Efficient carbonate synthesis under mild conditions through cycloaddition of carbon dioxide to oxiranes using a Zn(salphen) catalyst

Decortes, Antonello; Belmonte, Marta Martínez; Benet‐Buchholz, Jordi; Kleij, Arjan W.

doi:10.1039/c000493f

Cited by 269 publications

(136 citation statements)

References 23 publications

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“…[36][37][38] It can also be seen in Table 1 that increasing the amount of co-cata- [8]: I) catalyst system produces exclusively cyclic carbonates (i.e., selectivity is > 99%) and no polycarbonate formation could be observed.…”

Section: Resultsmentioning

confidence: 78%

“…We have chosen to use MEK as the solvent because carbonyl-containing solvents allow for a higher dissolution of carbon dioxide in the reaction mixture compared with other solvent types. [36,37] It can be seen from the results listed in Table 1 that neither the co-catalyst NBu 4 I (entry 1) nor the [FeA C H T U N G T R E N N U N G (TPhOA)] 2 catalyst alone is active (entry 2). However, the combination of both the Fe complex and the co-catalyst produces an active system giving good yields of the cyclic organic carbonate product when using the iodide nucleophile, even when ambient temperatures and carbon dioxide pressures as low as 0.2 MPa (i.e., 2 bar) are used (entry 5).…”

Section: Resultsmentioning

confidence: 95%

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An Efficient Iron Catalyst for the Synthesis of Five‐ and Six‐Membered Organic Carbonates under Mild Conditions

et al. 2012

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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.

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Section: Resultsmentioning

confidence: 78%

Section: Resultsmentioning

confidence: 95%

An Efficient Iron Catalyst for the Synthesis of Five‐ and Six‐Membered Organic Carbonates under Mild Conditions

et al. 2012

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“…The reaction conditions were chosen on the basis of the best results obtained in previous work using other metal complexes as catalysts. [11] Methyl ethyl ketone (MEK) was used as the solvent, taking into account that it is one of the most efficient solvents for solubilization of CO 2 . [12] The electronic effect of the substituents on the vanadium centers in these VO(salen) and VO(salphens) compounds was investigated with cyclic voltammetry (Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Vanadium Catalyzed Synthesis of Cyclic Organic Carbonates

et al. 2012

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Vanadium complexes bearing easily synthesized, differently functionalized salen and salphen ligands were prepared and tested for their ability to catalyze the cycloaddition of carbon dioxide to epoxides resulting in cyclic organic carbonates. The reactivity of the prepared catalysts dramatically increases when a coordinating hydroxyl group is present as a substituent in the organic epoxide. The commercially available [VO(acac)2] complex was used as reference compound, and, in this case, we found that V10O26·(NBu4)4 was formed during the catalytic reactions. This compound, characterized by X-ray diffraction analysis, is likely the active catalyst, and it results in significantly better yields of cyclic carbonates compared to those obtained with Schiff base containing vanadyl complexes. The high activity of the mixed polyoxo vanadyl-vanadate complex\ud marks it as a powerful catalyst within the context of CO2 fixation chemistry

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“…In particular, the Zn(salphen) system 2 ( Figure 1) reported by Kleij and co-workers showed a limited catalytic activity towards the conversion of internal epoxides 38,39 observing some degree of success when working with a CO 2 -rich or supercritical CO 2 reaction medium. 55 The bimetallic µ-oxo Al(salen) complex 1 ( Table 2).…”

Section: Conversion Of Internal Epoxides and Oxetanesmentioning

confidence: 99%

“…[35][36][37] Shortly hereafter, the group of Kleij reported on a mononuclear Zn(salphen) complex (Figure 1; 2) active towards CO 2 coupling with terminal epoxides under moderate CO 2 pressures [p(CO 2 ) = 0.2-1 MPa] and mild operating temperatures (T = 25−45 ºC). 38,39 The high activity of the Zn(salphen) complex was ascribed to its constrained geometry imposed by the ligand scaffold, which imparts increased Lewis-acid character to the catalytically active Zn ion. Moreover, the presence of bulky substituents (R = tBu) in the ortho-positions of the two iminiphenol donors prevents undesired dimerization and thus inactivation of the Zn(salphen) catalyst.…”

Section: Development Of Improved Reactivity In Coc Synthesismentioning

confidence: 99%

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

2015

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ABSTRACT:The catalytic formation of cyclic organic carbonates (COCs) using carbon dioxide (CO 2 ) as a renewable carbon feed stock is a highly vibrant area of research with an increasing amount of researchers focusing on this thematic investigation. These organic carbonates are highly useful building blocks and nontoxic reagents, and are most commonly derived from CO 2 coupling reactions with oxirane and di-alcohol precursors using homogeneous catalysis methodologies. The activation of suitable reaction partners using catalysis as a key technology is a requisite for efficient CO 2 conversion as its high kinetic stability poses a barrier to access functional organic molecules with added value in both academic and industrial laboratories. Though this area of science has been flourishing for at least a decade, in the last 2−3 years significant advancements have been made to address the general reactivity and selectivity issues that are associated with the formation of COCs. Here we present a concise overview of these activities with a primary focus to highlight the most important progress made and the opportunities that catalysis can bring about when the synthesis of these intermediates is optimized to a higher level of sophistication. The attention will be limited to those cases where homogeneous metal-containing systems have been employed as they possess the highest potential for directed organic synthesis using CO 2 as molecular building block. This review discusses examples of exceptional reactivity and selectivity taking into account the challenging nature of the substrates that were involved, and mechanistic understanding guiding the optimization of these protocols is also highlighted.

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Efficient carbonate synthesis under mild conditions through cycloaddition of carbon dioxide to oxiranes using a Zn(salphen) catalyst

Abstract: 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.

Cited by 269 publications

References 23 publications

An Efficient Iron Catalyst for the Synthesis of Five‐ and Six‐Membered Organic Carbonates under Mild Conditions

An Efficient Iron Catalyst for the Synthesis of Five‐ and Six‐Membered Organic Carbonates under Mild Conditions

Vanadium Catalyzed Synthesis of Cyclic Organic Carbonates

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

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