27797-53-1Relevant academic research and scientific papers
Efficient catalytic conversion of terminal/internal epoxides to cyclic carbonates by porous Co(ii) MOF under ambient conditions: Structure-property correlation and computational studies
Parmar, Bhavesh,Patel, Parth,Pillai, Renjith S.,Kureshy, Rukhsana I.,Khan, Noor-Ul H.,Suresh, Eringathodi
, p. 2884 - 2894 (2019)
A mixed ligand three-dimensional neutral porous framework, {[Co(OBA)(L)]xG}n (CoMOF-1) (H2OBA = 4,4′-oxybis(benzoic acid); L = (E)-N′-(pyridin-4-ylmethylene)isonicotinohydrazide; G = DMF, EtOH, MeOH, H2O), was successfully synthesized via a hydrothermal and reflux method. The activated MOF (CoMOF-1′) not only showed good affinity toward CO2 molecules, but also exhibited a good catalytic performance for CO2 conversion with a variety of terminal and internal epoxides. Grand Canonical Monte Carlo (GCMC) simulation proved the strong interactions of CO2 molecules with the amide functional groups of the MOF. The Lewis acidity of the Co(ii) centers endowed by the weakly chelated carboxylate from the OBA ligand and Lewis basicity originating from the acylamide functionality of the pyridyl-based Schiff base ligand L favored the efficient solvent-free cycloaddition reaction of CO2 with different epoxides. Strikingly, CoMOF-1′ exhibited good catalytic efficiency for CO2 coupled with various terminal epoxides at ambient temperature and pressure (1 bar, 60 °C, 12 h) and with a variety of internal epoxides at moderate reaction conditions (30 bar, 100 °C, and 8 h) with good yield and recyclability. Further, the binary heterogeneous catalyst showed good chemical stability, easy separation and recyclability (6 cycles) without a noticeable decrease in activity. To the best of our knowledge, this is the first investigation on a neutral porous MOF as a potential heterogeneous solvent-free catalyst toward CO2 utilization for internal epoxide under moderate reaction conditions. Based on the structural evidence, a plausible mechanism for the cycloaddition reaction was proposed, which is further reinforced by the relative energy of each stage obtained from periodic Density Functional Theory (DFT) calculations.
Rasta resin-DMAP and its use as a recyclable catalyst for the addition of carbon dioxide to epoxides
Lu, Jinni,Toy, Patrick H.
, p. 659 - 662 (2011)
Rasta resin-DMAP, a new heterogeneous polystyrene-based amine, has been synthesized and used as a catalyst in addition reactions of carbon dioxide to epoxides to afford cyclic carbonate products. This new material was found to be a more efficient catalyst than divinyl benzene cross-linked polystyrene- supported DMAP, and was readily recovered and reused without significant loss of catalytic activity. Georg Thieme Verlag Stuttgart - New York.
CO2 fixation by cycloaddition of mono/disubstituted epoxides using acyl amide decorated Co(II) MOF as a synergistic heterogeneous catalyst
Patel, Parth,Parmar, Bhavesh,Pillai, Renjith S.,Ansari, Amamudin,Khan, Noor-ul H.,Suresh, Eringathodi
, (2020)
Dual ligand 3D MOF {[Co(BDC)(L)]·2H2O.xG}n (CoMOF-2; G = guest) was synthesized via simple room temperature stirring method. Bulk Phase purity of CoMOF-2 was assessed by various physicochemical methods including X‐ray diffraction (XRD). CO2 adsorption isotherms indicate that activated CoMOF-2 is efficient in CO2 uptake, which has been utilized for the CO2-Epoxide cycloaddition. The catalytic ability of CoMOF-2 as a binary catalyst revealed excellent results for variety of monosubstituted epoxide under solvent‐free conditions (1 bar/40 °C/12 h). Interestingly CoMOF-2/KI also showed great potential as a heterogeneous catalyst for disubstituted epoxide (10 bar/120 °C/24 h) with high yields/selectivity. The catalytic efficiency of the present investigation for scantly explored disubstituted epoxide is better/on par with the earlier reports and the recyclability of the catalyst is an added advantage. Probable mechanism for the catalytic reaction is deduced and verified the representative energy profile for cycloaddition of CO2-Cyclohexane oxide (CHO) by DFT calculation.
Catalytic synthesis of cyclic carbonates from epoxides and carbon dioxide by magnetic UiO-66 under mild conditions
Delavari, Mahbube,Zadehahmadi, Farnaz,Tangestaninejad, Shahram,Moghadam, Majid,Mirkhani, Valiollah,Mohammadpoor-Baltork, Iraj,Kardanpour, Reihaneh
, (2017)
The catalytic activity of UiO-66@Fe3O4@SiO2 catalyst was investigated in the fixation of carbon dioxide with epoxides under mild conditions. In this manner, a facile magnetization of UiO-66 was achieved simultaneously by s
Catalytic, Kinetic, and Mechanistic Insights into the Fixation of CO2 with Epoxides Catalyzed by Phenol-Functionalized Phosphonium Salts
Hu, Yuya,Wei, Zhihong,Frey, Anna,Kubis, Christoph,Ren, Chang-Yue,Spannenberg, Anke,Jiao, Haijun,Werner, Thomas
, p. 363 - 372 (2020/11/30)
A series of hydroxy-functionalized phosphonium salts were studied as bifunctional catalysts for the conversion of CO2 with epoxides under mild and solvent-free conditions. The reaction in the presence of a phenol-based phosphonium iodide proceeded via a first order rection kinetic with respect to the substrate. Notably, in contrast to the aliphatic analogue, the phenol-based catalyst showed no product inhibition. The temperature dependence of the reaction rate was investigated, and the activation energy for the model reaction was determined from an Arrhenius-plot (Ea=39.6 kJ mol?1). The substrate scope was also evaluated. Under the optimized reaction conditions, 20 terminal epoxides were converted at room temperature to the corresponding cyclic carbonates, which were isolated in yields up to 99 %. The reaction is easily scalable and was performed on a scale up to 50 g substrate. Moreover, this method was applied in the synthesis of the antitussive agent dropropizine starting from epichlorohydrin and phenylpiperazine. Furthermore, DFT calculations were performed to rationalize the mechanism and the high efficiency of the phenol-based phosphonium iodide catalyst. The calculation confirmed the activation of the epoxide via hydrogen bonding for the iodide salt, which facilitates the ring-opening step. Notably, the effective Gibbs energy barrier regarding this step is 97 kJ mol?1 for the bromide and 72 kJ mol?1 for the iodide salt, which explains the difference in activity.
A Strained Ion Pair Permits Carbon Dioxide Fixation at Atmospheric Pressure by C-H H-Bonding Organocatalysis
Xu, Jiaxi,Xian, Anmei,Li, Zhenjiang,Liu, Jingjing,Zhang, Zhihao,Yan, Rui,Gao, Luoyu,Liu, Bo,Zhao, Lili,Guo, Kai
, p. 3422 - 3432 (2021/02/27)
The cycloadditions of carbon dioxide into epoxides to afford cyclic carbonates by H-bond donor (HBD) and onium halide (X) cocatalysis have emerged as a key strategy for CO2 fixation. However, if the HBD is also a halide receptor, the two will quench each other, decreasing the catalytic activity. Here, we propose a strained ion pair tris(alkylamino)cyclopropenium halide (TAC·X), in which TAC repels X. TAC possesses a positively charged cyclopropenium core that makes the vicinal C-H or N-H a nonclassical HBD. The interionic strain within TAC·X makes TAC a more electrophilic HBD, allowing it to activate the oxygen of the epoxide and making X more nucleophilic and better able to attack the methylene carbon of the epoxide. NMR titration spectra and computational studies were employed to probe the mechanism of the cycloaddition of CO2 to epoxides reactions under the catalysis of TAC·X. The 1H and 13C{1H}NMR titration spectra of the catalyst with the epoxide substrate unambiguously confirmed H-bonding between TAC and the epoxide. DFT computational studies identified the transition states in the ring-opening of the epoxide (TS1) and in the ring-closure of the cyclic carbonate (TS2).
Synthesis of cyclic carbonates by ruthenium(VI) bis -imido porphyrin/TBACl-catalyzed reaction of epoxide with CO2
Damiano, Caterina,Sonzini, Paolo,Intrieri, Daniela,Gallo, Emma
, p. 809 - 816 (2020/01/21)
The catalytic activity of the ruthenium(VI) bis-imido porphyrin complex/TBACl binary system in promoting the CO2 cycloaddition to epoxides forming cyclic carbonates is here reported. The system was very efficient in catalyzing the conversion of differently substituted epoxides under mild experimental conditions (100 degC and 0.6 MPa of CO2). Even if the sole TBACl resulted active under the optimized experimental conditions, the addition of ruthenium species was fundamental to maximizing the reaction productivity both in terms of epoxide conversions and cyclic carbonate selectivities. A preliminary mechanistic study indicated a positive role of ruthenium imido nitrogen atom in activating carbon dioxide.
Scalable, Durable, and Recyclable Metal-Free Catalysts for Highly Efficient Conversion of CO2 to Cyclic Carbonates
Li, Bo,Wu, Guang-Peng,Xie, Rui,Yang, Guan-Wen,Yang, Li,Zhang, Yao-Yao
supporting information, p. 23291 - 23298 (2020/10/19)
A series of highly active organoboron catalysts for the coupling of CO2 and epoxides with the advantages of scalable preparation, thermostability, and recyclability is reported. The metal-free catalysts show high reactivity towards a wide scope of cyclic carbonates (14 examples) and can withstand a high temperature up to 150 °C. Compared with the current metal-free catalytic systems that use mol % catalyst loading, the catalytic capacity of the catalyst described herein can be enhanced by three orders of magnitude (epoxide/cat.=200 000/1, mole ratio) in the presence of a cocatalyst. This feature greatly narrows the gap between metal-free catalysts and state-of-the-art metallic systems. An intramolecular cooperative mechanism is proposed and certified on the basis of investigations on crystal structures, structure–performance relationships, kinetic studies, and key reaction intermediates.
NNC-Scorpionate Zirconium-Based Bicomponent Systems for the Efficient CO2Fixation into a Variety of Cyclic Carbonates
Fernández-Baeza, Juan,Garcés, Andrés,Lara-Sánchez, Agustín,Martínez-Ferrer, Jaime,Navarro, Marta,Rodríguez, Ana M.,Sánchez-Barba, Luis F.,Sobrino, Sonia
supporting information, p. 12422 - 12430 (2020/09/15)
Two new derivatives of the bis(3,5-dimethylpyrazol-1-yl)methane modified by introduction of organosilyl groups on the central carbon atom, one of which bearing a chiral fragment, have been easily prepared. We verified the potential utility of these compou
An Aminopyridinium Ionic Liquid: A Simple and Effective Bifunctional Organocatalyst for Carbonate Synthesis from Carbon Dioxide and Epoxides
Al-Harrasi, Ahmed,Ebrahimi, Amirhossein,Khosravi, Hormoz,Rezazadeh, Mostafa,Rostami, Ali
, p. 1587 - 1595 (2020/08/05)
An aminopyridinium ionic liquid is presented as a green, tunable, and active metal-free one-component catalytic system for the atom-efficient transformation of oxiranes and CO2 to cyclic carbonates. Inclusion of a positively charged moiety into aminopyridines, through a simple single-step synthesis, provides a one-component ionic liquid catalytic system with superior activity; effective in ring opening of epoxide, CO2 inclusion, and stabilization of oxoanionic intermediates. An efficiency assessment of a variety of positively charged aminopyridines was pursued, and the impact of temperature, catalyst loading, and the kind of nucleophile on the catalytic performance was also investigated. Under solvent-free conditions, this bifunctional organocatalytic system was used for the preparation of 18 examples of cyclic carbonates from a broad range of alkyl- and aryl-substituted oxiranes and CO2, where up to 98 percent yield and high selectivity were achieved. DFT calculations validated a mechanism in which nucleophilic ring-opening and CO2 inclusion occur simultaneously towards cyclic carbonate formation.
