High activity and switchable selectivity in the synthesis of cyclic and polymeric cyclohexene carbonates with iron amino triphenolate catalysts

Taherimehr, Masoumeh; Al-Amsyar, Syed Muhammad; Whiteoak, Christopher J.; Kleij, Arjan W.; Pescarmona, Paolo P.

doi:10.1039/c3gc41303a

Cited by 145 publications

(144 citation statements)

References 39 publications

(54 reference statements)

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“…The use of a Fe(III)amino(trisphenolate) catalyst (14a; Figure 4) resulted in the selective formation of CHC or PCHC from CHO in CO 2 rich/scCO 2 reaction media. 86 The presence of an equimolar amount of a nucleophilic organic salt containing a poor leaving group (PPN-Cl) when compared to TBAB and TBAI suppressed the ring-closure reaction and selective and quantitative formation of PCHC was observed (cat/co-cat ratio 1:1; Entry 3, Table 4) under supercritical conditions. Since the catalysts employed were not chiral, an atactic polymer was obtained with M n = 6000 which is lower compared to those obtained with other catalytic systems (vide supra); moreover, 1 H NMR/MALDI analysis of the polymeric product indicated that the polycarbonate chains were end-capped predominantly with hydroxyl groups, suggesting that water was the main cause of the termination of the polymer growth (i.e., being a chain-transfer agent).…”

Section: Control Over Selectivity Features In Coc Preparationmentioning

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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Section: Control Over Selectivity Features In Coc Preparationmentioning

confidence: 99%

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

2015

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“…Iron is another potential element as it is the most abundant transition metal. This novel di- [98], corrole 18 and 19 [99] and amino triphenolate 20 [100] complexes.…”

Section: Homogeneous Catalystsmentioning

confidence: 99%

“…A wide range of catalysts has been successfully reported, leading to the production of polycarbonates. Homogeneous catalysts are classified in two broad types, bimetallic (Scheme 1.7) and monometallic (Scheme boxdipy titanium(IV) 15 [96], bimetallic iron(III) macrocyclic reduced "Robson" type ligand 16 [97], pyridylamino-bis(phenolate) 17 [98], iron-corrole 18 and 19 [99] and iron amino triphenolate 20 [100] catalysts.…”

Section: Homogeneous Catalystsmentioning

confidence: 99%

Copolymerization of cyclohexene oxide with CO₂catalyzed by tridentate N-heterocyclic carbene titanium(iv) complexes

Quadri

Roux

2014

Dalton Trans.

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“…As a potential solution for these challenges, other types of catalysts have to be considered. Kleij et al [34] developed a binary catalytic system (Scheme 3) that consists of a triphenolate complex acting as Lewis acid and tetrabutylammonium bromide (TBAB) as cocatalyst. In this case, the choice of cocatalyst and also the ratio between the iron catalyst and the nucleophilic cocatalyst are of high importance as this controls the activity and selectivity [50] of the reaction, Fig.…”

Section: Introductionmentioning

confidence: 99%

“…However, the use of metal complexes as substrate activators has resulted in far better catalyst systems enabling significantly higher reactivities and selectivities. Important advances in this area have been obtained by using complexes based on transition/main group metals such as aluminum, cobalt, or iron with ligand frameworks such as porphyrins [26], phthalocyanines [31][32][33], triphenolates [34], and salens ( Fig. 2) [35][36][37][38][39][40].…”

Section: Introductionmentioning

confidence: 99%

Metal Complexes Catalyzed Cyclization with CO2

Rintjema

Carrodeguas

Laserna

et al. 2015

Topics in Organometallic Chemistry

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This chapter describes in general terms the catalytic methodology that has been made available for the use of carbon dioxide (CO 2 ) in cyclization reactions that incorporate an intact CO 2 fragment without changing the formal oxidation state of the carbon center. The major focus of this chapter will be on the most successful organometallic/inorganic complexes that have been used as catalyst systems throughout the last decade and the preferred ligand frameworks leading to elevated reactivity and/or selectivity behavior in CO 2 coupling reactions. Attention will be especially given to homogeneous catalyst systems as they have proven to be more versatile in CO 2 conversion catalysis and often have modular characteristics that allow for optimization of structure-activity relationships. The most important reactions that have been studied in the current context are designated CO 2 "addition" reactions to small molecule heterocycles such as epoxides and aziridines, though more recently other coupling partners such as diamines, dialcohols, and amino nitriles have further advanced the use of CO 2 in organic synthesis providing access to a wider range of structures. This chapter will serve to demonstrate the utility of CO 2 as a carbon reagent in the catalytic formation of the most prominent organic structures using cyclization strategies specifically.

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High activity and switchable selectivity in the synthesis of cyclic and polymeric cyclohexene carbonates with iron amino triphenolate catalysts

Cited by 145 publications

References 39 publications

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

Copolymerization of cyclohexene oxide with CO₂catalyzed by tridentate N-heterocyclic carbene titanium(iv) complexes

Metal Complexes Catalyzed Cyclization with CO2

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High activity and switchable selectivity in the synthesis of cyclic and polymeric cyclohexene carbonates with iron amino triphenolate catalysts

Cited by 145 publications

References 39 publications

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

Copolymerization of cyclohexene oxide with CO2catalyzed by tridentate N-heterocyclic carbene titanium(iv) complexes

Metal Complexes Catalyzed Cyclization with CO2

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Copolymerization of cyclohexene oxide with CO₂catalyzed by tridentate N-heterocyclic carbene titanium(iv) complexes