Highly efficient synthesis of cyclic carbonates from epoxides catalyzed by indium tribromide system

Shibata, Ikuya; Mitani, Ikuko; Imakuni, Akira; Baba, Akio

doi:10.1016/j.tetlet.2010.12.009

Cited by 59 publications

(32 citation statements)

References 22 publications

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“…As the mechanism of the coupling of CO 2 with epoxides has not been elucidated completely, we propose reaction pathways A and B (Scheme ), similarly to Shibata et al.,10c and these paths are based on our observations of the reactions. In path A, epoxide 8 first coordinates to MgBr 2 to form complex 9 , which undergoes rapid rearrangement to form alkyl bromide 10 .…”

Section: Methodsmentioning

confidence: 52%

Efficient Synthesis of Cyclic Carbonates by Mg^II/Phosphine‐Catalyzed Coupling Reactions of Carbon Dioxide and Epoxides

Ren

Shim

2013

ChemCatChem

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Carbon dioxide (CO 2 ) is an abundant, cheap, and green solvent, and it is also a renewable C 1 source for chemical syntheses. [1] Nevertheless, the activation and fixation of CO 2 remains a challenging task for researchers in organic and organometallic chemistry because of its thermodynamic stability and low reactivity. [2] With regard to the depletion of petroleum reserves and the greenhouse effect from the increase in CO 2 emissions, catalytic processes that employ CO 2 as a feedstock have been investigated intensively over the last two decades. [3] Promising methodology in this area is the coupling reactions of CO 2 with epoxides to produce cyclic carbonates, [4] which are useful as synthetic intermediates, [5] aprotic polar solvents, and feedstock for engineering plastics. [6] Numerous catalysts have been developed for this reaction system. [7] Although the advances have been significant, there are drawbacks, such as low catalytic stability and reactivity, air sensitivity, and the need for a co-solvent, high pressures, or high temperatures.Continuous efforts have been made to improve existing techniques and to discover new methods for CO 2 activation, [2c, 8] which generally requires organometallic reagents, organic halides, [9] or other preactivated/in situ generated carboxyl zwitterionic complexes, such as compound 1, obtained from phosphines, [8a, 10] compound 2, obtained from tertiary amines or tetralkylammonium salts, [2a, 8b, 11] compound 3, obtained from N-heterocyclic carbenes (NHCs), [12] compound 4, obtained from 4-(dimethylamino)pyridine (DMAP), [2c, 13] and compound 5, obtained from 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) [8c, 14] (Scheme 1). Tetrabutylammonium bromide (TBAB), DMAP, and NHC-based catalyst systems have been studied extensively because of their ease of preparation and commercial availability. High temperatures are required in most cases, [2a, 6b] despite the heat that is released from the coupling reaction of epoxides with CO 2 . [15] Phosphine-based catalyst systems have attracted only a little attention. [16] Therefore, this study evaluated phosphines as potential co-catalysts for the activation of CO 2 at room temperature to reduce energy costs during the reaction.The synthesis of vinyl ethylene carbonate (VEC, 7 a), which is an effective electrolyte additive for high-performance Li ion battery applications and an important intermediate for fine chemicals, [6b, 17] was initially chosen as a model for investigating the reaction parameters (Table 1). Mg II complexes are used widely because they are relatively less expensive than other complexes, and they are efficient catalysts in organic syntheses. [18] Magnesium is the central ion of the porphyrin in the green pigment of plants, chlorophyll, which is widely distributed in natural metabolism systems, and it is essential for the photosynthesis of glucose from CO 2 . [19] A few studies have reported that Mg II -based catalysts for the coupling of epoxides with CO 2 still require further improvements. [20] Some of ...

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Section: Methodsmentioning

confidence: 52%

Efficient Synthesis of Cyclic Carbonates by Mg^II/Phosphine‐Catalyzed Coupling Reactions of Carbon Dioxide and Epoxides

Ren

Shim

2013

ChemCatChem

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“…81 It seems likely that a bis-or monophosphine In(III) tribromide complex initially forms in situ, enhancing the nucleophilicity of the In-Br bonds. Coordination of the epoxide to the In(III) center and subsequent ring opening by an In-Br moiety yields an In(III) 2-bromoethan-1-olate dibromide that further reacts/cyclizes with carbon dioxide to yield the final ethylene carbonate.…”

Section: Addition Of Carbon Dioxide To Epoxide: Synthesis Of Cyclic Cmentioning

confidence: 99%

Gallium and Indium Compounds in Homogeneous Catalysis

Dagorne

Fliedel

Frémont

2016

Encyclopedia of Inorganic and Bioinorganic Chemistry

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The present contribution highlights the most recent and representative developments on the use of Ga and In species in homogeneous catalysis. Recent studies of various ligand‐supported Ga(III) and In(III) compounds in cyclic esters polymerization catalysis for the production of biodegradable polyester materials are also included. Various organic transformations may now be catalyzed using Ga(III) and In(III) Lewis acids allowing access to a wide range of valuable organic molecules through diverse reaction sequences. The recent use of stable and robust N ‐heterocyclic carbene Ga(III) and In(III) compounds as strong π‐Lewis acid catalysts for various organic reactions is also discussed: such species are certainly promising for the future developments of Ga(III)‐ and In(III)‐mediated reactions. Although Lewis acid‐assisted reactions certainly dominate the field in Ga(III) and In(III) chemistry, discrete low‐valent In(I) species, presently emerging in catalysis, clearly display a distinct reactivity allowing their exploitation both as soft Lewis acids and alkyl‐/allyl‐/arylating agents.

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“…5 Recently, sophisticated catalysts were reported for the homogeneous‐phase synthesis of organic carbonates at room temperature and at atmospheric pressure, including two‐ or single‐component bimetallic aluminum–salen systems,6 iron7 and bismuth8 complexes, and μ‐oxotetranuclear zinc and cobalt clusters 9. Alternative catalytic tools formed by combining Lewis acidic metal halides with nucleophilic co‐catalysts (i.e., MoCl 5 /PPh 3 ,10 ZnCl 2 /NBu 4 I,11 InBr 3 /PPh 3 12) have so far shown only low to moderate levels of activity for the synthesis of PC under ambient conditions. Nevertheless, inorganic metal complexes are inexpensive, readily available, and can serve as useful benchmarks to examine the potential of a metal towards the development of more elaborate organometallic complexes and clusters with enhanced activities and stabilities.…”

Section: Screening Of Group 4–6 Transition‐metal Complexes For the Symentioning

confidence: 99%

Synthesis of Cyclic Carbonates from Epoxides and CO₂ under Mild Conditions Using a Simple, Highly Efficient Niobium‐Based Catalyst

et al. 2013

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Highly efficient synthesis of cyclic carbonates from epoxides catalyzed by indium tribromide system

Cited by 59 publications

References 22 publications

Efficient Synthesis of Cyclic Carbonates by Mg^II/Phosphine‐Catalyzed Coupling Reactions of Carbon Dioxide and Epoxides

Efficient Synthesis of Cyclic Carbonates by Mg^II/Phosphine‐Catalyzed Coupling Reactions of Carbon Dioxide and Epoxides

Gallium and Indium Compounds in Homogeneous Catalysis

Synthesis of Cyclic Carbonates from Epoxides and CO₂ under Mild Conditions Using a Simple, Highly Efficient Niobium‐Based Catalyst

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Highly efficient synthesis of cyclic carbonates from epoxides catalyzed by indium tribromide system

Cited by 59 publications

References 22 publications

Efficient Synthesis of Cyclic Carbonates by MgII/Phosphine‐Catalyzed Coupling Reactions of Carbon Dioxide and Epoxides

Efficient Synthesis of Cyclic Carbonates by MgII/Phosphine‐Catalyzed Coupling Reactions of Carbon Dioxide and Epoxides

Gallium and Indium Compounds in Homogeneous Catalysis

Synthesis of Cyclic Carbonates from Epoxides and CO2 under Mild Conditions Using a Simple, Highly Efficient Niobium‐Based Catalyst

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Efficient Synthesis of Cyclic Carbonates by Mg^II/Phosphine‐Catalyzed Coupling Reactions of Carbon Dioxide and Epoxides

Efficient Synthesis of Cyclic Carbonates by Mg^II/Phosphine‐Catalyzed Coupling Reactions of Carbon Dioxide and Epoxides

Synthesis of Cyclic Carbonates from Epoxides and CO₂ under Mild Conditions Using a Simple, Highly Efficient Niobium‐Based Catalyst