Asymmetric Copolymerization of CO<sub>2</sub> with <i>meso</i>‐Epoxides Mediated by Dinuclear Cobalt(III) Complexes: Unprecedented Enantioselectivity and Activity

Liu, Ye; Ren, Wei‐Min; Liu, Jie; Lu, Xiao‐Bing

doi:10.1002/anie.201305154

Cited by 220 publications

(177 citation statements)

References 51 publications

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“…Recently, we developed a chiral catalyst system based on the biphenol-linked dinuclear Co(III) complex (Fig. 1), which exhibited excellent activity, unprecedented enantioselectivity and molecular-weight control for the alternating copolymerization of CO 2 with mesoepoxides such as CPO under mild reaction conditions 25 . Previously, Coates and co-workers [26][27][28] have demonstrated that the dinuclear cobalt complexes based on binaphthol linker were highly active and enantioselective for homopolymerization of terminal epoxides.…”

Section: Resultsmentioning

confidence: 99%

Crystalline-gradient polycarbonates prepared from enantioselective terpolymerization of meso-epoxides with CO2

Liu

Ren

et al. 2014

Nat Commun

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The development of efficient processes for CO 2 transformation into useful products is a long-standing goal for chemists, since CO 2 is an abundant, inexpensive and non-toxic renewable C1 resource. Here we describe the enantioselective copolymerization of 3,4-epoxytetrahydrofuran with CO 2 mediated by biphenol-linked dinuclear cobalt complex, affording the corresponding polycarbonate with 499% carbonate linkages and excellent enantioselectivity (up to 99% enantiomeric excess). Notably, the resultant isotactic polycarbonate is a typical semicrystalline polymer, possessing a melting point of 271°C. Furthermore, the enantioselective terpolymerization of 3,4-epoxytetrahydrofuran, cyclopentene oxide and CO 2 mediated by this dinuclear cobalt complex gives novel gradient polycarbonates, in which the decrement of one component and the increment of the other component occur sequentially from one chain end to the other end. The resultant terpolymers show perfectly isotactic structure and have unique crystalline-gradient nature, in which the crystallinity continuously varies along the main chain.

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Section: Resultsmentioning

confidence: 99%

Crystalline-gradient polycarbonates prepared from enantioselective terpolymerization of meso-epoxides with CO2

Liu

Ren

et al. 2014

Nat Commun

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“…The selectivity for cyclic carbonate formation toward exclusive polymer formation in the coupling between an epoxide and CO 2 can be achieved by replacing the binary system for a bifunctional analogue. This feature was demonstrated by Lu and coworkers using Co(salen) derived catalyst, and its binary and bifunctional derivative were evaluated in terms of chemo-selectivity behavior in the asymmetric copolymerization of CO 2 and epoxides [75].…”

Section: Cyclohexyl Salensmentioning

confidence: 91%

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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“…25) [94]. For CPO/CO 2 copolymerisation (25 C, 20 bar CO 2 ), in the presence of PPNX (X ¼ 2,4-dinitrophenoxide), complexes 17a-b were highly enantioselective (ee >99%) and highly active (TOF, 200 h À1 ).…”

Section: Linked Bimetallic Salen Complexesmentioning

confidence: 98%

Dinuclear Metal Complex-Mediated Formation of CO2-Based Polycarbonates

Romain

Thevenon

Saini

et al. 2015

Topics in Organometallic Chemistry

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This review describes selected metal catalysts for the copolymerisation of epoxides and carbon dioxide to produce polycarbonates. It highlights kinetic and mechanistic studies which have implicated di-or (multi-) metallic pathways for this catalysis and the subsequent development of highly active and selective di-/(multi-) nuclear catalysts. The emphasis is on homogeneous di-/bimetallic catalysts.

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Asymmetric Copolymerization of CO₂ with meso‐Epoxides Mediated by Dinuclear Cobalt(III) Complexes: Unprecedented Enantioselectivity and Activity

Cited by 220 publications

References 51 publications

Crystalline-gradient polycarbonates prepared from enantioselective terpolymerization of meso-epoxides with CO2

Crystalline-gradient polycarbonates prepared from enantioselective terpolymerization of meso-epoxides with CO2

Metal Complexes Catalyzed Cyclization with CO2

Dinuclear Metal Complex-Mediated Formation of CO2-Based Polycarbonates

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Asymmetric Copolymerization of CO2 with meso‐Epoxides Mediated by Dinuclear Cobalt(III) Complexes: Unprecedented Enantioselectivity and Activity

Cited by 220 publications

References 51 publications

Crystalline-gradient polycarbonates prepared from enantioselective terpolymerization of meso-epoxides with CO2

Crystalline-gradient polycarbonates prepared from enantioselective terpolymerization of meso-epoxides with CO2

Metal Complexes Catalyzed Cyclization with CO2

Dinuclear Metal Complex-Mediated Formation of CO2-Based Polycarbonates

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Asymmetric Copolymerization of CO₂ with meso‐Epoxides Mediated by Dinuclear Cobalt(III) Complexes: Unprecedented Enantioselectivity and Activity