Polystyrene‐Supported N‐Heterocyclic Carbene–Silver Complexes as Robust and Efficient Catalysts for the Reaction of Carbon Dioxide and Propargylic Alcohols

Tang, Xiaodong; Qi, Chaorong; He, Haitao; Jiang, Huanfeng; Ren, Yanwei; Yuan, Gaoqing

doi:10.1002/adsc.201300007

Cited by 89 publications

(56 citation statements)

References 42 publications

(12 reference statements)

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“…The cyclic 25 carbonates, especially five-membered cyclic carbonates, are one kind of CO 2 fixation products and widely used as monomer for polymer synthesis, aprotic solvents, electrolytes for lithium-ion batteries, and as intermediates in the manufacture of fine chemicals. [12][13][14] This approach is 100% atom economical and 30 benefits from eliminating phosgene as a reagent.…”

Section: Introductionmentioning

confidence: 99%

Metal complexes bearing 2-(imidazol-2-yl)phenol ligands: synthesis, characterization and catalytic performance in the fixation of carbon dioxide with epoxides

2015

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A series of metal complexes bearing 2-(imidazol-2-yl)phenol ligands (Zn, Cu, Ni, Co, Pb) were synthesized and their structures were characterized by IR, NMR, elemental analysis and X-ray. The catalytical activities of all complexes for the coupling reaction of CO 2 and epoxide were then detected. The activity influence factors, such as temperature, time, pressure, substituents of ligands and metal 10 centre, were systematically investigated. All these complexes were efficient to catalyze the coupling of CO 2 and epoxide to generate cyclic carbonate in perfect yields (>90%) and selectivities (>99%) under optimized conditions of (2 MPa, 5 h, 110 °C) without any organic solvents. A 99.7% yield and >99% selectivity for propylene carbonate (PC) were obtained with C 7 /n-Bu 4 NI as catalyst system under the optimized conditions. The catalysts were also proved to be applicable to other terminal epoxides. It is 15 worthy noted that the Pb(II) complex was firstly used to catalyze the coupling reaction of epoxides with carbon dioxide. Moreover, these metal catalysts were recyclable with only minor losses in catalytic activity after simple separation. Finally, a plausible mechanism was given. 65 were distilled from CaH 2 .NMR spectra were recorded on a Bruker Al-400 MHz instrument using TMS as an internal standard. IR spectra were recorded on a Perkin-Elmer 2000 FT-IR spectrometer. Elemental analysis was conducted on a PE 2400 series II CHNS/O 70 elemental analyzer. Melting point was obtained from X-4-type digital micro-melting point apparatus. X-ray diffraction studies 65 each cycle, the catalyst C 1 could be easily separated from the product by the addition of ethanol, subsequent filtration and then used for the next run directly. The results in Fig. 5 exhibited that the catalyst C 1 could be reusable for at least 5 times without significant loss of activity, while the selectivity of the product 70 remained the same.

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Section: Introductionmentioning

confidence: 99%

Metal complexes bearing 2-(imidazol-2-yl)phenol ligands: synthesis, characterization and catalytic performance in the fixation of carbon dioxide with epoxides

2015

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“…Interestingly, this system may be recycled many times by simple distillation of the product, and the reused catalyst shows stable activity during a large period of time providing high turnover numbers. In this regard, the results obtained by Ma [51] and Jiang [52] are remarkable ( Figure 6) as these heterogeneous binary catalysts are able to combine low-temperature reactivity with excellent recyclability features. A similar approach was reported for a Zn-centered "salphen" complex combined with Bu 4 NI [48].…”

Section: Green Synthesis Of 13-dioxolan-2-ones and 13-dioxan-2-onesmentioning

confidence: 89%

“…The purpose of the Lewis acid is to activate the oxirane (by coordination; see Figure 5) after which the nucleophile can then more easily open the coordinated epoxide-ring. Demonstrative examples of effective binary catalysts that can be operated under mild reaction conditions, thereby marking these procedures relatively green, were reported by North [47], Kleij [48][49][50], Ma [51], and Jiang [52]. The most favorable features of a binary catalyst system combine a highly Lewis acidic metal center with relatively low affinity for the nucleophile (X) whereas the counter-cation Y should preferably form a weak contact ion pair with X.…”

Section: Green Synthesis Of 13-dioxolan-2-ones and 13-dioxan-2-onesmentioning

confidence: 99%

Green Catalytic Synthesis of Heterocyclic Structures Using Carbon Dioxide and Related Motifs

Kleij

2015

Green Synthetic Approaches for Biologically Relevant Heterocycles

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“…An interesting contribution to this field was made by the group of Jiang that reported on N-heterocyclic carbene-Ag complexes immobilized on a polystyrene support [90]. Various terminal secondary and tertiary propargylic alcohols were conveniently converted to their cyclic carbonate products by this supported catalyst with excellent selectivity and yield.…”

Section: Addition Of Carbon Dioxide To Double and Triple Bondsmentioning

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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Polystyrene‐Supported N‐Heterocyclic Carbene–Silver Complexes as Robust and Efficient Catalysts for the Reaction of Carbon Dioxide and Propargylic Alcohols

Cited by 89 publications

References 42 publications

Metal complexes bearing 2-(imidazol-2-yl)phenol ligands: synthesis, characterization and catalytic performance in the fixation of carbon dioxide with epoxides

Metal complexes bearing 2-(imidazol-2-yl)phenol ligands: synthesis, characterization and catalytic performance in the fixation of carbon dioxide with epoxides

Green Catalytic Synthesis of Heterocyclic Structures Using Carbon Dioxide and Related Motifs

Metal Complexes Catalyzed Cyclization with CO2

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