Carbon Dioxide Fixation by Cycloaddition with Epoxides, Catalyzed by Biomimetic Metalloporphyrins

Authors

  • Dongsheng Bai,

    1. State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, Gansu 730000 (China), Fax: (+86) 931-891-2582
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  • Shuhui Duan,

    1. State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, Gansu 730000 (China), Fax: (+86) 931-891-2582
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  • Long Hai,

    1. State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, Gansu 730000 (China), Fax: (+86) 931-891-2582
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  • Prof. Dr. Huanwang Jing

    Corresponding author
    1. State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, Gansu 730000 (China), Fax: (+86) 931-891-2582
    • State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, Gansu 730000 (China), Fax: (+86) 931-891-2582
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Abstract

Several biomimetic metalloporphyrin complexes (M(TPP)XY; in which TPP=meso-porphyrin; M=MgII, AlIII, SnII, or SnIV; X=OAc, F, Cl, Br, I, OTf, or none; and Y=Cl, Br, I, OTf, or none) were prepared, characterized, and used effectively in the “green” synthesis of cyclic carbonates from epoxides and CO2. The catalytic systems of Mg(TPP)/tetrabutylammonium iodide and Al(TPP)Cl/phenyltrimethyl ammonium tribromide can initiate the cycloaddition of epoxides and CO2 at room temperature to generating cyclic carbonates in excellent yield. Chlorophyll A is shown to induce enantioselectivity of racemic propylene oxide. All reactions displayed excellent selectivity to cyclic carbonate without polycarbonate and other by-products. Chloropropylene carbonate is shown to be obtained under CO2 bubbling conditions catalyzed by Al(TPP)Cl/phenyltrimethylammonium tribromide. The catalytic order of activity for biomimetic metalloporphyrins is AlIII>MgII>SnIV>SnII. These phenomena are explained with respect to the Lewis acidity of metal center in metalloporphyrins.

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