Advanced Synthesis & Catalysis
10.1002/adsc.201801229
After this time, the reaction mixture was allowed to cool to
rt. The solid product was isolated via sintered funnel and
washed with EtOAc (2 × 10 mL). The isolated solid was
transferred to a 50 mL round-bottom flask and BnBr (0.28
g), TBAB (0.36 g) and MeCN (20 mL) were added. The
reaction mixture was heated under reflux (86 °C) with
stirring for 16 h. After this time, the reaction mixture was
allowed to cool to rt. The solid product was isolated via
sintered funnel filtration and washed with EtOAc (2×10
mL) to yield the bimetallic aluminium-salen catalyst
functionalised silica as a powdery orange solid.
[
[
6] S. Fukuoka, M. Kawamura, K. Komiya, M. Tojo, H.
Hachiya, K. Hasegawa, M. Aminaka, H. Okamoto, I.
Fukawa, S. Konno, Green Chem. 2003, 5, 497–507.
7] J. W. Comerford, I. D. V. Ingram, M. North, X. Wu,
Green Chem. 2015, 17, 1966–1987.
[8] C. Martín, G. Fiorani, A. W. Kleij, ACS Catal. 2015, 5,
353–1370.
1
[
9] G. Fiorani, W. Guo, A. W. Kleij, Green Chem. 2015,
17, 1375–1389.
General procedure for catalyst screening. A glass vial
was charged with mesoporous silica-supported catalyst
(
0.25 mol%) and an epoxide (3.30 mmol), sealed and
[10] M. North, R. Pasquale, Angew. Chem. Int. Ed. 2009,
8, 2946–2948.
®
purged with CO
heating block. A balloon filled with CO
the reaction mixture was gently stirred at 50 or 100 ˚C for
4 h. After this time, the reaction mixture was allowed to
2
, and then placed in a pre-heated DrySyn
4
2
was attached and
[
[
[
11] J. Melendez, M. North, P. Villuendas, C. Young,
2
1
Dalton Trans. 2011, 40, 3885–3902.
cool to rt. Conversions were determined by H NMR
spectroscopy of the reaction mixture. When good
conversions were obtained using SBA-15-10-7 catalyst, the
reaction mixture was purified by column chromatography
on silica gel, eluting first with hexane:EtOAc 5:1, then
hexane:EtOAc 1:1 and finally with just EtOAc to give the
12] M. North, P. Villuendas, C. Young, Chem. Eur. J.
2
009, 15, 11454–11457.
13] M. North, B. Wang, C. Young, Energy Env. Sci. 2011,
4, 4163–4170.
[
42-49]
pure cyclic carbonates 2b-m.
copies of spectra for compounds 2b-m are given in the
Characterising data and
supporting information.
[14] M. North, P. Villuendas, ChemCatChem 2012, 4,
89–794.
7
General procedure for reusability study. A glass vial
was charged with catalyst-loaded SBA-15-10-7 (1 mol%)
[
15] N. Hiyoshi, K. Yogo, T. Yashima, Micro. Meso.
Mater. 2005, 84, 357–365.
and butyl glycidyl ether 1d (3.30 mmol), sealed and purged
®
with CO
2
, and then placed in a pre-heated DrySyn heating
block. A balloon filled with CO
2
was attached and the
[16] R. K. Zeidan, S.-J. Hwang and M. E. Davis, Angew.
Chem. Int. Ed. 2006, 45, 6332–6335.
reaction mixture was gently stirred at 25 ˚C for 24 h. After
this time, the reaction mixture was diluted with EtOAc (3
mL) and the washings were isolated and separated by
centrifugation, and then concentrated to dryness under
[
[
[
17] Z. Zhou, M. Hartmann, Chem. Soc. Rev. 2013, 42,
3894–3912.
1
vacuum. Conversions were determined by H NMR
spectroscopy of the residue. The isolated catalyst was dried
under vacuum and then re-used directly in the next run.
After 5 uses, the catalyst (200 mg), benzyl bromide (144
mg) and TBAB (50 mg) were added to MeCN (5 mL) and
heated under reflux (86 °C) with stirring for 2 days. After
this time, the reaction mixture was allowed to cool to rt.
The solid product was isolated via sintered funnel filtration,
washed with EtOAc (2×10 mL) to give the reactivated
catalyst as a beige solid.
18] V. Fathi Vavsari, G. Mohammadi Ziarani, A. Badiei,
RSC Advances 2015, 5, 91686–91707.
19] J. W. Comerford, T. J. Farmer, D. J. Macquarrie, S.
W. Breeden, J. H. Clark, Arkivoc 2012, 7, 282–293.
[20] M. Kruk, Acc. Chem. Res. 2012, 45, 1678–1687.
[
21] M. Liu, B. Liu, L. Liang, F. Wang, L. Shi, J. Sun, J.
Mol. Cat. A: Chem. 2016, 418–419, 78–85.
Acknowledgements
[
22] S. Ravi, R. Roshan, J. Tharun, A. C. Kathalikkattil, D.
W. Park, J. CO
2
Utilization 2015, 10, 88–94.
We gratefully acknowledge financial support from the European
Union Seventh Framework Programme FP7–NMP–2012 under
grant agreement number 309497. We thank Jon Sinclair
[23] L. Han, S.-W. Park, D.-W. Park, Energy Env. Sci.
2
009, 2, 1286–1292.
(
University of York) for help with powder X-ray diffraction and
Heather Fish (University of York) for help with solid state NMR.
[
[
[
[
[
[
24] T. Takahashi, T. Watahiki, S. Kitazume, H. Yasuda,
T. Sakakura, Chem. Commun. 2006, 1664–1666.
25] Y. Xie, K. Ding, Z. Liu, J. Li, G. An, R. Tao, Z. Sun,
References
Z. Yang, Chem. Eur. J. 2010, 16, 6687–6692.
[
1] Carbon Dioxide as Chemical Feedstock (Ed.: M.
26] T. Ema, Y. Miyazaki, T. Taniguchi, J. Takada, Green
Chem. 2013, 15, 2485–2492.
Aresta), Wiley-VCH, Weinheim, 2010, 1–375.
[
[
[
2] W. J. Peppel, Ind. Eng. Chem. 1958, 50, 767–770.
3] K. Xu, Chem. Rev. 2004, 104, 4303–4417.
27] U. R. Seo, Y. K. Chung, Adv. Synth. Catal. 2014, 356,
1
955–1961.
28] W. Zhang, Q. Wang, H. Wu, P. Wu, M. He, Green
Chem. 2014, 16, 4767–4774.
4] B. Schaffner, F. Schaffner, S. P. Verevkin, A. Borner,
Chem. Rev. 2010, 110, 4554–4581.
29] B. Chatelet, L. Joucla, J.-P. Dutasta, A. Martinez, V.
[
5] A. A. G. Shaikh, S. Sivaram, Chem. Rev. 1996, 96,
Dufaud, J. Mater. Chem. A 2014, 2, 14164–14172.
9
51–976.
8
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