellent electrochemical stability and unique ion conduction behavior, giving superior lithium ion battery performance. Moreover, through solvent extraction of the liquid components, hybrid scaffolds with well-defined, interconnected mesopores are utilized as heterogeneous catalysts for the CO2-catalyzed cycloaddition of epoxides. Excellent catalytic performance, as well as highly efficient recyclability are observed when compared to other previous literature materials.

Imidazolinium based porous hypercrosslinked ionic polymers for efficient CO2 capture and fixation with epoxides

2-Phenylimidazoline based porous hypercrosslinked ionic polymers afforded high yields in the cycloaddition of epoxides with ambient or diluted CO2 (0.15 bar CO2 and 0.85 bar N2) under low or room temperature.

Scalable and super-stable exfoliation of graphitic carbon nitride in biomass-derived γ-valerolactone: enhanced catalytic activity for the alcoholysis and cycloaddition of epoxides with CO2

γ-Valerolactone could exfoliate bulk g-C3N4 to form a super-stable dispersion of few-layer g-C3N4 nanosheets with a high concentration of 0.8 mg mL−1, showing enhanced activity for non-photocatalytic reactions.

A chiral salen-based MOF catalytic material with high thermal, aqueous and chemical stabilities.

A highly stable chiral salen-based metal-organic framework [(Cu4I4)2L4]·20DMF·3CH3CN (1) [L = (R,R)-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene)-1,2-diphenylethylenediamine nickel(ii)] has been synthesized and characterized by single crystal X-ray diffraction and other physicochemical methods. 1 exhibits a rare 8-fold interpenetrated 3D framework constructed by a 4-connecting Cu4I4 cluster and a 2-coordinating L ligand. Remarkably, in spite of 8-fold interpenetration, 1 still possesses two types of 1D chiral hydrophobic channels with pore window sizes of 6.77 × 8.64 Å2 and 6.09 × 10.96 Å2 along the crystallographic a axis. All Ni(salen) moieties of L lie inside the 1D channels and the empty coordination sites of Ni2+ are oriented to the cavities. PXRD and N2 adsorption measurements confirmed that 1 is extremely stable under high temperature (>400 °C), in water vapor (90% relative humidity), in acid/base aqueous solution (pH 0-14), and in saturated NaOH solution at 100 °C, as well as in 30 wt% H2O2 and 70 wt% tert-butyl hydroperoxide solution. 1 was proved to be an excellent recycled heterogeneous catalyst for the conversion of simulated industrial CO2 (that is, involving tiny amounts of water vapor and other acidic gases) with epoxides into cyclic carbonates under mild conditions for the first time. The synthesis of β-hydroxy-1,2,3-triazoles from the same epoxides, alkyne and sodium azide was also catalyzed by 1 in aqueous solution with high yield. Interestingly, the cycloaddition reaction of CO2 to bulky epoxides shows a decrease in the activity with an increase in the alkyl chain length of the substrate because of confinement of the channel size of 1, showing size-dependent selectivity. The plausible catalytic mechanisms for these two reactions have also been proposed.

Noncovalent immobilization of pyrene-terminated hyperbranched triazole-based polymeric ionic liquid onto graphene for highly active and recyclable catalysis of CO2/epoxide cycloaddition

Combination of bifunctional HBP and rGO for highly active, selective and recyclable catalysis for CO2/epoxide cycloaddition.

Inverse relationship of dimensionality and catalytic activity in CO2transformation: a systematic investigation by comparing multidimensional metal–organic frameworks

The correlation between dimensionality and active sites on deciding the catalytic performance of an MOF catalyst in CO2–epoxide cycloaddition reactions has been studied.

Porous Ionic Polymers as a Robust and Efficient Platform for Capture and Chemical Fixation of Atmospheric CO2.

Direct use of atmospheric CO2 as a C1 source to synthesize high-value chemicals through environmentally benign processes is of great interest, yet challenging. Porous heterogeneous catalysts that are capable of simultaneously capturing and converting CO2 are promising candidates for such applications. Herein, a family of organic ionic polymers with nanoporous structure, large surface area, strong affinity for CO2 , and very high density of catalytic active sites (halide ions) was synthesized through the free-radical polymerization of vinylfunctionalized quaternary phosphonium salts. The resultant porous ionic polymers (PIPs) exhibit excellent activities in the cycloaddition of epoxides with atmospheric CO2 , outperforming the corresponding soluble phosphonium salt analogues and ranking among the highest of known metal-free catalytic systems. The high CO2 uptake capacity of the PIPs facilitates the enrichment of CO2 molecules around the catalytic centers, thereby benefiting its conversion. We have demonstrated for the first time that atmospheric CO2 can be directly converted to cyclic carbonates at room temperature using a heterogeneous catalytic system under metal-solvent free conditions. Moreover, the catalysts proved to be robust and fully recyclable, demonstrating promising potential for practical utilization for the chemical fixation of CO2 . Our work thereby paves a way to the advance of PIPs as a new type of platform for capture and conversion of CO2 .

New rht-Type Metal-Organic Frameworks Decorated with Acylamide Groups for Efficient Carbon Dioxide Capture and Chemical Fixation from Raw Power Plant Flue Gas.

The combination of carbon dioxide capture and chemical fixation in a one-pot process is attractive for both chemists and governments. The cycloaddition of carbon dioxide with epoxides to produce cyclic carbonates is an atomic economical reaction without any side products. By incorporating acylamide to enhance the binding affinity toward CO2, new rht-type metal-organic frameworks (MOFs) with (3, 28) and (3, 24) connected units were constructed. Zn-NTTA with two types of dinuclear paddlewheel building blocks-{Zn2(OOC-)4} and {Zn2(OOC-)3}. The high uptake of CO2 (115.6 cm3·g-1) and selectivity over N2 (30:1) at 273 K indicated that these MOFs are excellent candidates for postcombustion CO2 isolation and capture. The MOFs feature high catalytic activity, rapid dynamics of transformation and excellent stability with turnover number (TON) values up to 110 000 per paddlewheel unit after 5 × 6 rounds of recyclability, demonstrating that they are promising heterogeneous catalysts for CO2 cyclo-addition to value-added cyclic carbonates. The cycloaddition of epoxides with wet gases demonstrated that the catalyst activity was not affected by moisture, and the indices of the PXRD patterns of the bulk samples filtered from the catalytic reaction revealed that the crystallinities were maintained. The combination of the selective capture and catalytic transformation in one-pot enables the use of a negative-cost feedstock-raw power plant flue gas without any separation and purification-revealing the broad prospects of such MOFs for practical CO2 fixation in industry.

“Fiddler crab-type” imidazolium salt as remote substituents tuning organocatalyst for the cycloaddition of epoxides with carbon dioxide

A series of unsymmetrical pyridine-bridged pincer-type imidazolium salts are synthesized and demonstrated as highly active catalyst. This catalyst is for the cycloaddition of carbon dioxide with a broad range of terminal epoxides without organic solvent, and co-catalyst. The performance of catalyst considerably depends on the remote structural feature bearing pyridine ring. In addition, bulky internal epoxide is efficiently converted to the desired product. The robustness of the catalytic system is shown by recycling the catalyst over seven consecutive times without significant loss of activity.

ChemInform Abstract: Cooperative Calcium‐Based Catalysis with 1,8‐Diazabicyclo[5.4.0]‐undec‐7‐ene for the Cycloaddition of Epoxides with CO2 at Atmospheric Pressure.

ChemInformVolume 47, Issue 38 Heterocyclic Compounds ChemInform Abstract: Cooperative Calcium-Based Catalysis with 1,8-Diazabicyclo[5.4.0]-undec-7-ene for the Cycloaddition of Epoxides with CO2 at Atmospheric Pressure. Xi Liu, Xi Liu Inst. Elem.-Org. Chem., Nankai Univ., Tianjin 300071, Peop. Rep. ChinaSearch for more papers by this authorShuai Zhang, Shuai Zhang Inst. Elem.-Org. Chem., Nankai Univ., Tianjin 300071, Peop. Rep. ChinaSearch for more papers by this authorQing-Wen Song, Qing-Wen Song Inst. Elem.-Org. Chem., Nankai Univ., Tianjin 300071, Peop. Rep. ChinaSearch for more papers by this authorXiao-Fang Liu, Xiao-Fang Liu Inst. Elem.-Org. Chem., Nankai Univ., Tianjin 300071, Peop. Rep. ChinaSearch for more papers by this authorRan Ma, Ran Ma Inst. Elem.-Org. Chem., Nankai Univ., Tianjin 300071, Peop. Rep. ChinaSearch for more papers by this authorLiang-Nian He, Liang-Nian He Inst. Elem.-Org. Chem., Nankai Univ., Tianjin 300071, Peop. Rep. ChinaSearch for more papers by this author Xi Liu, Xi Liu Inst. Elem.-Org. Chem., Nankai Univ., Tianjin 300071, Peop. Rep. ChinaSearch for more papers by this authorShuai Zhang, Shuai Zhang Inst. Elem.-Org. Chem., Nankai Univ., Tianjin 300071, Peop. Rep. ChinaSearch for more papers by this authorQing-Wen Song, Qing-Wen Song Inst. Elem.-Org. Chem., Nankai Univ., Tianjin 300071, Peop. Rep. ChinaSearch for more papers by this authorXiao-Fang Liu, Xiao-Fang Liu Inst. Elem.-Org. Chem., Nankai Univ., Tianjin 300071, Peop. Rep. ChinaSearch for more papers by this authorRan Ma, Ran Ma Inst. Elem.-Org. Chem., Nankai Univ., Tianjin 300071, Peop. Rep. ChinaSearch for more papers by this authorLiang-Nian He, Liang-Nian He Inst. Elem.-Org. Chem., Nankai Univ., Tianjin 300071, Peop. Rep. ChinaSearch for more papers by this author First published: 01 September 2016 https://doi.org/10.1002/chin.201638140Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume47, Issue38September, 2016 RelatedInformation

Ionic liquids-functionalized porphyrins as bifunctional catalysts for cycloaddition of carbon dioxide to epoxides

Six ionic liquids-functionalized metallophorphyrins have been designed, prepared and characterized by NMR, MS and elemental analysis. They were applied as efficient bifunctional catalysts to the cycloaddition of epoxides and carbon dioxide without additive and organic solvent yielding cyclic carbonates. 5,15-Di[4-(4-tributylammoniobutoxy)phenyl]porphyrin zinc(II) dibromide (JBp) and 5,15-di[3-(4-tributylammoniobutoxy)phenyl]porphyrin zinc(II) dibromide (JBm) have been demonstrated excellent activities under optimized conditions. It has been found that both the structure of porphyrin complex cations and the anion moieties would strongly affect their catalytic performance. The catalysts were versatile for the cycloaddition of CO2 to various terminal epoxides in satisfying yields with excellent selectivities. Moreover, phenoxypropylene carbonate was able to be obtained under atmosphere pressure of CO2 and in large-scale. Furthermore, a plausible mechanism involving Lewis acid-base synergistic catalysis has been proposed according to our experimental results.

Dinuclear Aluminum Poly(phenolate) Complexes as Efficient Catalysts for Cyclic Carbonate Synthesis

A series of dinuclear aluminum complexes 1–4 stabilized by amine-bridged poly(phenolato) ligands have been synthesized, which are highly active in catalyzing the cycloaddition of epoxides and CO2. In the presence of 0.3 mol % complex 3 and 0.9 mol % NBu4Br at 1 bar CO2 pressure, terminal epoxides bearing different functional groups were converted to cyclic carbonates in 60–97% yields. Complex 3 is one of the rare examples of Al-based catalysts capable of promoting the cycloaddition at 1 bar pressure of CO2. Moreover, reactions of more challenging disubstituted epoxides also proceeded at an elevated pressure of 10 bar and afforded cyclic carbonates in 52–90% yields.

Chiral oligomers of spiro-salencobalt(III)X for catalytic asymmetric cycloaddition of epoxides with CO2

Several new chiral oligomers of spiro-salenCo(III)X (spiro=1.1′-spirobiindane-7.7′-diol) complexes have been designed, synthesized, and characterized by nuclear magnetic resonance (NMR), infrared (IR), and elemental analyses, in which, the chiral spiro moieties are first introduced into a scaffold of chiral salenCo catalysts. They were used to catalyze the asymmetric cycloaddition of epoxides with carbon dioxide. Under very mild reaction conditions, a kinetic resolution of racemic epoxides with CO2 was smoothly initiated by these chiral oligomer catalysts with good enantioselectivities, which can be attributed to the match effect between chiral backbones of salen and spiro. High stability and easy recyclability are their major advantages.

ChemInform Abstract: An Efficient and Recyclable Tetraoxo‐Coordinated Zinc Catalyst for the Cycloaddition of Epoxides with Carbon Dioxide at Atmospheric Pressure.

AbstractVarious cyclic carbonates are synthesized from the corresponding epoxides and carbon dioxide using an efficient and recyclable catalytic system of a Zn(O)4‐coordinated complex and Bu4NI.

Metalated porous porphyrin polymers as efficient heterogeneous catalysts for cycloaddition of epoxides with CO2 under ambient conditions

We have successfully synthesized a porphyrin based porous organic polymer (POP-TPP) from free-radical polymerization of tetrastyrylporphyrin monomer under solvothermal conditions. Besides high surface area (1200m2/g) and high thermal stability, the obtained polymer features open metal chelating sites, and thus the catalytic activities of metalloporphyrins can be reasonably adjusted by introducing various metal ions. After metalation with Co3+, Zn2+, and Mg2+, the Co/POP-TPP, Zn/POP-TPP, and Mg/POP-TPP as heterogeneous catalysts are very active for cycloaddition of epoxides with CO2 to cyclic carbonates at ambient conditions with n-Bu4NBr as a nucleophilic additive. Particularly, under the relatively low CO2 concentration (15% in volume), the activity of heterogeneous Co/POP-TPP catalyst is even higher than that of the corresponding homogeneous Co/TPP catalyst. More importantly, there is no activity loss even if the Co/POP-TPP is recycled for 18 times. The excellent catalytic activity and superior recyclability of the obtained catalysts indicate that the porphyrin based porous organic polymer is a promising candidate for construction of efficient heterogeneous catalysts in the future.

Cycloaddition of epoxides and CO2 catalyzed by bisimidazole-functionalized porphyrin cobalt(iii) complexes

Bisimidazole-functionalized cobaltoporphyrin acted as efficient bifunctional catalysts to facilitate the synthesis of cyclic carbonates from epoxides and CO2.

Hollow-structured Si/SiC@C nanospheres as highly active catalysts for cycloaddition of epoxides with CO2 under mild conditions.

Hollow-structured Si/SiC@C nanospheres were prepared through a magnesiothermic reduction of resin-coated SiO2 spheres. These nanostructured materials with high surface area not only show high adsorption capacities of industrial dyes from wastewater, but also exhibit excellent catalytic activities for chemical fixation of CO2 under mild, solvent-free conditions.

DBU/benzyl bromide: an efficient catalytic system for the chemical fixation of CO2 into cyclic carbonates under metal- and solvent-free conditions

A simple, mild and inexpensive catalytic system, DBU and benzyl bromide, was developed for the cycloaddition of epoxides to ambient CO2 under metal-free and solvent-free conditions and a wide range of epoxides was converted to the corresponding cyclic carbonates with good to excellent yields (81–95%).

An efficient and recyclable tetraoxo-coordinated zinc catalyst for the cycloaddition of epoxides with carbon dioxide at atmospheric pressure

Zn(OPO)2/TBAI was developed as a highly efficient and recyclable catalyst for CO2 conversion with a TOF up to 22 000 h−1.