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Synlett 2012; 23(9): 1343-1348
DOI: 10.1055/s-0031-1290957
letter
© Georg Thieme Verlag Stuttgart · New York

Cycloaddition of CO2 to Epoxides Catalyzed by N-Heterocyclic Carbene (NHC)–ZnBr2 System under Mild Conditions

Xiang Liu
a   College of Chemistry and Chemical Engineering, Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Xuzhou Normal University, Xuzhou, Jiangsu 221116, P. R. of China, Fax: +86(516)83500349   Email: yhshi@xznu.edu.cn
,
Changsheng Cao*
a   College of Chemistry and Chemical Engineering, Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Xuzhou Normal University, Xuzhou, Jiangsu 221116, P. R. of China, Fax: +86(516)83500349   Email: yhshi@xznu.edu.cn
,
Yunfei Li
a   College of Chemistry and Chemical Engineering, Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Xuzhou Normal University, Xuzhou, Jiangsu 221116, P. R. of China, Fax: +86(516)83500349   Email: yhshi@xznu.edu.cn
,
Pei Guan
a   College of Chemistry and Chemical Engineering, Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Xuzhou Normal University, Xuzhou, Jiangsu 221116, P. R. of China, Fax: +86(516)83500349   Email: yhshi@xznu.edu.cn
,
Longguang Yang
a   College of Chemistry and Chemical Engineering, Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Xuzhou Normal University, Xuzhou, Jiangsu 221116, P. R. of China, Fax: +86(516)83500349   Email: yhshi@xznu.edu.cn
,
Yanhui Shi*
a   College of Chemistry and Chemical Engineering, Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Xuzhou Normal University, Xuzhou, Jiangsu 221116, P. R. of China, Fax: +86(516)83500349   Email: yhshi@xznu.edu.cn
b   State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, P. R. of China
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Further Information

Publication History

Received: 17 February 2012

Accepted after revision: 12 March 2012

Publication Date:
08 May 2012 (online)

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Abstract

A very simple and convenient method toward coupling of CO2 with epoxides catalyzed by NHC/ZnBr2 has been developed. This catalytic system exhibits excellent activity and selectivity in the cycloaddition reactions of CO2 to terminal epoxides. The reactions can even be carried out under CO2 pressure as low as 0.05 MPa and give carbonates in high yields.

Key words

N-heterocyclic carbenes - NHC–CO2 adducts - carbon dioxide - epoxides - cyclic carbonates

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
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  • References and Notes

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  • 15 General Procedure for the Cycloaddition Reaction of Epoxides with CO2 An oven-dried 50 mL of round-bottom flask containing 2 mol% of catalyst 3 (0.149 g, 0.35 mmol), 2 mol% of K2CO3 (0.048 g, 0.35 mmol), and 2 mol% of ZnBr2 (0.079 g, 0.35 mmol) was purged with CO2 under atmosphere pressure three times. Then epoxide (17.5 mmol) and DMSO (10 mL) were injected into the flask by syringe, and CO2 was provided by a balloon. The reaction was stirred at 80 °C for 24 h. After the reaction was cooled down, H2O (200 mL) was added to the reaction mixture. The organic layer was extracted with CH2Cl2 (3 × 20 mL), and filtered through a silica plug. The products were collected by evaporating volatiles and dried under vacuum. Using high-purity or low-grade CO2 had no impact on the results. 4-Ethyl-1,3-dioxolan-2-one 16 Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 4.69–4.62 (m, 1 H), 4.52 (t, J = 8.0 Hz, 1 H), 4.08 (t, J = 7.6 Hz, 1 H), 1.87–1.68 (m, 2 H), 1.02 (t, J = 7.6 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 155.1 (C=O), 78.0, 69.0, 26.9, 8.5. IR: ν = 1799 (CO) cm–1. 4-Butyl-1,3-dioxolan-2-one 17 Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 4.72–4.65 (m, 1 H), 4.51 (t, J = 8.0 Hz, 1 H), 4.05 (t, J = 8.0 Hz, 1 H), 1.82–1.61 (m, 2 H), 1.46–1.27 (m, 4 H), 0.89 (t, J = 6.8 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 155.0 (C=O), 69.3, 53.4, 33.4, 26.3, 22.1, 13.7. IR: ν = 1790 (CO) cm–1. 4-(Chloromethyl)-1,3-dioxolan-2-one 18 Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 4.99–4.93 (m, 1 H), 4.59 (app. t, J = 8.4 Hz, 1 H), 4.41 (dd, J = 6.0, 8.8 Hz, 1 H), 3.78 (dd, J = 12.0, 5.6 Hz, 1 H), 3.73 (dd, J = 12.0, 4.0 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 154.0 (C=O), 74.2, 66.9, 43.5. IR: ν = 1790 (CO) cm–1. 4-(Bromomethyl)-1,3-dioxolan-2-one 19 Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 4.97–4.90 (m, 1 H), 4.60 (app. t, J = 8.4 Hz, 1 H), 4.36 (dd, J = 6.0, 9.0 Hz, 1 H), 3.61–3.52 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ = 154.2 (C=O), 73.9, 68.0, 31.7. IR: ν = 1794 (CO) cm–1. 4-Phenyl-1,3-dioxolan-2-one 18 White solid. 1H NMR (400 MHz, CDCl3): δ = 7.47–7.35 (m, 5 H), 5.68 (t, J = 8.0 Hz, 1 H), 4.80 (t, J = 8.4 Hz, 1 H), 4.35 (t, J = 8.4 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 154.8 (C=O), 135.8, 129.7, 129.2, 125.8, 77.9, 71.1. IR: ν = 1775 (CO) cm–1. 4-Benzyl-1,3-dioxolan-2-one 20 Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.36–7.21 (m, 5 H), 4.96–4.89 (m, 1 H), 4.44 (t, J = 8.0 Hz, 1 H), 4.17 (t, J = 7.2 Hz, 1 H), 3.15 (dd, J = 14.0, 6.4 Hz, 1 H), 2.99 (dd, J = 14.2, 6.4 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 154.8 (C=O), 133.8, 129.3, 128.9, 127.5, 76.7, 68.4, 39.5. IR: ν = 1791 (CO) cm–1. 4-(Phenoxymethyl)-1,3-dioxolan-2-one 21 White solid. 1H NMR (400 MHz, CDCl3): δ = 7.31 (t, J = 7.6 Hz, 2 H), 7.02 (t, J = 7.2 Hz, 1 H), 6.91 (d, J = 8.4 Hz, 2 H), 5.06–5.00 (m, 1 H), 4.62 (t, J = 8.8 Hz, 1 H), 4.54 (dd, J = 8.4, 6.0 Hz, 1 H), 4.24 (dd, J = 10.0, 4.0 Hz, 1 H), 4.15 (dd, J = 10.4, 3.2 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 157.7, 154.6 (C=O), 129.7, 121.9, 114.5, 74.1, 66.8, 66.2. IR: ν = 1803 (CO) cm–1. 4-(Benzyloxymethyl)-1,3-dioxolan-2-one 20 Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.39–7.30 (m, 5 H), 4.85–4.79 (m, 1 H), 4.60 (dd, J = 22.8, 12.0 Hz, 2 H), 4.49 (app. t, J = 8.4 Hz, 1 H), 4.39 (dd, J = 8.4, 6.0 Hz, 1 H), 3.71 (dd, J = 10.8, 3.6 Hz, 1 H), 3.62 (dd, J = 10.8, 3.6 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 154.8 (C=O), 137.0, 128.6, 128.1, 127.7, 74.9, 73.7, 68.8, 66.3. IR: ν = 1790 (CO) cm–1. (2-Oxo-1,3-dioxolan-4-yl)methyl Benzoate 22 Yellow oil. 1H NMR (400 MHz, CDCl3): δ = 8.02 (d, J = 8.0 Hz, 2 H), 7.60 (t, J = 7.2 Hz, 1 H), 7.47 (t, J = 7.6 Hz, 2 H), 5.09–5.03 (m, 1 H), 4.65–4.57 (m, 2 H), 4.51 (dd, J = 12.8, 4.0 Hz, 1 H), 4.43 (dd, J = 8.4, 5.6 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 165.9 (C=O), 154.4 (C=O), 133.7, 129.8, 128.6, 128.4, 73.8, 66.0, 63.6. IR: ν = 1793 (CO) cm–1
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  • 23 Zn–NHC Complex (3c–ZnCl2) 1H NMR (400 MHz, CDCl3): δ = 7.28 (t, J = 8.0 Hz, 2 H), 7.08 (d, J = 8.0 Hz, 4 H), 4.81 (s, 4 H), 2.95 (sext, J = 6.8 Hz, 4 H), 1.21 (d, J = 6.8 Hz, 12 H), 1.02 (d, J = 6.8 Hz, 12 H). 13C NMR (100 MHz, CDCl3): δ = 156.6, 146.5, 131.3, 129.4, 124.9, 55.7, 28.9, 25.4, 23.8. Anal. Calcd (%) for C27H38Cl2N2Zn (526.9 g/mol): C, 61.55; H, 7.27; N, 5.32. Found: C, 61.41; H, 7.57; N, 5.27
  • 24 1,3-Bis(2,6-diisopropylphenyl)imidazolinium-2-carboxylate (3–CO2) 1H NMR (400 MHz, CDCl3): δ = 7.48 (t, J = 8.0 Hz, 2 H), 7.28 (d, J = 7.6 Hz, 4 H), 4.88 (s, 4 H), 3.02 (sext, J = 6.8 Hz, 4 H), 1.40 (d, J = 6.8 Hz, 12 H), 1.25 (d, J = 6.8 Hz, 12 H). IR: ν = 1681 (CO) cm–1