Challenges in the catalytic synthesis of cyclic and polymeric carbonates from epoxides and CO2

Pescarmona, Paolo P.; Taherimehr, Masoumeh

doi:10.1039/c2cy20365k

Cited by 349 publications

(294 citation statements)

References 98 publications

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“…This may help to identify, where possible, improvements that lead to a more widespread use of organocatalysts in CO 2 conversion. Other excellent reviews focusing on the use of hetero-and/or homogenous catalyst systems have recently appeared, 4,[7][8][9][10]18,19,[39][40][41][42] and may serve as a reference point.…”

Section: Introductionmentioning

confidence: 99%

Sustainable conversion of carbon dioxide: the advent of organocatalysis

2015

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The conversion of carbon dioxide (CO 2 ), an abundant renewable carbon reagent, into chemicals of academic and industrial interest is of imminent importance to create a higher degree of sustainability in chemical processing and production. Recent progress in this field is characterised by a plethora of organic molecules able to mediate the conversion of suitable substrates in the presence of CO 2 into a variety of value-added commodities with advantageous features combining cost-effectiveness, metalfree transformations and general substrate activation profiles. In this review, the latest developments are discussed in the field of CO 2 catalysis with a focus on organo-mediated conversions and their increasing importance as to serve as practicable alternatives for metal-based processes. Also a critical assessment of the state-of-the-art is presented with attention on those features that need further attention to lift the usefulness of organocatalysis in the production of organic molecules of potential commercial interest.

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Section: Introductionmentioning

confidence: 99%

Sustainable conversion of carbon dioxide: the advent of organocatalysis

2015

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“…1,2,6 Despite the disadvantage of CO 2 having sluggish reactivity, recent work has unambiguously demonstrated that new opportunities may become available when proper catalytic methods are designed that help to improve the reactivity, selectivity and/or sustainability profiles of such processes. Among the most widely studied reactions in CO 2 catalysis is the formation of cyclic organic carbonates (COCs) [11][12][13][14][15][16][17][18] apart from their analogous and related linear carbonates 19 and poly(carbonates). [20][21][22] These COCs have been frequently associated with numerous applications involving them as non-protic solvents, precursors for poly(carbonate) synthesis, electrolyte solvents and more recently as useful intermediates in organic synthesis.…”

Section: Introductionmentioning

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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“…The mechanism of the reaction is well known and was already reported in various publications. 6 The reaction is initiated by the attack of a nucleophile (usually represented by a halide) to the C1 or the C2 carbon, depending on the substituents, of the epoxide via a S N 2 mechanism. The ring opening is followed by CO 2 insertion with generation of a cyclic carbonate.…”

Section: Introductionmentioning

confidence: 99%

Bi-functional heterogeneous catalysts for carbon dioxide conversion: enhanced performances at low temperature

et al. 2018

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Novel heterogeneous bi-functional catalysts bearing tin or zinc inserted as single sites within the silica architecture acting as acid centres and decorated with imidazolium moieties as the nucleophile source were successfully synthesized. The materials were extensively characterized via various techniques including N 2 physisorption, solid state nuclear magnetic resonance, X-ray photoelectron spectroscopy, transmission electron microscopy and adsorption microcalorimetry. The solids were tested as catalysts for the conversion of carbon dioxide, selecting the synthesis of styrene carbonate as the target reaction.Both materials exhibited improved performances compared to the analogous solids functionalized with the sole imidazolium salt as well as to other materials reported in the literature. The Sn-based catalyst displayed excellent conversion also in the presence of various epoxides. In all experiments the bifunctional solid allowed reducing the reaction temperature below 150 C. In the presence of glycidol the temperature was decreased down to 30 C. The short synthesis protocol of the heterogeneous catalysts, together with the 100% atom economy of the target reaction and the low reaction temperature, make the entire process highly sustainable. Moreover, the Sn-based catalyst was stable under the selected reaction conditions and reusable for multiple catalytic cycles.

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Challenges in the catalytic synthesis of cyclic and polymeric carbonates from epoxides and CO2

Cited by 349 publications

References 98 publications

Sustainable conversion of carbon dioxide: the advent of organocatalysis

Sustainable conversion of carbon dioxide: the advent of organocatalysis

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

Bi-functional heterogeneous catalysts for carbon dioxide conversion: enhanced performances at low temperature

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