Mechanism of Cyclic Carbonate Synthesis from Epoxides and CO<sub>2</sub>

North, Michael; Pasquale, Riccardo

doi:10.1002/ange.200805451

Cited by 157 publications

(89 citation statements)

References 49 publications

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“…So lots of attentions have been paid on this reaction due to its high atom utilisation, cheap, and low generation of by-product [7,8]. Numerous catalysts have been proposed for incorporating CO 2 into cyclic carbonates including alkali metal salts [9,10], metal oxides [11,12], ionic liquids (ILs) [13][14][15][16], and others [17][18][19][20][21]. Although significant advances have been made, the harsh reaction condition, water sensitivity, and the requirement of organic solvent are still the disadvantages those are necessary to be surmounted.…”

Section: Introductionmentioning

confidence: 99%

Insight into the activity of efficient acid–base bifunctional catalysts for the coupling reaction of CO₂

et al. 2015

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2015): Insight into the activity of efficient acid-base bifunctional catalysts for the coupling reaction of CO 2 ,The fixation of carbon dioxide with epoxide catalysed by a series of carboxylic acidic functionalised ionic liquids (ILs) catalysts is investigated by density functional theory method. Except for the catalysts reported by the experiment, the catalytic activity of a new designed catalyst (4c see Scheme 1) is also explored. These ILs are categorised into four groups according to the different cation structures and number of functional groups. The effects of different chain length, anion, and cation structure on the catalytic activity are explored. The elongation of alkyl chain length in cation will increase the product yield, while increasing the chain bulk has almost negligible effect on the enhancement of catalytic activity. Utilisation of imidazole group as the cation is better than pyridine group. And the cation with two functional groups will have a better catalytic activity than that with one functional group.

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Section: Introductionmentioning

confidence: 99%

Insight into the activity of efficient acid–base bifunctional catalysts for the coupling reaction of CO₂

et al. 2015

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“…Polycarbonate and cyclic carbonate synthesis catalysed by chromiumA C H T U N G T R E N N U N G (salen) complexes are known to be bimolecular; [25] therefore, we reasoned that a suitable bimetallic salen complex might display significantly improved catalytic activity in the reaction between carbon dioxide and epoxides. In this paper we give full details of our work in this area, [30] which was aimed at developing a catalyst, which would be sufficiently active to allow the synthesis of cyclic carbonates from waste carbon dioxide without requiring energy input.…”

Section: Introductionmentioning

confidence: 99%

Cyclic Carbonate Synthesis Catalysed by Bimetallic Aluminium–Salen Complexes

Clegg¹,

Harrington²,

North³

et al. 2010

Chemistry A European J

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174

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The development of bimetallic aluminium-salen complexes [{Al(salen)}(2)O] as catalysts for the synthesis of cyclic carbonates (including the commercially important ethylene and propylene carbonates) from a wide range of terminal epoxides in the presence of tetrabutylammonium bromide as a cocatalyst is reported. The bimetallic structure of one complex was confirmed by X-ray crystallography. The bimetallic complexes displayed exceptionally high catalytic activity and in the presence of tetrabutylammonium bromide could catalyse cyclic carbonate synthesis at atmospheric pressure and room temperature. Catalyst-reuse experiments demonstrated that one bimetallic complex was stable for over 60 reactions, though the tetrabutylammonium bromide decomposed in situ by a retro-Menschutkin reaction to form tributylamine and had to be regularly replaced. The mild reaction conditions allowed a full analysis of the reaction kinetics to be carried out and this showed that the reaction was first order in aluminium complex concentration, first order in epoxide concentration, first order in carbon dioxide concentration (except when used in excess) and unexpectedly second order in tetrabutylammonium bromide concentration. Further kinetic experiments demonstrated that the tributylamine formed in situ was involved in the catalysis and that addition of butyl bromide to reconvert the tributylamine into tetrabutylammonium bromide resulted in inhibition of the reaction. The reaction kinetics also indicated that no kinetic resolution of racemic epoxides was possible with this class of catalysts, even when the catalyst was derived from a chiral salen ligand. However, it was shown that if enantiomerically pure styrene oxide was used as substrate, then enantiomerically pure styrene carbonate was formed. On the basis of the kinetic and other experimental data, a catalytic cycle that explains why the bimetallic complexes display such high catalytic activity has been developed.

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“…[5][6][7][8][9][10] This atom economical reaction represents a sustainable route to cyclic carbonates in contrast to other routes e.g. [27][28][29][30][31][32] In general the reaction between epoxides and heterocumulenes is a straightforward approach to a wide range of five-membered ring heterocycles. [11][12][13] Frequently employed catalytic systems are based on Lewis acidic metal complexes, [14][15][16] alkali metal halides 17,18 as well as imidazolium, 19-21 phosphonium [22][23][24][25][26] or ammonium salts.…”

Section: Introductionmentioning

confidence: 99%

Atom economical synthesis of di- and trithiocarbonates by the lithium tert-butoxide catalyzed addition of carbon disulfide to epoxides and thiiranes

2016

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Alkali metal alkoxides were studied as catalysts for the addition of CS2 to epoxides. A screening of several commercially available alkoxides revealed lithium tert-butoxide as an active and selective catalyst for this reaction. The influence of different reaction parameters as well as the substrate scope under optimized reaction conditions has been studied. Terminal and highly substituted epoxides as well as thiiranes were converted. In total 28 products were prepared and isolated in yields up to 95%. Notably, the reactions were performed under mild conditions without additional solvents. The regio- and stereoselectivity of the reaction has been studied e.g. by converting (R)-styrene and (R)-propylene oxide. Moreover, the test reaction was monitored by (13)C NMR and a plausible mechanism for the conversion of terminal and internal epoxides is given. This proposal is in agreement with the observed regio- and stereoselectivity of the reaction.

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Mechanism of Cyclic Carbonate Synthesis from Epoxides and CO₂

Cited by 157 publications

References 49 publications

Insight into the activity of efficient acid–base bifunctional catalysts for the coupling reaction of CO₂

Insight into the activity of efficient acid–base bifunctional catalysts for the coupling reaction of CO₂

Cyclic Carbonate Synthesis Catalysed by Bimetallic Aluminium–Salen Complexes

Atom economical synthesis of di- and trithiocarbonates by the lithium tert-butoxide catalyzed addition of carbon disulfide to epoxides and thiiranes

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Mechanism of Cyclic Carbonate Synthesis from Epoxides and CO2

Cited by 157 publications

References 49 publications

Insight into the activity of efficient acid–base bifunctional catalysts for the coupling reaction of CO2

Insight into the activity of efficient acid–base bifunctional catalysts for the coupling reaction of CO2

Cyclic Carbonate Synthesis Catalysed by Bimetallic Aluminium–Salen Complexes

Atom economical synthesis of di- and trithiocarbonates by the lithium tert-butoxide catalyzed addition of carbon disulfide to epoxides and thiiranes

Contact Info

Product

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About

Mechanism of Cyclic Carbonate Synthesis from Epoxides and CO₂

Insight into the activity of efficient acid–base bifunctional catalysts for the coupling reaction of CO₂

Insight into the activity of efficient acid–base bifunctional catalysts for the coupling reaction of CO₂