- Efficient catalytic conversion of terminal/internal epoxides to cyclic carbonates by porous Co(ii) MOF under ambient conditions: Structure-property correlation and computational studies
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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.
- Parmar, Bhavesh,Patel, Parth,Pillai, Renjith S.,Kureshy, Rukhsana I.,Khan, Noor-Ul H.,Suresh, Eringathodi
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- Rasta resin-DMAP and its use as a recyclable catalyst for the addition of carbon dioxide to epoxides
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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.
- Lu, Jinni,Toy, Patrick H.
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- CO2 fixation by cycloaddition of mono/disubstituted epoxides using acyl amide decorated Co(II) MOF as a synergistic heterogeneous catalyst
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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.
- Patel, Parth,Parmar, Bhavesh,Pillai, Renjith S.,Ansari, Amamudin,Khan, Noor-ul H.,Suresh, Eringathodi
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- Catalytic synthesis of cyclic carbonates from epoxides and carbon dioxide by magnetic UiO-66 under mild conditions
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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
- Delavari, Mahbube,Zadehahmadi, Farnaz,Tangestaninejad, Shahram,Moghadam, Majid,Mirkhani, Valiollah,Mohammadpoor-Baltork, Iraj,Kardanpour, Reihaneh
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- Catalytic, Kinetic, and Mechanistic Insights into the Fixation of CO2 with Epoxides Catalyzed by Phenol-Functionalized Phosphonium Salts
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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.
- Hu, Yuya,Wei, Zhihong,Frey, Anna,Kubis, Christoph,Ren, Chang-Yue,Spannenberg, Anke,Jiao, Haijun,Werner, Thomas
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p. 363 - 372
(2020/11/30)
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- A Strained Ion Pair Permits Carbon Dioxide Fixation at Atmospheric Pressure by C-H H-Bonding Organocatalysis
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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).
- Xu, Jiaxi,Xian, Anmei,Li, Zhenjiang,Liu, Jingjing,Zhang, Zhihao,Yan, Rui,Gao, Luoyu,Liu, Bo,Zhao, Lili,Guo, Kai
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p. 3422 - 3432
(2021/02/27)
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- One-pot synthesis of oxazolidinones and five-membered cyclic carbonates from epoxides and chlorosulfonyl isocyanate: Theoretical evidence for an asynchronous concerted pathway
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The one-pot reaction of chlorosulfonyl isocyanate (CSI) with epoxides having phenyl, benzyl and fused cyclic alkyl groups in different solvents under mild reaction conditions without additives and catalysts was studied. Oxazolidinones and five-membered cyclic carbonates were obtained in ratios close to 1:1 in the cyclization reactions. The best yields of these compounds were obtained in dichloromethane (DCM). Together with 16 known compounds, two novel oxazolidinone derivatives and two novel cyclic carbonates were synthesized with an efficient and straightforward method. Compared to the existing methods, the synthetic approach presented here provides the following distinct advantageous: being a one-pot reaction with metal-free reagent, having shorter reaction times, good yields and a very simple purification method. Moreover, using the density functional theory (DFT) method at the M06-2X/6-31+G(d,p) level of theory the mechanism of the cycloaddition reactions has been elucidated. The further investigation of the potential energy surfaces associated with two possible channels leading to oxazolidinones and five-membered cyclic carbonates disclosed that the cycloaddition reaction proceeds via an asynchronous concerted mechanism in gas phase and in DCM.
- Demir, Esra,Sari, Ozlem,?etinkaya, Yasin,Atmaca, Ufuk,Erdem, Safiye Sa?,?elik, Murat
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p. 1805 - 1819
(2020/11/07)
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- An Aminopyridinium Ionic Liquid: A Simple and Effective Bifunctional Organocatalyst for Carbonate Synthesis from Carbon Dioxide and Epoxides
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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.
- Al-Harrasi, Ahmed,Ebrahimi, Amirhossein,Khosravi, Hormoz,Rezazadeh, Mostafa,Rostami, Ali
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p. 1587 - 1595
(2020/08/05)
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- Plasma-Assisted Immobilization of a Phosphonium Salt and Its Use as a Catalyst in the Valorization of CO2
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The first plasma-assisted immobilization of an organocatalyst, namely a bifunctional phosphonium salt in an amorphous hydrogenated carbon coating, is reported. This method makes the requirement for prefunctionalized supports redundant. The immobilized catalyst was characterized by solid-state 13C and 31P NMR spectroscopy, SEM, and energy-dispersive X-ray spectroscopy. The immobilized catalyst (1 mol %) was employed in the synthesis of cyclic carbonates from epoxides and CO2. Notably, the efficiency of the plasma-treated catalyst on SiO2 was higher than those of the SiO2 support impregnated with the catalyst and even the homogeneous counterpart. After optimization of the reaction conditions, 13 terminal and four internal epoxides were converted with CO2 to the respective cyclic carbonates in yields of up to 99 %. Furthermore, the possibility to recycle the immobilized catalyst was evaluated. Even though the catalyst could be reused, the yields gradually decreased from the third run. However, this is the first example of the recycling of a plasma-immobilized catalyst, which opens new possibilities in the recovery and reuse of catalysts.
- Brüser, Volker,Epping, Jan Dirk,Frank, Marcus,Hu, Yuya,Longwitz, Lars,Peglow, Sandra,Werner, Thomas
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- Synthesis of cyclic carbonates by ruthenium(VI) bis -imido porphyrin/TBACl-catalyzed reaction of epoxide with CO2
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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.
- Damiano, Caterina,Sonzini, Paolo,Intrieri, Daniela,Gallo, Emma
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p. 809 - 816
(2020/01/21)
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- Scalable, Durable, and Recyclable Metal-Free Catalysts for Highly Efficient Conversion of CO2 to Cyclic Carbonates
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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.
- Li, Bo,Wu, Guang-Peng,Xie, Rui,Yang, Guan-Wen,Yang, Li,Zhang, Yao-Yao
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supporting information
p. 23291 - 23298
(2020/10/19)
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- NNC-Scorpionate Zirconium-Based Bicomponent Systems for the Efficient CO2Fixation into a Variety of Cyclic Carbonates
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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
- Fernández-Baeza, Juan,Garcés, Andrés,Lara-Sánchez, Agustín,Martínez-Ferrer, Jaime,Navarro, Marta,Rodríguez, Ana M.,Sánchez-Barba, Luis F.,Sobrino, Sonia
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supporting information
p. 12422 - 12430
(2020/09/15)
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- Synthesis of helical aluminium catalysts for cyclic carbonate formation
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Helical aluminium complexes [Al2X4(μ-nbptam)] (X = Me 1, Et 2), [Al2X4(μ-fbpam)] (R = Me 3, Et 4), [Al3X7(μ-nbptam)] (X = Me 5, Et 6) and [Al3X7(μ-fbpam)] (X = Me 7, E
- Gaona, Miguel A.,De La Cruz-Martínez, Felipe,Fernández-Baeza, Juan,Sánchez-Barba, Luis F.,Alonso-Moreno, Carlos,Rodríguez, Ana M.,Rodríguez-Diéguez, Antonio,Castro-Osma, José A.,Otero, Antonio,Lara-Sánchez, Agustín
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supporting information
p. 4218 - 4227
(2019/04/01)
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- Influence of the Counterion on the Synthesis of Cyclic Carbonates Catalyzed by Bifunctional Aluminum Complexes
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New bifunctional aluminum complexes have been prepared with the aim of studying the effect of a counterion on the synthesis of cyclic carbonates from epoxides and carbon dioxide (CO2). Neutral ligand 1 was used as a precursor to obtain four nov
- Martínez, Javier,De La Cruz-Martínez, Felipe,Gaona, Miguel A.,Pinilla-Pealver, Esther,Fernández-Baeza, Juan,Rodríguez, Ana M.,Castro-Osma, José A.,Otero, Antonio,Lara-Sánchez, Agustín
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supporting information
p. 3396 - 3408
(2019/02/19)
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- Efficient Aluminum Catalysts for the Chemical Conversion of CO2 into Cyclic Carbonates at Room Temperature and Atmospheric CO2 Pressure
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A series of dimeric aluminum compounds [Al(OCMe2CH2N(R)CH2X)]2 [X=pyridin-2-yl, R=H (PyrH); X= pyridin-2-yl, R=Me (PyrMe); X=furan-2-yl, R=H (FurH); X= furan-2-yl, R=Me (FurMe); X=thiophen-2-yl, R=H (ThioH); X= thiophen-2-yl, R=Me (ThioMe)] containing heterocyclic pendant group attached to the nitrogen catalyze the coupling of CO2 with epoxides under ambient conditions. In a comparison of their catalytic activities with those of aluminum complexes without pendant groups at N [X=H, R=H (HH); X=H, R=Me (HMe)] or with non-heterocyclic pendant groups [X=CH2CH2OMe, R=H (OMeH); X=CH2CH2NMe2, R=H (NMe2H); X=CH2CH2NMe2, R=Me (NMe2Me)], complexes containing heterocycles, in conjunction with (nBu)4NBr as a cocatalyst, show higher catalytic activities for the synthesis of cyclic carbonates under the same ambient conditions. The best catalyst system for this reaction is PyrH/(nBu)4NBr system, which gives a turnover number of 99 and a turnover frequency of 4.1 h?1, making it 14- and 20-times more effective than HH/(nBu)4NBr and HMe/(nBu)4NBr, respectively. Although there are no direct interactions between the aluminum and the heteroatoms in the heterocyclic pendants, electronic effects combined with the increased local concentration of CO2 around the active centers influences the catalytic activity in the coupling of CO2 with epoxides. In addition, PyrH/(nBu)4NBr shows broad epoxide substrate scope and seven terminal epoxides and two internal epoxides undergo the designed reaction.
- Kim, Yoseph,Hyun, Kyunglim,Ahn, Duseong,Kim, Ran,Park, Myung Hwan,Kim, Youngjo
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p. 4211 - 4220
(2019/08/12)
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- Amidinate Aluminium Complexes as Catalysts for Carbon Dioxide Fixation into Cyclic Carbonates
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A series of inexpensive and sustainable amidinate aluminium complexes has been developed as catalysts for the chemical fixation of carbon dioxide into cyclic carbonates. The reactions using terminal epoxides as substrates were carried out at room temperat
- Meléndez, Danay Osorio,Lara-Sánchez, Agustín,Martínez, Javier,Wu, Xiao,Otero, Antonio,Castro-Osma, José A.,North, Michael,Rojas, René S.
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p. 2271 - 2277
(2018/03/27)
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- Diphenyl Carbonate: A Highly Reactive and Green Carbonyl Source for the Synthesis of Cyclic Carbonates
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A practical, safe, and highly efficient carbonylation system involving a diphenyl carbonate, an organocatalyst, and various diols is presented herein and produces highly valuable cyclic carbonates. In reactions with a wide range of diols, diphenyl carbonate was activated by bicyclic guanidine 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a catalyst, which successfully replaced highly toxic and unstable phosgene or its derivatives while maintaining the desired high reactivity. Moreover, this new system can be used to synthesize sterically demanding cyclic carbonates such as tetrasubstituted pinacol carbonates, which are not accessible via other conventional methods.
- Baral, Ek Raj,Lee, Jun Hee,Kim, Jeung Gon
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p. 11768 - 11776
(2018/09/27)
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- Highly efficient 3d/4d-4f coordination polymer catalysts for carbon dioxide fixation into cyclic carbonates
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Two novel highly efficient 3d/4d-4f one-dimensional (1D) double-chain coordination polymer catalysts with unique structures were synthesized for the first time. An X-ray single crystal structure analysis revealed that the two compounds are isomorphous and have a 1D metal-organic network coordination polymer structure. Both compounds also showed significant thermal stability and their structures remained stable up to 325 °C. The reaction conditions, type of substrate, amount of catalyst and its catalytic mechanism were investigated. The catalysts ([Dy2M2L4 (OAc)2 (MeOH)5 (H2O)]) (M = Zn, Cd) exhibited excellent catalytic activity in the cycloaddition of CO2 and styrene oxide (C8H8O, SO). High product yields, high selectivity, and the highest turnover frequency (TOF) of 28 400 h-1 were achieved. Additionally, the catalysts can significantly enhance the application of the present types of 3d/4d-4f catalysts in catalysis for transformations involving the fixation of CO2.
- Wang, Gang,Xu, Cong,Wang, Li,Liu, Weisheng
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supporting information
p. 12711 - 12717
(2018/09/27)
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- Vanadium(V) Catalysts with High Activity for the Coupling of Epoxides and CO2: Characterization of a Putative Catalytic Intermediate
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Vanadium(V) complexes derived from aminotriphenolate ligands are demonstrated to be highly active catalysts for the coupling of various terminal and internal epoxides with carbon dioxide to afford a series of substituted organic carbonates in good yields.
- Miceli, Claudia,Rintjema, Jeroen,Martin, Eddy,Escudero-Adán, Eduardo C.,Zonta, Cristiano,Licini, Giulia,Kleij, Arjan W.
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p. 2367 - 2373
(2017/05/31)
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- Pushing the Limits with Squaramide-Based Organocatalysts in Cyclic Carbonate Synthesis
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Squaramides are presented as modular, easy to optimize, and effective catalysts for the conversion of epoxides and carbon dioxide into cyclic organic carbonates (COCs). The catalytic potential of these squaramides, in combination with a suitable halide nucleophile, is particularly noted when internal epoxides are examined as substrates, and their transformation into disubstituted COCs marks a rare case of an effective organocatalyst for these challenging conversions. Control experiments support the mechanistic view that the squaramides are predominantly involved in the stabilization of intermediate oxo and carbonato anions which, after their formation, are able to displace a bromide nucleophile from an initially formed 1:1 assembly comprising the squaramide host.
- Sope?a, Sergio,Martin, Eddy,Escudero-Adán, Eduardo C.,Kleij, Arjan W.
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p. 3532 - 3539
(2017/06/09)
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- An Efficient and Versatile Lanthanum Heteroscorpionate Catalyst for Carbon Dioxide Fixation into Cyclic Carbonates
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A new lanthanum heteroscorpionate complex has shown exceptional catalytic activity for the synthesis of cyclic carbonates from epoxides and carbon dioxide. This catalyst system also promotes the reaction of bio-based epoxides to give an important class of bis(cyclic carbonates) that can be further used for the production of bio-derived non-isocyanate polyurethanes. The catalytic process requires low catalyst loading and mild reaction conditions for the synthesis of a wide range of cyclic carbonates.
- Martínez, Javier,Fernández-Baeza, Juan,Sánchez-Barba, Luis F.,Castro-Osma, José A.,Lara-Sánchez, Agustín,Otero, Antonio
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p. 2886 - 2890
(2017/07/25)
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- One-Component Aluminum(heteroscorpionate) Catalysts for the Formation of Cyclic Carbonates from Epoxides and Carbon Dioxide
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New neutral and zwitterionic chiral NNO-donor scorpionate ligands 1 and 2 were designed to obtain new mononuclear and dinuclear NNO-heteroscorpionate aluminum complexes. Reaction of 1 with [AlR3] (R=Me, Et) in a 1:1 or 1:2 molar ratio afforded
- Martínez, Javier,Castro-Osma, José A.,Alonso-Moreno, Carlos,Rodríguez-Diéguez, Antonio,North, Michael,Otero, Antonio,Lara-Sánchez, Agustín
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p. 1175 - 1185
(2017/03/29)
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- Aluminum-Mediated Formation of Cyclic Carbonates: Benchmarking Catalytic Performance Metrics
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We report a comparative study on the activity of a series of fifteen binary catalysts derived from various reported aluminum-based complexes. A benchmarking of their initial rates in the coupling of various terminal and internal epoxides in the presence of three different nucleophilic additives was carried out, providing for the first time a useful comparison of activity metrics in the area of cyclic organic carbonate formation. These investigations provide a useful framework for how to realistically valorize relative reactivities and which features are important when considering the ideal operational window of each binary catalyst system.
- Rintjema, Jeroen,Kleij, Arjan W.
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p. 1274 - 1282
(2017/03/29)
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- Convenient synthesis of ethylene carbonates from carbon dioxide and 1,2-diols at atmospheric pressure of carbon dioxide
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An efficient and convenient synthesis of ethylene carbonates was achieved by the reaction of carbon dioxide with 1,2-diols in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), followed by treatment with 1-bromobutane. This DBU-promoted transformation proceeded at an atmospheric pressure of carbon dioxide at 25 °C and gave ethylene carbonates in good yields.
- Kitamura, Tsugio,Inoue, Yusuke,Maeda, Taisei,Oyamada, Juzo
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- Cr(salophen) Complex Catalyzed Cyclic Carbonate Synthesis at Ambient Temperature and Pressure
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The combination of a chromium(III) salophen bromide complex and tetrabutylammonium bromide is shown to catalyze the reaction between terminal epoxides and carbon dioxide at ambient temperature and 1 bar carbon dioxide pressure and between internal epoxide
- Castro-Osma, José A.,Lamb, Katie J.,North, Michael
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p. 5012 - 5025
(2016/08/18)
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- Highly Active and Robust Metalloporphyrin Catalysts for the Synthesis of Cyclic Carbonates from a Broad Range of Epoxides and Carbon Dioxide
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Bifunctional metalloporphyrins with quaternary ammonium bromides (nucleophiles) at the meta, para, or ortho positions of meso-phenyl groups were synthesized as catalysts for the formation of cyclic carbonates from epoxides and carbon dioxide under solvent-free conditions. The meta-substituted catalysts exhibited high catalytic performance, whereas the para- and ortho-substituted catalysts showed moderate and low activity, respectively. DFT calculations revealed the origin of the advantage of the meta-substituted catalyst, which could use the flexible quaternary ammonium cation at the meta position to stabilize various anionic species generated during catalysis. A zinc(II) porphyrin with eight nucleophiles at the meta positions showed very high catalytic activity (turnover number (TON)=240 000 at 120 °C, turnover frequency (TOF)=31 500h-1 at 170°C) at an initial CO2 pressure of 1.7MPa; catalyzed the reaction even at atmospheric CO2 pressure (balloon) at ambient temperature (20°C); and was applicable to a broad range of substrates, including terminal and internal epoxides. In a fix! Bifunctional metalloporphyrins act as catalysts for the formation of cyclic carbonates from epoxides and CO2 (see scheme). A comparison of the catalytic activities shows the superior performance of meta-substituted catalysts. A robust zinc(II) porphyrin with eight nucleophiles at the meta positions shows the highest catalytic activity and a broad substrate scope, including terminal and internal epoxides.
- Maeda, Chihiro,Shimonishi, Junta,Miyazaki, Ray,Hasegawa, Jun-Ya,Ema, Tadashi
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supporting information
p. 6556 - 6563
(2016/05/02)
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- Synthesis of cyclic carbonates from diols and CO2 catalyzed by carbenes
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The synthesis of cyclic carbonates from epoxides and CO2 is a well-established reaction, whereas the synthesis of cyclic carbonates from diols and CO2 is considerably more challenging, and few efficient catalysts are available. Here, we describe heterocyclic carbene catalysts, including one derived from a cheap and efficient thiazolium salt, for this latter reaction. The reaction proceeds at atmospheric pressure in the presence of an alkyl halide and Cs2CO3. Reaction mechanisms for the transformations involved are also proposed.
- Bobbink, Felix D.,Gruszka, Weronika,Hulla, Martin,Das, Shoubhik,Dyson, Paul J.
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supporting information
p. 10787 - 10790
(2016/09/07)
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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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- Synthesis of Cyclic Carbonates Catalysed by Aluminium Heteroscorpionate Complexes
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New aluminium scorpionate based complexes have been prepared and used for the synthesis of cyclic carbonates from epoxides and carbon dioxide. Bimetallic aluminium(heteroscorpionate) complexes 9-14 were synthesised in very high yields. The single-crystal X-ray structures of 12 and 13 confirm an asymmetric κ2-NO-μ-O arrangement in a dinuclear molecular disposition. These bimetallic aluminium complexes were investigated as catalysts for the synthesis of cyclic carbonates from epoxides and carbon dioxide in the presence of ammonium salts. Under the optimal reaction conditions, complex 9 in combination with tetrabutylammonium bromide acts as a very efficient catalyst system for the conversion of both monosubstituted and internal epoxides into the corresponding cyclic carbonates showing broad substrate scope. Complex 9 and tetrabutylammonium bromide is the second most efficient aluminium-based catalyst system for the reaction of internal epoxides with carbon dioxide. A kinetic study has been carried out and showed that the reactions were first order in complex 9 and tetrabutylammonium bromide concentrations. Based on the kinetic study, a catalytic cycle is proposed.
- Martínez, Javier,Castro-Osma, José A.,Earlam, Amy,Alonso-Moreno, Carlos,Otero, Antonio,Lara-Sánchez, Agustín,North, Michael,Rodríguez-Diéguez, Antonio
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p. 9850 - 9862
(2015/06/30)
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- Efficient fixation of CO2 by a zinc-coordinated conjugated microporous polymer
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Zinc-coordinated conjugated microporous polymers (Zn-CMPs), prepared by linking salen zinc and 1,3,5-triethynylbenzene, exhibit extraordinary activities (turnover frequencies of up to 11600 h-1), broad substrate scope, and group tolerance for the synthesis of functional organic carbonates by coupling epoxides with CO2 at 120 °C and 3.0 MPa without the use of additional solvents. The catalytic activity of Zn-CMP is comparable to those of homogeneous catalysts and superior to those of other heterogeneous catalysts. This catalyst could be reused more than ten times without a significant decrease in performance.
- Xie, Yong,Wang, Ting-Ting,Yang, Rui-Xia,Huang, Nian-Yu,Zou, Kun,Deng, Wei-Qiao
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p. 2110 - 2114
(2014/10/15)
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- Pd/C: An efficient and heterogeneous protocol for oxidative carbonylation of diols to cyclic carbonate
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The present protocol involves highly efficient and practical approach for the synthesis of cyclic carbonate via oxidative carbonylation of diols, glycerol, and its derivatives using Pd/C as a heterogeneous, inexpensive, and recyclable catalyst. The effect of various reaction parameters, such as solvent, base, time, and temperature was investigated and applied for the synthesis of value added cyclic carbonates in a good to excellent yield within shorter reaction time. The developed catalytic system circumvents the use of ligand and dehydrating agent with an additional advantage of palladium catalyst recovery and reuse for up to four consecutive cycles.
- Chavan, Sujit P.,Bhanage, Bhalchandra M.
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supporting information
p. 1199 - 1202
(2014/02/14)
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- A powerful aluminum catalyst for the synthesis of highly functional organic carbonates
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An aluminum complex based on an amino triphenolate ligand scaffold shows unprecedented high activity (initial TOFs up to 36 000 h-1), broad substrate scope, and functional group tolerance in the formation of highly functional organic carbonates prepared from epoxides and CO2. The developed catalytic protocol is further characterized by low catalyst loadings and relative mild reaction conditions using a cheap, abundant, and nontoxic metal.
- Whiteoak, Christopher J.,Kielland, Nicola,Laserna, Victor,Escudero-Adán, Eduardo C.,Martin, Eddy,Kleij, Arjan W.
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supporting information
p. 1228 - 1231
(2013/03/14)
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- A general and expedient synthesis of 5- and 6-membered cyclic carbonates by palladium-catalyzed oxidative carbonylation of 1,2- and 1,3-diols
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We present a general, practical, and efficient approach to 5- and 6-membered organic carbonates by palladium-catalyzed direct oxidative carbonylation of 1,2- and 1,3-diols, respectively. Reactions were carried out at 100 °C in N,N-dimethylacetamide as the solvent under 20 atm (at 25 °C; 1 atm=101.3 kPa) of a 4:1 v/v CO/air mixture in the presence of 0.5-2 mol % of PdI2 and KI (KI/PdI2 molar ratio=10). Excess dehydrating agent, such as trimethyl orthoacetate, was necessary in several cases to obtain appreciable results. The method could also be applied to the synthesis of a high-value-added glycerol carbonate from glycerol, a readily available raw material. When applied to α-D-glucose, a double carbonylation process took place, with direct formation of α-D-glucofuranose 1,2:5,6-dicarbonate.
- Gabriele, Bartolo,Mancuso, Raffaella,Salerno, Giuseppe,Veltri, Lucia,Costa, Mirco,Dibenedetto, Angela
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experimental part
p. 1778 - 1786
(2012/04/04)
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- Synthesis of cyclic carbonates from atmospheric pressure carbon dioxide using exceptionally active aluminium(salen) complexes as catalysts
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Dimetallic aluminium(salen) complexes show exceptionally high catalytic activity for the synthesis of cyclic carbonates from terminal epoxides at ambient temperature and pressure. The process has the potential to contribute towards decreasing atmospheric
- Melendez, Jaisiel,North, Michael,Pasquale, Riccardo
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p. 3323 - 3326
(2008/03/18)
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- Mechanistic study on nitrosation-deaminocyclization of mono-carbamoylated vicinal amino alcohols and diols: a new preparative in situ formation of ethanediazo hydroxide for the ethylation of carboxylates under mild conditions
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While the cyclization of N-carbamoylamino alcohols into oxazolidinones via the activation with NO(1+) underwent smoothly, we found that similar reactions of vicinal diol monocarbamates were very slow. Mechanistic studies by means of time-resolved IR measurements of the former reaction suggested that the initial O-nitrosation was the rate-determining step. Indeed, the introduction of an ethyl group on the nitrogen terminus of diol monocarbamate promoted the desired cyclic carbonate formation. The concomitantly formed ethanediazo hydroxide, the precursor of the protonated form of diazoethane, was evidenced by trapping with p-nitrobenzoic acid as an ethyl ester. The formation of ethyl ester accelerates the reaction in an irreversible manner. Based on an elaboration of the substrates and reaction conditions, 2,3-dimethyl-2,3-butanediol mono-N-ethyl-N-nitrosocarbamate, which is easily prepared in situ from the corresponding ethylcarbamate and t-butyl nitrite, was developed as a new ethylation reagent of various carboxylic acids under mild conditions.
- Suzuki, Masumi,Sugai, Takeshi
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p. 1217 - 1228
(2007/10/03)
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- Novel cyclization of dimeric dianions anils or aldehydes with triphosgene: A safe and efficient synthesis of substituted imidazolidin-2-ones and 4,5-diaryl-1,3-dioxolan-2-ones
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Substituted imidazolidin-2-ones and 4,5-diaryl-1,3-dioxolan-2-ones, were synthesized from the reaction of Schiff bases or aldehydes with samarium diiodide in dry THF, followed by addition of triphosgene. The reactions were clean and only imidazolidin-2-ones could be detected by examination of 1H nuclear magnetic resonance spectra of crude products. All reactions were completed within 2-4 h, with moderate to good yields of immidazolidin-2-ones being isolated.
- Li, Zhifang,Zhang, Yongmin
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- Efficient synthesis and hydrolysis of cyclic oxalate esters of glycols.
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Based on the mechanism postulated for the formation of the cyclic carbonates 3 in the reactions of glycols 1 with oxalyl chloride in the presence of triethylamine, we present here three efficient syntheses of the cyclic oxalates 2 of various glycols 1 by controlling the formation of 3: replacement of the base by pyridine markedly diminishes yields of 3 in all reactions, realizing dramatic reversals of the product ratios in the reactions with the (R*,R*)-compounds 1g-i,q,r and pinacol (1k); although considerable amounts of the oxalate polymers are formed in the reactions with some (R*,S*)-glycols, this drawback can be removed by the use of 2,4,6-collidine instead of pyridine; 1,1'-oxalyldiimidazole is useful for the synthesis of two selected cyclic oxalates 2e,f. The cyclic oxalates 2 other than trisubstituted and tetrasubstituted ones were found to be very reactive: kinetic studies on the hydrolysis of 1,4-dioxane-2,3-dione (2a) as well as its mono- and some selected 5,6-disubstituted derivatives 2 have revealed that they undergo hydrolysis 260-1500 times more rapidly than diethyl oxalate (12) in acetate buffer-acetonitrile (pH 5.69) at 25 degrees C. Although the cyclic oxalate 21 from cis-1,2-cyclopentanediol (11) was 1.5 times more reactive than 2a, it has been shown with other substrates that increasing number of the alkyl substituents decreases the rate of hydrolysis. On the contrary, the phenyl group was found to have somewhat accelerative effect.
- Itaya, Taisuke,Iida, Takehiko,Gomyo, Yasuko,Natsutani, Itaru,Ohba, Masashi
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p. 346 - 353
(2007/10/03)
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- Reaction of various oxiranes and carbon dioxide. Synthesis and aminolysis of five-membered cyclic carbonates
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Various oxiranes reacted with carbon dioxide at 100 °C using lithium bromide as a catalyst under atmospheric pressure to afford the corresponding five-membered cyclic carbonates quantitatively. The rate of the reaction increased as the bulkiness of substituents on the oxirane ring was reduced or an electron-withdrawing group was introduced on the oxirane ring. The stereochemistry of the reaction of oxirane and carbon dioxide was retention without loss of optical purity. When substituted phenylethylene carbonates were reacted with benzylamine, the selectivity to afford secondary alcohol increased as the electron-withdrawing ability of the para-substituent increased.
- Iwasaki, Takeshi,Kihara, Nobuhiro,Endo, Takeshi
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p. 713 - 719
(2007/10/03)
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- Electrogenerated base-promoted synthesis of organic carbonates from alcohols and carbon dioxide
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Electrogenerated bases promote the reaction between primary alcohols and carbon dioxide to give organic carbonates in excellent yields. Secondary alcohols are converted in moderate yields, whereas tertiary alcohols and phenols are unreactive. 1,2-Diols give a mixture of both cyclic and linear diand monocarbonates. These latter are intermediates in the reaction pathway leading to the cyclic derivatives.
- Casadei, Maria Antonietta,Cesa, Stefania,Rossi, Leucio
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p. 2445 - 2448
(2007/10/03)
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- One-Pot Formation of Carbonates from the Reactions of Carbonyl Compounds with Samarium Diiodide and Methyl Chloroformate
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Treatment of carbonyl compounds with SmI2 and methyl chloroformate in the presence of molecular sieves provides the cyclic carbonates or biscarbonates of pinacols. This one-pot reaction proceeds rapidly even with aliphatic ketones. The stereoch
- Lu, Ling,Fang, Jim-Min,Lee, Gene-Hsiang,Wang, Yu
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p. 279 - 289
(2007/10/03)
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- Synthesis of the Cyclic Oxalates of 1,2-Glycols by Controlling the Formation of the Cyclic Carbonates
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Cyclic oxalates 2 have been efficiently synthesized by the reaction of 1,2-glycols 1 with oxalyl chloride in the presence of pyridine or 2,4,6-trimethylpyridine, rather than triethylamine, or by reaction with 1,1'-oxalyldiimidazole.
- Itaya, Taisuke,Iida, Takehiko
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p. 1671 - 1672
(2007/10/02)
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- Formation of cyclic carbonates in the reactions of 1,2-glycols with oxalyl chloride
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Oxalyl chloride reacts with a wide range of 1,2-glycols in the presence of triethylamine to produce 1,3-dioxolan-2-ones together with 1,4-dioxane-2,3-diones; the ratio of the products largely depends on the structure of the 1,2-glycol. The formation of the cyclic carbonates may be rationalized in terms of stereoelectronically controlled cleavage of the tetrahedral intermediates.
- Itaya,Iida,Eguchi
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p. 408 - 410
(2007/10/02)
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- Cyclocondensation of oxalyl chloride with 1,2-glycols
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Oxalyl chloride reacts with a wide range of acyclic 1,2-glycols 1 in the presence of triethylamine to produce 1,3-dioxolan-2-ones 3 together with 1,4-dioxane-2,3-diones 2. Ethylene glycol (1d), monosubstituted ethylene glycols 1e, j-l, and erythro-1,2-disubstituted ethylene glycols 1f, m, o provide the cyclic carbonates 3 as the minor products, while the threo-compounds 1g, i, n, p, q and pinacol (1h) afford 3 as the main products. The formation of 3 may be rationalized in terms of stereoelectronically controlled cleavage of the conjugate base 17- of the tetrahedral intermediates. The rate of the conformational change of 17- into 18- and the equilibrium constant between these conformers are proposed to be the major factors affecting the reaction pattern.
- Iida,Itaya
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p. 10511 - 10530
(2007/10/02)
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- REACTION OF CHLOROSULFONYL ISOCYANATE WITH 1,2-DIOLS: REARRANGEMENT AND FORMATION OF CARBONATES
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1,2-Diols, 1a-e, upon reaction with chlorosulfonyl isocyanate (CSI) gave the ketones, 3a-e.Under similar experimental conditions, 1,2-diols, 1f-k, gave carbonyl compounds, 3f-k, carbonates, 6f-k, carboxamides, 7h,i, and the epoxide, 5i.
- Joseph, Sajan P.,Dhar, D. N.
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p. 2295 - 2302
(2007/10/02)
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- RING ENLARGING DIPOLAR CYCLOADDITIONS OF CHLOROSULFONYLISOCYANATE TO EPOXIDES
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Chlorosulfonyl isocyanate cycloadds to epoxides at -78 deg C to give 1,3-dioxolan-2-ones and/or 2-oxazolidones in moderate yields after aqueous work-up.
- Lorincz, Tibor,Erden, Ihsan,Naeder, Reinhard,Meijere, Armin de
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p. 123 - 130
(2007/10/02)
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- The Reaction of Chlorosulfonyl Isocyanate with Epoxides. A Novel Conversion of Epoxides to Cyclic Carbonates
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The facile reaction of chlorosulfonyl isocyanate (CSI) with epoxides is described.The initially formed 2-chlorosulfonylimino-1,3-dioxolane 2a-e and N-chlorosulfonyl-1,3-oxazolidin-2-one 3a-e derivatives undergo smooth hydrolysis to yield the corresponding 1,3-dioxolan-2-one 4a-e and 1,3-oxazolidin-2-one 5a-e derivatives respectively.This reaction sequence provides a convenient one-pot method for the conversion of epoxides to cylic carbonates.Substrates such as 1g-i are exceptions to this otherwise general reaction pathway.
- Keshava Murthy, K. S.,Dhar, D. N.
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p. 1721 - 1725
(2007/10/02)
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- A CONVENIENT ONE-POT SYNTHESIS OF 1,3-DIOXOLAN-2-ONES FROM EPOXIDES USING CHLOROSULFONYL ISOCYANATE
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An efficient, simple and stereospecific one-pot method is described for the conversion of epoxides to 1,3-dioxolan-2-ones, by using chlorosulfonyl isocyanate (CSI).
- Murthy, K. S. Keshava,Dhar, D. N.
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p. 687 - 696
(2007/10/02)
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