Green Chemistry
Communication
Dalton Trans., 2010, 39, 3347–3357; (d) M. Mikkelsen,
M. Jorgensen and F. C. Krebs, Energy Environ. Sci., 2010, 3,
43–81; (e) I. Omae, Catal. Today, 2006, 115, 33–52;
(f) K. Huang, C.-L. Sun and Z.-J. Shi, Chem. Soc. Rev., 2011,
40, 2435–2452; (g) A. M. Appel, J. E. Bercaw, A. B. Bocarsly,
H. Dobbek, D. L. DuBois, M. Dupuis, J. G. Ferry, E. Fujita,
R. Hille, P. J. A. Kenis, C. A. Kerfeld, R. H. Morris,
C. H. F. Peden, A. R. Portis, S. W. Ragsdale,
T. B. Rauchfuss, J. N. H. Reek, L. C. Seefeldt, R. K. Thauer
and G. L. Waldrop, Chem. Rev., 2013, 113, 6621–6658;
(h) M. Y. He, Y. H. Sun and B. X. Han, Angew. Chem., Int. Ed.,
2013, 52, 9620–9633.
2 Z.-Z. Yang, L.-N. He, J. Gao, A.-H. Liu and B. Yu, Energy
Environ. Sci., 2012, 5, 6602–6639.
3 (a) C. J. Whiteoak, N. Kielland, V. Laserna, E. C. Escudero-
Adán, E. Martin and A. W. Kleij, J. Am. Chem. Soc., 2013,
135, 1228–1231; (b) T. Sakakura and K. Kohno, Chem.
Commun., 2009, 1312–1330.
4 (a) S. Wesselbaum, T. vom Stein, J. Klankermayer and
W. Leitner, Angew. Chem., Int. Ed., 2012, 51, 7499–7502;
(b) G. A. Olah, A. Goeppert and G. K. S. Prakash, J. Org.
Chem., 2009, 74, 487–498.
5 (a) L. Zhang and Z. Hou, Chem. Sci., 2013, 4, 3395–3403;
(b) D. Yu and Y. Zhang, Proc. Natl. Acad. Sci. U. S. A., 2010,
107, 20184–20189.
6 (a) Y. Jiang, O. Blacque, T. Fox and H. Berke, J. Am. Chem.
Soc., 2013, 135, 7751–7760; (b) M. J. Sgro and
D. W. Stephan, Angew. Chem., Int. Ed., 2012, 51, 11343–
11345.
7 Z.-Z. Yang, Y.-N. Zhao, L.-N. He, J. Gao and Z.-S. Yin, Green
Chem., 2012, 14, 519–527.
8 (a) T. Ohishi, M. Nishiura and Z. Hou, Angew. Chem., Int.
Ed., 2008, 47, 5792–5795; (b) K. Burgemeister, G. Francio,
H. Hugl and W. Leitner, Chem. Commun., 2005, 6026–6028;
(c) E. J. Beckman, Chem. Commun., 2004, 1885–1888;
(d) Y. Hu, W. Chen, A. M. B. Osuna, J. A. Iggo and J. Xiao,
Chem. Commun., 2002, 788–789; (e) W. Chen, L. Xu and
J. Xiao, Chem. Commun., 2000, 839–840; (f) D. E.
Bergbreiter, J. G. Franchina and B. L. Case, Org. Lett., 2000,
2, 393–395.
Fig. 3 Recycle test of F-PIL-Br. Conversion of styrene oxide and the
yield of styrene carbonate were determined by 1H NMR using mesitylene
as the internal standard.
electron-donating (Table 2, entries 1–5) and electron-withdraw-
ing groups (Table 2, entry 6) could be transformed to the
corresponding cyclic carbonates with almost quantitative
yields (93–99%) within 9 h under 1 MPa CO2 pressure at
120 °C.
To test the catalyst reusability, the reaction of styrene oxide
with CO2 catalyzed by a catalytic amount of F-PIL-Br was per-
formed. The catalyst was recovered through centrifugation
after the reaction mixture was washed with dichloromethane,
dried and then used directly for the next run without any
further purification. The results shown in Fig. 3 indicate that
the yield of styrene carbonate was almost constant after five
successive recycles. Peaks in the FTIR spectra of the catalyst
showed no difference between the fresh and the recycled cata-
lyst (Fig. 1A), suggesting that F-PIL-Br had excellent stability
under the experimental conditions.
Conclusions
F-PILs were designed for the cycloaddition reaction of CO2
with epoxides. The catalytic activity of the resulting F-PILs
increased with the fluorine content in the cations, and
F-PIL-Br showed the highest efficiency, producing a series of
cyclic carbonates with excellent yields (93–99%) under 1 MPa
CO2 pressure. In addition, it showed high stability and easy
recyclability. Design and application of other fluorous
materials for CO2 activation and transformation is under inves-
tigation in our lab.
9 Q.-W. Song, L.-N. He, J.-Q. Wang, H. Yasuda and
T. Sakakura, Green Chem., 2013, 15, 110–115.
10 (a) M. Yoshida and M. Ihara, Chem. – Eur. J., 2004, 10,
2886–2893; (b) J. H. Clements, Ind. Eng. Chem. Res., 2003,
42, 663–674; (c) J. Sun, S.-I. Fujita and M. Arai, J. Organo-
met. Chem., 2005, 690, 3490–3497; (d) W.-L. Dai, S.-L. Luo,
S.-F. Yin and C.-T. Au, Appl. Catal., A, 2009, 366, 2–12.
11 (a) M. M. Dharman, J.-I. Yu, J.-Y. Ahn and D.-W. Park,
Green Chem., 2009, 11, 1754–1757; (b) J. Song, Z. Zhang,
S. Hu, T. Wu, T. Jiang and B. Han, Green Chem., 2009, 11,
1031–1036; (c) Y. Xie, T.-T. Wang, X.-H. Liu, K. Zou and
W.-Q. Deng, Nat. Commun., 2013, 4.
This work was financially supported by the National
Natural Science Foundation of China (grant no. 21125314 and
21021003).
Notes and references
12 (a) I. Shibata, I. Mitani, A. Imakuni and A. Baba, Tetra-
hedron Lett., 2011, 52, 721–723; (b) A. Buchard,
M. R. Kember, K. G. Sandeman and C. K. Williams, Chem.
Commun., 2011, 47, 212–214; (c) A. Decortes, M. Martinez
1 (a) T. Sakakura, J.-C. Choi and H. Yasuda, Chem. Rev., 2007,
107, 2365–2387; (b) M. Aresta and A. Dibenedetto, Dalton
Trans., 2007, 2975–2992; (c) S. N. Riduan and Y. Zhang,
This journal is © The Royal Society of Chemistry 2014
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