- Coupling reactions of CO2 with neat epoxides catalyzed by PPN salts to yield cyclic carbonates
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The off-the-shelf reagent PPN+Cl- and PPN-manganese carbonylates [PPN]+[Mn(CO)4L]- (L = CO, PPh3) are good catalysts for the coupling reactions of CO2 with neat epoxides without the use of organic solvents to afford cyclic carbonates. PPN salts with weak nucleophilic anions such as PPN +BF4- and PPN+OTf- are, however, inactive for the coupling reactions.
- Sit, Wing Nga,Ng, Siu Man,Kwong, Kar Yan,Lau, Chak Po
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- Co(III) porphyrin/DMAP: An efficient catalyst system for the synthesis of cyclic carbonates from CO2 and epoxides
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CoTPP(Cl)/DMAP was found to be a highly active catalyst system for the chemical fixation of CO2 via reaction with epoxides. The corresponding cyclic carbonate products are produced in high yield and selectivity for a variety of terminal mono and disubstituted epoxides. 1,2-Disubstituted internal epoxides were also investigated as substrates and found to react with very high stereospecificity.
- Paddock, Robert L.,Hiyama, Yaeko,McKay, Jonathan M.,Nguyen, SonBinh T.
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- Highly Active Chromium Complexes Supported by Constrained Schiff-Base Ligands for Cycloaddition of Carbon Dioxide to Epoxides
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Novel constrained Schiff-base ligands (inden) were developed based on the well-known salen ligands. Chromium complexes supported by the constrained inden ligands were successfully synthesized and used as catalysts for the synthesis of cyclic carbonates from epoxides and carbon dioxide (CO2). The catalyst having tert-butyl (tBu) groups as substituents in combination with tetrabutylammonium bromide (TBAB) as a cocatalyst exhibited very high catalytic activity with a turnover frequency of up to 14800 h-1 for the conversion of CO2 and propylene oxide into propylene carbonate exclusively at 100 °C and 300 psi of CO2 under solvent-free conditions. The catalyst was found to be highly active for various epoxide substrates to produce terminal cyclic carbonates in 100% selectivity.
- Kiriratnikom, Jiraya,Laiwattanapaisarn, Nattiya,Vongnam, Kunnigar,Thavornsin, Nopparat,Sae-Ung, Pornpen,Kaeothip, Sophon,Euapermkiati, Anucha,Namuangruk, Supawadee,Phomphrai, Khamphee
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- A novel and effective Ni complex catalyst system for the coupling reactions of carbon dioxide and epoxides
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The coupling of carbon dioxide and mono-substituted terminal epoxides or cyclohexene oxide to form cyclic carbonates under a Ni complex catalyst system without using additional organic solvents was achieved in excellent selectivity and TOF.
- Li, Fuwei,Xia, Chungu,Xu, Liwen,Sun, Wei,Chen, Gexin
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- A Thermomorphic Polyethylene-Supported Imidazolium Salt for the Fixation of CO2 into Cyclic Carbonates
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An imidazolium catalyst supported on thermomorphic polyethylene (PE) was prepared from 1-methylimidazole and polyethylene iodide (PE?I). The catalyst was characterized by 1H and 13C NMR, SEC and MALDI-ToF mass spectrometry. Its catalytic activity was evaluated in the ring-opening of epoxides with carbon dioxide to give cyclic carbonates under solvent-free conditions. The catalyst proved to be active at low catalyst loading (down to 0.1 mol%) and allows the reaction to occur at low CO2 pressure (1–5 bar) and moderate temperature (100 °C). A range of terminal and internal epoxides was converted to the corresponding cyclic carbonates with high yields and selectivities. The recyclability of the catalyst was studied and no significant loss of activity was observed after 5 runs. (Figure presented.).
- Grollier, Kevin,Vu, Nam Duc,Onida, Killian,Akhdar, Ayman,Norsic, Sébastien,D'Agosto, Franck,Boisson, Christophe,Duguet, Nicolas
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- PALLADIUM CATALYZED REACTION OF BUTADIENE MONOXIDE WITH CARBON DIOXIDE
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Carbon dioxide readily reacts with 1,3-butadiene monoxide in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium under ordinary pressure at 0 deg C to afford vinylethylene carbonate in a quantitative yield.
- Fujinami, Tatsuo,Suzuki, Takehiro,Kamiya, Masakuni,Fukuzawa, Shin-ichi,Sakai, Shizuyoshi
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- Synthesis of heterobimetallic Ru-Mn complexes and the coupling reactions of epoxides with carbon dioxide catalyzed by these complexes
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The heterobimetallic complexes [(η5-C5H 5)Ru(CO)(μ-dppm)Mn(CO)4] and [(η5-C 5Me5)Ru(μ-dppm)(μ-CO)2Mn(CO) 3] (dppm= bisdiphenylphosphinomethane) have been prepared by reacting the hydridic complexes [(η5-C5H5)Ru(dppm) H] and [(η-C5Me5)Ru(dppm)H], respectively, with the protonic [HMn(CO)5] complex. The bimetallic complexes can also be synthesized through metathetical reactions between [(η5-C 5R5)Ru-(dppm)Cl] (R = H or Me) and Li+ [Mn(CO)5]-. Although the complexes fail to catalyze the hydrogenation of CO2 to formic acid, they catalyze the coupling reactions of epoxides with carbon dioxide to yield cyclic carbonates. Two possible reaction pathways for the coupling reactions have been proposed. Both routes begin with heterolytic cleavage of the Ru-Mn bond and coordination of an epoxide molecule to the Lewis acidic ruthenium center. In Route I, the Lewis basic manganese center activates the CO2 by forming the metallocarboxylate anion which then ring-opens the epoxide: subsequent ring-closure gives the cyclic carbonate. In Route II, the nucleophilic manganese center ring-opens the ruthenium-attached epoxide to afford an alkoxide intermediate; CO2 insertion into the Ru-O bond followed by ring-closure yields the product. Density functional calculations at the B3LYP level of theory were carried out to understand the structural and energetic aspects of the two possible reaction pathways. The results of the calculations indicate that Route II is favored over Route I.
- Man, Man Lok,Lam, King Chung,Sit, Wing Nga,Ng, Siu Man,Zhou, Zhongyuan,Lin, Zhenyang,Lau, Chak Po
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- Cycloaddition of CO2 to epoxides over solid base catalysts
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The cycloaddition of CO2 to various epoxides, i.e., ethylene oxide, epoxybutene, and epoxypropylbenzene over solid base catalysts (KX zeolite, Cs-loaded KX zeolite, Cs-doped alumina, and MgO) was performed in a batch autoclave reactor at 423 K and with excess CO2. The occluded base sites on the Cs/KX were actually composed of occluded Cs and K species that could be removed by washing with water. The activity of the zeolite catalysts for ethylene oxide conversion to ethylene carbonate depended on the basicity of the sample, with the sample containing occluded alkali metal oxides being the most active. In addition, the site-time yields of ethylene carbonate formation, based on CO2 adsorption capacity, over Cs/KX, Cs/Al2O3, and MgO were similar to each other and were within a factor of 4 of the site-time yield seen with the homogeneous catalyst [N(C2H5)4Br. The rates of epoxypropylebenzene conversion over the solid base catalysts were much lower than the rates of ethylene oxide conversion, presumably due to steric hindrance of the bulky side group on the former. CO2 addition to ethylene oxide was effectively catalyzed by Cs/KX, MgO, and Cs/Al2O3. Porosity and Lewis acidity influenced the reactivity of epoxybutene and epoxypropylbenzene more than that of ethylene oxide. Zeolites provided a unique reaction environment allowing water to play a beneficial part in base catalysis involving CO2 cycloaddition reactions.
- Tu, Mai,Davis, Robert J.
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- Bifunctional zinc and magnesium Schiff-base complexes containing quaternary ammonium side-arms for epoxide/CO2coupling reactions
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Novel bifunctional zinc and magnesium Schiff-base complexes containing quaternary ammonium halide side-arms were developed. Zinc complex1Et-I(0.02 mol%) having an iodide anion has shown the highest TOF for the propylene oxide/CO2coupling reaction of up to 459 h?1. This TOF value was maintained even when the catalyst loading was reduced to 0.005 mol%.
- Chainok, Kittipong,Laiwattanapaisarn, Nattiya,Phomphrai, Khamphee,Virachotikul, Arnut
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- Synthesis and high-throughput testing of multilayered supported ionic liquid catalysts for the conversion of CO2 and epoxides into cyclic carbonates
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Multilayered covalently supported ionic liquid phase (mlc-SILP) materials were synthesised by grafting different bis-vinylimidazolium salts on thiol-functionalised silica. These materials, which contain a cross-linked oligomeric network of imidazolium units, were characterised and tested as catalysts for the reaction of carbon dioxide with various epoxides to produce cyclic carbonates. The materials prepared by supporting a bis-imidazolium iodide salt with xylene or octane as a linker between the imidazolium units were identified as the most active catalysts and displayed high turnover numbers and improved productivity compared to known supported ionic liquid catalysts. The most promising mlc-SILP catalysts were further studied to tune the reaction conditions towards optimum catalytic performance and to investigate their versatility with different substrates and their reusability. The rapid and parallel screening of the catalysts was efficiently carried out by means of high-throughput (HT) experimentation. This journal is the Partner Organisations 2014.
- Agrigento, Paola,Al-Amsyar, Syed M.,Soree, Benjamin,Taherimehr, Masoumeh,Gruttadauria, Michelangelo,Aprile, Carmela,Pescarmona, Paolo P.
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- Mesoporous Ta–W Composite Oxides: A Highly Effective and Reusable Acid–Base Catalysts for the Cycloaddition Reaction of Carbon Dioxide with Epoxides
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Cycloadditions of epoxides and carbon dioxide into corresponding cyclic carbonates were performed over mesoporous Ta–W composite oxides prepared by a modified hydrolytic method. The best yields of styrene carbonate were obtained when the Ta/W mole ratio was 2:1 (labeled as Ta0.67W0.33Os). Under optimal reaction conditions, the conversion of styrene oxide and selectivity of styrene carbonate reached 95 and 97%, respectively. These Ta–W composite oxides have been extensively characterized by several techniques. X-ray diffraction (XRD) patterns and Transmission Electron Microscope (TEM) revealed that Ta2O5 was completely dispersed in WOx. Scanning electron microscopy (SEM) exhibited that the particle size distributions become more and more uniform with increment of tungsten content. CO2 and NH3 temperature-programmed desorption (CO2 and NH3-TPD) revealed that Ta0.67W0.33Os catalyst had the strongest acid and base strength. X-ray photoelectron spectroscopy (XPS) shows that the strongest acid–base sites of Ta0.67W0.33Os catalyst origin from its highest lattice oxygen concentration and W 4f5/2 species with Bronsted acidity. We discussed the reaction kinetics and proposed a possible mechanism, indicating the excellent catalytic activity is attributed to the cooperative action of acidic and neighboring basic sites on the catalyst surface. Graphic Abstract: Cycloaddition reactions of carbon dioxide with epoxides into corresponding cyclic carbonates were performed over mesoporous Ta–W composite oxides prepared by a modified hydrolytic method. The best yields for cyclic carbonates were obtained when the Ta/W mole ratio was 2:1 (denoted as Ta0.67W0.33Os). Acid-base synergy, specific surface area and mesoporous structure could be ascribed to the main reasons for the highest catalytic activity of Ta0.67W0.33Os catalyst. Meanwhile, reaction kinetics was discussed and a possible reaction pathway was proposed.[Figure not available: see fulltext.]
- Liu, Gui,Liu, Junhua,Mao, Weizhong,Miao, Shiwen,Wang, Fang,Yin, Bingqian
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- Conversion of dilute CO2to cyclic carbonates at sub-atmospheric pressures by a simple indium catalyst
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The transformation of CO2to value added commodity chemicals presents an impactful strategy to obtain products that are less dependent on fossil fuels. In this study, indium tribromide (InBr3) mixed with tetrabutylammonium bromide (NBu4Br) co-catalyst has been identified as a simple, highly efficient catalyst for the synthesis of cyclic carbonates from epoxides and CO2at sub-atmospheric pressures, room temperature, and under solvent-free conditions. The InBr3/NBu4Br catalytic system is tolerant toward different functional groups with high conversions and >99% selectivity for cyclic carbonate without resorting to high pressures and temperatures. Moreover, a combination ofin situIR, NMR spectroscopy, and substrate labelling experiments enabled the proof of key catalytic steps and detection of reaction intermediates to elucidate the reaction mechanism. This technology represents a potential scalable system for the utilization of waste CO2
- Baalbaki, Hassan A.,Roshandel, Hootan,Hein, Jason E.,Mehrkhodavandi, Parisa
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p. 2119 - 2129
(2021/04/09)
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- Method for preparing cyclic carbonate by immobilizing CO2 under catalysis of organic boric acid
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The invention discloses a synthesis method for synergistically catalyzing carbon dioxide immobilization through weak Lewis acid phenylboronic acid and tetrabutylammonium bromide. According to the method, CO2 is immobilized by epoxide, and a cyclic carbonate product is generated. The method comprises the following step: under the concerted catalysis of phenylboronic acid and tetrabutylammonium bromide, performing reaction on epoxide as shown in a formula IV, a formula V or a formula VI and carbon dioxide to respectively obtain a cyclic carbonate product as shown in a formula I, a formula II or a formula III. According to the method, raw materials are convenient and easy to obtain, reaction conditions are mild, operation is easy and convenient, and the yield can reach 97%.
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Paragraph 0119-0124
(2021/06/22)
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- Zinc triazole-appended dipyrromethene complex as a new catalyst for the carbonation reaction
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Triazole-Appended Dipyrromethenes (TADs) constitute a highly tunable and versatile family of ligands. Thus, well designed 1:1/Zn:L complexes incorporating a macrocyclic TAD member were proven very efficient in the carbonation of epoxides at low CO2 pressure (1 bar) and 100 ?C. Interestingly, the non-macrocyclized analogue was catalytically inactive in the presence of Zn(OAc)2 and dimerized instantly. Hence, engineering a structure preventing the dimerization was proven critical to restore the catalytic activity of the zinc complex.
- Andrioletti, Bruno,Framery, Eric,Rago, Aurélie
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- Catalytic Formation of Cyclic Carbonates using Gallium Aminotrisphenolate Compounds and Comparison to their Aluminium Congeners: A Combined Experimental and Computational Study
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This work reports on the use of gallium aminotrisphenolate compounds as catalysts for the synthesis of cyclic carbonates from epoxides and CO2. The results show that they are highly active, and more so than the corresponding aluminium congeners. The catalyst system is applicable at low and elevated temperatures across a wide substrate scope including terminal, internal, multiple and fully deuterated epoxides. Applying low catalyst loadings has allowed for a TON of 344,000 to be obtained, highlighting their stability. A DFT investigation has confirmed that the gallium catalysts have lower energetic profiles compared to the aluminium congeners. Measurement of the Lewis acidity of both the gallium and aluminium aminotrisphenolate compounds using the Gutmann-Beckett method provides the experimental proof that the gallium compounds are more Lewis acidic than their aluminium congeners. Finally, Ab-Initio Molecular Dynamic (AIMD) simulations have investigated and quantified the dynamic behaviour of the catalytic systems, highlighting an important increase in fluxionality in some cases which helps to explain the increase in catalytic activity.
- álvarez-Miguel, Lucía,Burgoa, Jesús Damián,Mosquera, Marta E. G.,Hamilton, Alex,Whiteoak, Christopher J.
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p. 4099 - 4110
(2021/08/23)
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- Cycloaddition of carbon dioxide to epoxides by highly active constrained aluminum chloride complexes
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The transformation of carbon dioxide (CO2) and epoxides to cyclic carbonates has gained much interest due to its low cost, abundance, low toxicity, and renewability. Therefore, novel constrained aluminum chloride complexes were developed based on bis(salicylimine) ligands for epoxides/CO2 coupling reactions. The five-membered rings attached to the aromatic rings were designed to enlarge the coordination pocket around the aluminum center as demonstrated by single-crystal X-ray crystallography. Addition of propylene oxide (PO) to a mixture of an aluminum chloride complex and tetrabutylammonium bromide (TBAB) rapidly gave (ligand)Al-OCH(Me)CH2Cl and (ligand)Al-OCH(Me)CH2Br in similar quantities. The anion exchange between (ligand)Al-Cl and TBAB was found to be faster than the ring-opening of PO. From a series of catalyst screening and optimization, the combination of catalyst 2g having no substituent on the aromatic rings and TBAB displayed very high activity (TOF up to 10?800 h-1) for the PO/CO2 coupling reaction. This catalyst system was extended to eleven more examples of epoxides. Moreover, excellent selectivity for cyclic carbonate production was observed for both terminal and internal epoxides.
- Laiwattanapaisarn, Nattiya,Phomphrai, Khamphee,Virachotikul, Arnut
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p. 11039 - 11048
(2021/08/24)
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- Stereodivergent Synthesis of Enantioenriched γ-Butyrolactones Bearing Two Vicinal Stereocenters Enabled by Synergistic Copper and Iridium Catalysis
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By virtue of a fundamentally new reaction model of azomethine ylide serving as a two-atom synthon, we present the first example of stereodivergent preparation of γ-butyrolactones via synergistic Cu/Ir-catalyzed asymmetric cascade allylation/lactonization, and all four stereoisomers of γ-butyrolactones bearing two vicinal stereocenters are accessible with excellent diastereoselective and enantioselective control. The chiral IrIII-π-allyl intermediate was separated and characterized to understand the origin of the regio- and stereoselectivity of the initial C?C bond formation process. Control experiments shed some light on the catalyst/substrate and catalyst/catalyst interactions in this dual catalytic system to rationalize the related kinetic/dynamic kinetic resolution process with different catalyst combinations. The enantioenriched γ-butyrolactone products were converted into an array of structurally complex chiral molecules and organocatalysts that were otherwise inaccessible.
- Wang, Chun-Jiang,Wei, Liang,Xiao, Lu
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supporting information
p. 24930 - 24940
(2021/10/23)
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- Palladium-catalyzed stereoselective (3 + 2) cycloaddition of vinylethylene carbonates with cyclicN-sulfonyl ketimines
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A diastereoselective (3 + 2) cycloaddition ofN-sulfonyl ketimines with vinylethylene carbonates (VECs) in the presence of Pd2dba3·CHCl3and PPh3has been developed. The reaction of various substituted VECs and diverse cyclicN-sulfonyl ketimines proceeded smoothly under mild conditions, giving highly functionalized oxazolidine frameworks in good to excellent yields with moderate to good diastereoselectivities. With the use of spiroketal-based diphosphine SKP as a chiral ligand, an asymmetric version of the current (3 + 2) cycloaddition was achieved, and chiral products were obtained in >99% ee in most cases.
- Gao, Xing,Zhu, Dongyu,Jiang, Feng,Liao, Jianning,Wang, Wei,Wu, Yongjun,Zheng, Lufei,Guo, Hongchao
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supporting information
p. 4877 - 4881
(2021/06/16)
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- Triazole based cobalt catalyst for CO2 insertion into epoxide at ambient pressure
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Over the past decades, a lot of efforts have been made for the fixation of carbon dioxide (CO2) into epoxide for the synthesis of industrially important cyclic carbonates. Here, a cobalt(II) complex based on triazole, namely Co(II)-1,2,3-1H-triazole-4-carboxylate, was synthesized, fully characterized by FTIR, NMR, mass spectrometry, and single crystal X-ray diffraction, and used as a catalyst for the cycloaddition of CO2 to epoxides. The catalytic studies demonstrated that the catalyst is highly active for the CO2 fixation, with high turnover number (TON, 85 × 103) even without the use of solvent and at ambient pressure (1 bar) to produce a variety of different cyclic carbonates depending on the epoxide. Remarkably, the catalyst was used continuously further by the addition of a fresh amount of the substrate within the same reaction mixture for at least five successive reaction cycles without any loss in the catalytic activity.
- Suleman, Suleman,Younus, Hussein A.,Ahmad, Nazir,Khattak, Zafar A.K.,Ullah, Habib,Park, Jihae,Han, Taejun,Yu, Baoyi,Verpoort, Francis
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- 3-Bromo-1,1,1-trifluoro-2-propanol assisted chemical fixation of CO2 and epoxides
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3-Bromo-1,1,1-trifluoro-2-propanol (3-BTFP) in combination with n-butylammonium iodide (TBAI) was proved to be an efficient organocatalyst for chemical fixation of CO2 with various epoxides to the respective cyclic carbonates. A possible reaction mechanism was proposed wherein 3-BTFP activated epoxide through hydrogen bonding interaction. This mechanism is revealed by the results of FT-IR spectra and 1H NMR titration, and the synergetic effect functioned by 3-BTFP and TBAI ensures the reaction proceeding effectively. Herein, 3-BTFP represents a commercially available, stable and metal-free hydrogen-bonding donor for CO2 transformation, which has a potential application for the large-scale synthesis of cyclic carbonates.
- Ma, Hui,Zeng, Ji-jun,Tu, Dong-huai,Mao, Wei,Zhao, Bo,Wang, Kuan,Liu, Zhao-tie,Lu, Jian
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supporting information
(2020/01/22)
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- Preparation method of cyclic carbonate
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The invention belongs to the technical field of green catalytic synthesis, and particularly relates to a preparation method of cyclic carbonate. And catalyzing the epoxide shown in the formula III orIV and carbon dioxide by using a catalyst shown in the formula I or II to obtain the cyclic carbonate. The synthesis method is simple, the cost is low, the catalyst has high activity and high selectivity, the reaction conditions are mild, and the reusability is good.
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Paragraph 0061-0062
(2020/06/20)
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- Preparation method of cyclic carbonate
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The invention belongs to the technical field of green catalytic synthesis, and particularly relates to a preparation method of cyclic carbonate. Epoxide and carbon dioxide are catalyzed by using a catalyst provided by the invention to obtain the cyclic carbonate. According to the invention, the synthesis method is simple, cost is low, the catalyst has high activity and high selectivity, a reactioncondition is mild, and good reusability is realized.
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Paragraph 0073; 0076-0077
(2020/07/02)
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- Asymmetric Synthesis of N-Fused 1,3-Oxazolidines via Pd-Catalyzed Decarboxylative (3+2) Cycloaddition
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Efficient synthesis of optically active N-fused 1,3-oxazolidines containing quaternary and tertiary stereocenters was achieved via Pd-catalyzed asymmetric (3+2) cycloadditions of sulfamate-derived cyclic imines and vinylethylene carbonates. Using a chiral phosphoramidite ligand, the cycloadditions proceeded effectively providing sulfamidate-fused 1,3-oxazolidines in high yields (up to 96%) with stereoselectivities (up to 25:1 dr; >99% ee). Additionally, the scale-up reaction and further transformations of the product were also achieved demonstrating the synthetic utility toward the construction of useful heterocycles such as chiral oxazoline bearing a quaternary stereocenter. (Figure presented.).
- Ahn, Hye-In,Cho, Ho-Jun,Kim, Ju Hyun,Park, Jong-Un,Xuan, Zi
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supporting information
(2020/04/22)
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- Pd-Catalyzed Decarboxylative Olefination: Stereoselective Synthesis of Polysubstituted Butadienes and Macrocyclic P-glycoprotein Inhibitors
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The efficient and stereoselective synthesis of polysubstituted butadienes, especially the multifunctional butadienes, represents a great challenge in organic synthesis. Herein, we wish to report a distinctive Pd(0) carbene-initiated decarboxylative olefination approach that enables the direct coupling of diazo esters with vinylethylene carbonates (VECs), vinyl oxazolidinones, or vinyl benzoxazinones to afford alcohol-, amine-, or aniline-containing 1,3-dienes in moderate to high yields and with excellent stereoselectivity. This protocol features operational simplicity, mild reaction conditions, a broad substrate scope, and gram-scalability. Notably, a structurally unique allylic Pd(II) intermediate was isolated and characterized. DFT calculation and control experiments demonstrated that a rare Pd(0) carbene intermediate could be involved in this reaction. Moreover, the polysubstituted butadienes as novel building blocks were unprecedentedly assembled into macrocycles, which efficiently inhibited the P-glycoprotein and dramatically reversed multidrug resistance in cancer cells by 190-fold.
- Chen, Xiangyang,Hao, Jiping,Houk, K. N.,Li, Yingzi,Lou, Liguang,Quan, Haitian,Song, Bichao,Wang, Lu,Xia, Yuanzhi,Xie, Peipei,Xu, Zhongliang,Yang, Weibo
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supporting information
p. 9982 - 9992
(2020/06/27)
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- ONO pincer type ligand complexes of Al(III) as efficient catalyst for chemical fixation of CO2 to epoxides at atmospheric pressure
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Carbon dioxide, the main cause of environmental pollution, its utilization to produce valuable products is of utmost interest. A series ONO pincer hydrazone based most active mono-nuclear Al(III) complexes were successfully synthesized and characterized with the help of NMR, IR, mass spectrometry and only complex 2a was confirmed by single-crystal analysis. The synthesized Al(III) complexes were then employed as capable catalysts for the solvent-free chemical fixation of CO2 with epoxides at atmospheric pressure and could be reused five times without loss of any catalytic activity. In addition, the catalytic mechanism was investigated by analyzing intermediates via 1H NMR, 13C NMR, and mass MALDI-TOF. The excellent catalytic performance could be due to simultaneous attack and the opening of the epoxide by metal centers to form an alkoxide ion which activates the CO2 the same time.
- Ullah, Habib,Mousavi, Bibimaryam,Younus, Hussein A.,Khattak, Zafar A.K.,Suleman, Suleman,Jan, Muhammad T.,Yu, Baoyi,Chaemchuen, Somboon,Verpoort, Francis
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p. 190 - 198
(2019/08/07)
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- Transfer hydrogenation of cyclic carbonates and polycarbonate to methanol and diols by iron pincer catalysts
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Herein, we report the first example on the use of an earth-abundant metal complex as the catalyst for the transfer hydrogenation of cyclic carbonates to methanol and diols. The advantage of this method is the use of isopropanol as the hydrogen source, thus avoiding the handling of flammable hydrogen under high pressure. The reaction offers an indirect route for the reduction of CO2 to methanol. In addition, poly(propylene carbonate) was converted to methanol and propylene glycol. This methodology can be considered as an attractive opportunity for the chemical recycling of polycarbonates.
- Liu, Xin,De Vries, Johannes G.,Werner, Thomas
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p. 5248 - 5255
(2019/10/11)
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- (Thio)urea containing quaternary ammonium salts for the CO2-fixation with epoxides
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Abstract: A detailed screening of differently substituted chiral and achiral (thio)urea-containing quaternary ammonium salts revealed their potential as catalysts for the CO2-fixation with epoxides to obtain cyclic carbonates in high yields under operationally simple atmospheric pressure conditions. Additional DFT calculations substantiate a mechanism involving an initial addition of the nucleophilic iodide counter anion of the ammonium salt to the H-bonding activated epoxide, followed by stepwise CO2-fixation and cyclization. Graphical abstract: [Figure not available: see fulltext.].
- Sch?rgenhumer, Johannes,Tiffner, Maximilian,Waser, Mario
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- Zinc single atoms on N-doped carbon: An efficient and stable catalyst for CO2 fixation and conversion
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The cycloaddition of epoxides and carbon dioxide represents a straightforward and atom-efficient method for synthesis of cyclic carbonates and utilization of CO2. So far, homogeneous metal complexes have been mainly applied for such transformations. Here, we describe the synthesis of novel heterogeneous Zn-based catalysts, which were conveniently prepared by pyrolysis of an active-carbon-supported phenanthroline-ligated Zn(OAc)2 complex. Detail structural characterizations proved the existence of single zinc sites in the active material. Compared to a Zn-based nanoparticle (Zn-NP) catalyst, the resulting single metal atom catalyst (SAC) displayed improved activity and stability for the cycloaddition of epoxides. By applying the optimal catalyst, a variety of carbonates were successfully obtained in high yields with good functional group tolerance.
- Cui, Xinjiang,Dai, Xingchao,Surkus, Annette-Enrica,Junge, Kathrin,Kreyenschulte, Carsten,Agostini, Giovanni,Rockstroh, Nils,Beller, Matthias
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p. 1679 - 1685
(2019/11/11)
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- Highly regio- And stereoselective synthesis of cyclic carbonates from biomass-derived polyols: Via organocatalytic cascade reaction
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The cascade reaction of CO2, vicinal diols, and propargylic alcohol, was firstly achieved by dual Lewis base (LB) organocatalytic systems involving LB-CO2 adducts and commercially available organic amines. This methodology could overcome the chemical inertness of CO2, providing an alternative route to various functionalized five-membered cyclic carbonates in moderate to high yields under mild reaction conditions (25 °C, 1.0 atm of CO2). More importantly, this method could also be applied for facile and efficient synthesis of chiral polycyclic carbonates from biomass-derived polyols with complete configuration retention of chiral centers. This study provides an environment-friendly, scalable and cost effective protocol to construct value-added cyclic carbonates with multi-functional groups and chiral centers.
- Zhou, Hui,Zhang, Hui,Mu, Sen,Zhang, Wen-Zhen,Ren, Wei-Min,Lu, Xiao-Bing
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supporting information
p. 6335 - 6341
(2019/12/03)
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- Versatile and scalable synthesis of cyclic organic carbonates under organocatalytic continuous flow conditions
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The benchmark route for the preparation of cyclic organic carbonates starts from toxic, volatile and unstable epoxides. In this work, cyclic organic carbonates are prepared according to alternative sustainable and intensified continuous flow conditions from the corresponding 1,2-diols. The process utilizes dimethyl carbonate (DMC) as a low toxicity carbonation reagent and relies on the organocatalytic activity of widely available and cheap organic ammonium and phosphonium salts. Glycerol is selected as a model substrate for preliminary optimization with a library of homogeneous ammonium and phosphonium salts. The nature of the anion dramatically influences the catalytic activity, while the nature of the cation does not impact the reaction. Upon optimization, glycerol carbonate is obtained in 95% conversion and 79% selectivity within 3 min residence time at 180 °C (11 bar) with 3.5 mol% of tetrabutylammonium bromide as the organocatalyst. A straightforward liquid-liquid extraction procedure enables both the purification of glycerol carbonate and the recycling of the homogeneous catalyst. The conditions are amenable to refined and crude bio-based glycerol, although conversions are lower in the latter case. Control experiments suggest that water present in the crude samples induces significant hydrolysis of glycerol carbonate. The reaction conditions are then successfully applied on a wide variety of substrates, affording the corresponding cyclic carbonates in overall good to excellent yields (20 examples, 45-95%). The substrate scope notably encompasses bio-based starting materials such as glycerol ethers and erythritol-derived diols. In-line NMR is featured as a qualitative analytical tool for real-time reaction monitoring. The scalability of this carbonation procedure on glycerol is assessed in a commercial pilot-scale silicon carbide continuous flow reactor of 60 mL internal volume. Glycerol carbonate is obtained in 76% yield, corresponding to a productivity of 13.6 kg per day.
- Gérardy, Romaric,Estager, Julien,Luis, Patricia,Debecker, Damien P.,Monbaliu, Jean-Christophe M.
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p. 6841 - 6851
(2019/12/24)
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- Synthesis of Cyclic Organic Carbonates Using Atmospheric Pressure CO2 and Charge-Containing Thiourea Catalysts
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Cycloadditions of epoxides with CO2 to synthesize cyclic five-membered ring organic carbonates are of broad interest from a synthetic, environmental, and green chemistry perspective, and the development of effective catalysts for these transformations is an ongoing challenge. A series of eight charge-containing thiourea salts that catalyze these reactions under mild conditions (i.e., 60 °C and atmospheric CO2 pressure) are reported. Substrate scope and mechanistic studies were also carried out, isotope effects were measured, and a reactive intermediate was isolated revealing a surprising pathway in which a thiourea catalyst serves as a nucleophile in the cleavage of the epoxide ring.
- Fan, Yang,Tiffner, Maximilian,Sch?rgenhumer, Johannes,Robiette, Rapha?l,Waser, Mario,Kass, Steven R.
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p. 9991 - 10000
(2018/07/30)
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- Formal [5+3] Cycloaddition of Zwitterionic Allylpalladium Intermediates with Azomethine Imines for Construction of N,O-Containing Eight-Membered Heterocycles
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A formal [5+3] cycloaddition of zwitterionic allylpalladium intermediates with 1,3-dipoles is developed, providing N,O-containing eight-membered heterocyclic compounds in high yields. Catalytically generated zwitterionic allylpalladium intermediates in situ from vinylethylene carbonates or vinyloxiranes acted as dipolarophile. (Figure presented.).
- Yuan, Chunhao,Wu, Yang,Wang, Dongqi,Zhang, Zhenhua,Wang, Chang,Zhou, Leijie,Zhang, Cheng,Song, Baoan,Guo, Hongchao
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supporting information
p. 652 - 658
(2017/12/26)
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- A versatile biobased continuous flow strategy for the production of 3-butene-1,2-diol and vinyl ethylene carbonate from erythritol
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A versatile, tunable and robust continuous flow procedure for the deoxydehydration (DODH) of biobased erythritol toward 3-butene-1,2-diol is described. The procedure relies on specific assets of multistep continuous flow processing. Detailed mechanistic and computational studies on erythritol show that either 3-butene-1,2-diol or butadiene are obtained in high selectivity and yield on demand, as a function of the DODH reagent/substrate ratio and of the process parameters. Short reaction times (1-15 min) at high temperature (225-275 °C) and moderate pressure are reported. 3-Butene-1,2-diol is then further converted downstream into its corresponding carbonate, i.e. 4-vinyl-1,3-dioxolan-2-one (vinyl ethylene carbonate), an important industrial building block. The carbonation step uses a supported organocatalyst, and could be directly concatenated to the first DODH step. This unprecedented procedure also relies on a unique combination of on- and off-line analytical protocols for reaction monitoring and product quantification, and offers a biobased strategy toward important industrial building blocks otherwise petrosourced.
- Tshibalonza, Nelly Ntumba,Gérardy, Romaric,Alsafra, Zouheir,Eppe, Gauthier,Monbaliu, Jean-Christophe M.
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supporting information
p. 5147 - 5157
(2018/11/26)
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- Poly(ethylene glycol)s as Ligands in Calcium-Catalyzed Cyclic Carbonate Synthesis
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Herein the use of CaI2 in combination with poly(ethylene glycol) dimethyl ether (PEG DME 500) as an efficient catalyst system for the addition of CO2 to epoxides is reported. This protocol is based on a nontoxic and abundant metal in conjunction with a polymeric ligand. Fifteen terminal epoxides were converted at room temperature to give the desired products in yields up to 99 %. Notably, this system was also effective for the synthesis of twelve challenging internal carbonates in yields up to 98 %.
- Steinbauer, Johannes,Werner, Thomas
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p. 3025 - 3029
(2017/08/18)
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- CO2 Fixation with Epoxides under Mild Conditions with a Cooperative Metal Corrole/Quaternary Ammonium Salt Catalyst System
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The cooperative catalytic activity of several metal corrole complexes in combination with tetrabutyl-ammonium bromide (TBAB) has been investigated for the reaction of epoxides with CO2 leading to cyclic carbonates. It was found that the use of just 0.05 mol % of a manganese(III)corrole with 2 mol % TBAB exhibits excellent catalytic activity under an atmosphere of CO2.
- Tiffner, Maximilian,Gonglach, Sabrina,Haas, Michael,Sch?fberger, Wolfgang,Waser, Mario
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supporting information
p. 1048 - 1051
(2017/05/26)
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- Fully meta-Substituted 4,4′-Biphenyldicarboxylate-Based Metal–Organic Frameworks: Synthesis, Structures, and Catalytic Activities
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Fully meta-substituted 2,2′,6,6′-tetramethoxy-4,4′-biphenyldicarboxylic acid (H2L) was synthesized and applied in the construction of three metal–organic frameworks (MOFs), {[Cu3L3(H2O)2(DMF)]n (1), [Zn4OL3]n (2), and [Zn4OL3(H2O)(DEF)]n (3)}. For 1, the approximately vertical twist of two benzene rings in L leads to the formation of a twofold-interpenetrated 3D structure with 1D open channels (11 × 15 ?). MOFs 2 and 3 have classical twofold-interpenetrated isoreticular MOF structures, and reversible transformation of the oxozinc carboxylate clusters of 2 and 3 could be realized via a solvent-exchange-induced single-crystal-to-single-crystal pathway, which provides direct structural evidence for a Zn4O core as Lewis acidic site in MOFs. Desolvated framework 1′ exhibits high permanent porosity (Langmuir surface area = 555 m2/g), high thermal stability (up to 300 °C), and highly active catalytic properties for cyanosilylation and olefin epoxidation. MOF 2 exhibits moderate carbon dioxide uptake ability and can efficiently catalyze the cycloaddition of CO2 with epoxides under mild conditions.
- Li, Jiawei,Ren, Yanwei,Qi, Chaorong,Jiang, Huanfeng
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p. 1478 - 1487
(2017/03/31)
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- Asymmetric Hydroformylation of 4-Vinyl-1,3-dioxolan-2-one
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A chiral cyclic carbonate, 4-vinyl-1,3-dioxolan-2-one was used as racemic substrate in asymmetric hydroformylation. The catalysts were formed in situ from “pre-formed” PtCl2(diphosphine) and tin(II) chloride. (2S,4S)-2,4-Bis(diphenylphosphinopentane ((S,S)-BDPP)), (S,S)-2,3-O-izopropylidine-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane ((S,S)-DIOP)), and (R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl ((R)-BINAP)) were used as optically active diphosphine ligands. The platinum-containing catalytic systems provided surprisingly high activity. The hydroformylation selectivities of up to 97% were accompanied by perfect regioselectivity towards the dioxolane-based linear aldehyde. The enantiomeric composition of all components in the reaction mixture was determined and followed throughout the reaction. The unreacted 4-vinyl-1,3-dioxolan-2-one was recovered in optically active form. The kinetic resolution was rationalized using the enantiomeric composition of the substrate and the products.
- Pongrácz, Péter,Kollár, László
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p. 1430 - 1436
(2017/03/27)
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- Preparation method of vinyl ethylene carbonate
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The invention provides a preparation method of vinyl ethylene carbonate. The preparation method includes: adopting butenediol and dialkyl ester carbonate as raw materials for transesterification to generate vinyl ethylene carbonate; before reaction, using a dehydrating agent to pre-treat the raw materials, and adding an acid binding agent and a catalyst into a reaction system. The preparation method has high reaction rate, short reaction time, high yield and high product purity.
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Paragraph 0027; 0028
(2017/02/24)
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- Synthesis of Cyclic Carbonates from Epoxides and Carbon Dioxide by Using Bifunctional One-Component Phosphorus-Based Organocatalysts
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Numerous bifunctional organocatalysts were synthesized and tested for the atom-efficient addition of carbon dioxide and epoxides to produce cyclic carbonates. These catalysts are based on phosphonium salts containing an alcohol moiety in the side chain for substrate activation through hydrogen bonding. In the model reaction, converting 1,2-butylene oxide with CO2, 19 catalysts were tested to determine structure-activity relationships. In total, 28 epoxides were converted with CO2 to give the respective cyclic carbonates in yields of up to 99%. Even at 45C, the most active catalyst was able to produce cyclic carbonates selectively in high yields. The carbonates were generally obtained as analytically pure products after simple filtration over silica gel. This single-component catalyst system works under neat and mild reaction conditions and tolerates several useful moieties. Two heads are better than one! Bifunctional organocatalysts are synthesized and tested in the catalytic reaction of epoxides and carbon dioxide to give the respective cyclic carbonates. Product formation is significantly increased by hydrogen-bond donation from the bifunctional phosphonium catalyst.
- Büttner, Hendrik,Steinbauer, Johannes,Werner, Thomas
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p. 2655 - 2669
(2015/09/02)
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- Hydroxyl-functionalized imidazoles: Highly active additives for the potassium iodide-catalyzed synthesis of 1,3-dioxolan-2-one derivatives from epoxides and carbon dioxide
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4(5)-(Hydroxymethyl)imidazole and potassium iodide were identified as an efficient catalyst system for the cycloaddition of epoxides and carbon dioxide producing 1,3-dioxolan-2-one derivatives under solvent-free conditions. The high activity of the catalyst system even at 60 C was probably due to synergistic effects between potassium iodide and the substituted imidazole. Various functionalized and nonfunctionalized terminal epoxides as well as internal epoxides were converted into the corresponding cyclic carbonates in high yields (up to 99 %) under mild reaction conditions within a short reaction time. Compared with the previously reported amino alcohols e.g. triethanolamine based catalyzed synthesis of cyclic carbonates, the catalyst system described herein demonstrates a higher activity toward a broad substrate scope A perfect combination: The combination of commercially available 4(5)-(hydroxymethyl)imidazole (HMI) and potassium iodide serves as a simple and efficient catalyst system for the coupling reaction of epoxides with carbon dioxide. Several epoxides are converted into cyclic carbonates in high yields (up to 99 %) under mild and solvent-free conditions within a short reaction time. This new catalyst system demonstrates higher activity than the previously reported potassium iodide/triethanolamine (TEA) system.
- Werner, Thomas,Tenhumberg, Nils,Büttner, Hendrik
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p. 3493 - 3500
(2015/04/16)
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- Direct cyclic carbonate synthesis from CO2 and diol over carboxylation/hydration cascade catalyst of CeO2 with 2-cyanopyridine
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We first achieved direct synthesis of propylene carbonate from CO 2 and 1,2-propanediol in excellent yield (>99%) using a carboxylation/hydration cascade catalyst of CeO2 with 2-cyanopyridine. The catalyst system can be applied to syntheses of various cyclic carbonates, including 6-membered ring carbonates that are difficult to synthesize in high yields (62->99%).
- Honda, Masayoshi,Tamura, Masazumi,Nakao, Kenji,Suzuki, Kimihito,Nakagawa, Yoshinao,Tomishige, Keiichi
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p. 1893 - 1896
(2014/06/24)
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- One-pot synthesis of cyclic carbonates from aldehydes, sulfur ylide, and CO2
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Treatment of aldehydes with sulfur ylide (CH2=SOMe2 or CH2=SMe2), in the presence of CO2 (1 atm) bubbled sequentially under mild conditions, produces cyclic carbonates in preparative yields. Sodium iodide formed in situ promotes the reaction between epoxide as intermediate and CO2 at ambient conditions, thus constituting a powerful metal-free synthesis of organic cyclic carbonates directly from aldehydes. Georg Thieme Verlag Stuttgart · New York.
- Aher, Ravindra D.,Kumar, B. Senthil,Sudalai, Arumugam
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- Bromine-catalyzed conversion of CO2 and epoxides to cyclic carbonates under continuous flow conditions
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A continuous method for the formation of cyclic carbonates from epoxides and carbon dioxide (CO2) is described. The catalysts used are inexpensive and effective in converting the reagents to the products in a residence time (tR) of 30 min. The cyclic carbonate products are obtained in good to excellent yield (51-92%). On the basis of a series of kinetics experiments, we propose a reaction mechanism involving epoxide activation by electrophilic bromine and CO2 activation by an amide.
- Kozak, Jennifer A.,Wu, Jie,Su, Xiao,Simeon, Fritz,Hatton, T. Alan,Jamison, Timothy F.
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supporting information
p. 18497 - 18501
(2014/01/06)
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- METHODS AND SYSTEMS FOR THE FORMATION OF CYCLIC CARBONATES
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Described herein are inventive methods for synthesis of cyclic carbonates from C02 and epoxide. In some embodiments, the methods are carried out in the presence of a catalyst comprising an electrophilic halogen. In some embodiments, the methods are carried out in a flow reactor.
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Page/Page column 30; 33
(2013/12/03)
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- A bifunctional catalyst for carbon dioxide fixation: Cooperative double activation of epoxides for the synthesis of cyclic carbonates
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We have developed a very active bifunctional porphyrin catalyst showing a high turnover number (TON = 103000) for the synthesis of cyclic carbonates from CO2 and epoxides under solvent-free conditions.
- Ema, Tadashi,Miyazaki, Yuki,Koyama, Shohei,Yano, Yuya,Sakai, Takashi
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supporting information; experimental part
p. 4489 - 4491
(2012/05/20)
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- Merging sustainability with organocatalysis in the formation of organic carbonates by using CO2 as a feedstock
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The use of phenolic compounds as organocatalysts is discussed in the context of the atom-efficient cycloaddition of carbon dioxide to epoxides, forming useful cyclic organic carbonate products. The presence and cooperative nature of adjacent phenolic groups in the catalyst structure results in significantly enhanced catalytic efficiencies, allowing these CO2 fixation reactions to operate efficiently under virtually ambient conditions. The cooperative effect has also been studied by computational methods. Furthermore, when the cycloaddition reactions are carried out on a larger scale and under solvent-free conditions, further enhancements in activity are observed, combined with the advantageous requirement of reduced loadings of the binary organocatalyst system. The reported system is among one of the mildest and most effective metal-free catalysts for this conversion and contributes to a much more sustainable development of organic carbonate production; this feature has not been the main focus of previous contributions in this area. In a fix: A new organocatalytic method for organic carbonate synthesis is reported and allows attractive conditions (25 °C, 10 bar, no solvent) to be used (see picture). Cyclic carbonates produced from CO2 and epoxides are isolated in high yields. The mild nature of this process increases the overall process sustainability for this type of widely studied carbon dioxide fixation process.
- Whiteoak, Christopher J.,Nova, Ainara,Maseras, Feliu,Kleij, Arjan W.
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supporting information
p. 2032 - 2038
(2013/01/15)
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- An efficient iron catalyst for the synthesis of five- and six-membered organic carbonates under mild conditions
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An iron(III) amine triphenolate complex, [FeTPhOA]2, able to efficiently catalyze the cycloaddition of carbon dioxide to a range of terminal epoxides under mild conditions, is described. In addition, it has also been found that the complex is able to catalyze the conversion with more sterically congested oxiranes and oxetanes which are generally considered challenging substrates to activate. Variation of the co-catalyst, required for ring-opening of the substrates, has also been examined. The results show that terminal epoxide substrates are converted more efficiently with an iodide co-catalyst, whereas more bulky oxirane substrates give better product yields in the presence of a bromide co-catalyst. The combined results demonstrate the broad applicability of these iron(III) complexes in this type of carbon dioxide fixation chemistry. Copyright
- Whiteoak, Christopher J.,Martin, Eddy,Belmonte, Marta Martinez,Benet-Buchholz, Jordi,Kleij, Arjan W.
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experimental part
p. 469 - 476
(2012/04/04)
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- Mild formation of cyclic carbonates using Zn(II) complexes based on N 2S2-chelating ligands
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We have prepared a series of Zn(II) complexes (1-3) based on a versatile N2S2-chelating ligand abbreviated as btsc [btsc = bis-(thiosemicarbazonato)] derived from simple and accessible building blocks. These complexes comprise a Lewis acidic Zn(II) center useful for substrate activation, and we have investigated the potential of these compounds in the cyclo-addition reaction of carbon dioxide to various epoxides yielding cyclic carbonate structures. Initial screening studies with complexes 1-3 showed that complex 3 is most suited for this CO2 fixation reaction under particularly mild conditions (45 °C, pCO2 = 10 bar) and low catalyst loadings (1 mol%). Furthermore, upon examination of the substrate scope, complex 3 shows appreciable catalytic turnover for a range of terminal epoxides, while for the sterically more challenging epoxides almost no conversion was achieved under comparable conditions. Additional experiments indicated that higher yields of cyclic carbonates may be realized by simply increasing the (co)catalyst loading up to 3%, while maintaining mild reaction conditions. The use of a relatively non-toxic and abundant metal and an environmentally benign solvent system (MEK, methyl ethyl ketone) mark this protocol as an attractive way for organic carbonate production.
- Anselmo, Daniele,Bocokic, Vladica,Decortes, Antonello,Escudero-Adan, Eduardo C.,Benet-Buchholz, Jordi,Reek, Joost N.H.,Kleij, Arjan W.
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experimental part
p. 49 - 53
(2012/03/12)
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- Highly efficient synthesis of cyclic carbonates from epoxides catalyzed by indium tribromide system
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A novel, efficient synthesis of cyclic carbonates from the reaction of epoxides and 1 atom of CO2 under mild conditions (no solvent, 1 atom, room temperature) was achieved in good yields by using indium catalyst system.
- Shibata, Ikuya,Mitani, Ikuko,Imakuni, Akira,Baba, Akio
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experimental part
p. 721 - 723
(2011/03/20)
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- Palladium-catalyzed carbonylation of diols to cyclic carbonates
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The catalytic alkoxycarbonylation of 1,2-diols by (neocuproine) palladium(II) acetate (neocuproine=2,9-dimethyl-1,10-phenanthroline) or palladium(II) acetate/(-)-sparteine using N-chlorosuccinimide as the oxidant affords cyclic carbonates. The oxidative carbonylation of diols proceeds under mild conditions, requiring only 1 atm of carbon monoxide, and produces cyclic carbonates in moderate to good yields. Both 1,2- and 1,3-diols can be carbonylated using (neocuproine)Pd(OAc)2 and sodium dichloroisocyanuric acid, which serves as a competent oxidant and base for this system, to yield 5- and 6-membered cyclic carbonates. Copyright
- Pearson, David M.,Conley, Nicholas R.,Waymouth, Robert M.
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supporting information; experimental part
p. 3007 - 3013
(2011/12/16)
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- Efficient carbonate synthesis under mild conditions through cycloaddition of carbon dioxide to oxiranes using a Zn(salphen) catalyst
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Zn(salphen) complexes are reported as effective, cheap, robust and relatively green catalysts for the cycloaddition of carbon dioxide to terminal epoxides to afford cyclic carbonates in good yields.
- Decortes, Antonello,Martinez Belmonte, Marta,Benet-Buchholz, Jordi,Kleij, Arjan W.
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supporting information; experimental part
p. 4580 - 4582
(2010/11/18)
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- Synthesis of Cyclic Organic Carbonates from C3-C16 Epoxides
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Cyclic organic carbonates were prepared from epoxides (derivatives of C3-C16 olefins, C4 and C8 dienes, styrene; epichlorohydrin) in the presence of a catalytic system consisting of CoCl2 · 6H2O and dimethylformamide.
- Rybina,Srednev,Bobyleva
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p. 842 - 843
(2007/10/03)
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