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E. Brule´, Y. R. de Miguel / Tetrahedron Letters 43 (2002) 8555–8558
cycles, only a small decrease in activity (from 86% to
75%) was observed, and moreover, no manganese por-
phyrin was detected in the solution when analysed by
UV spectroscopy.
Ceulemans, E.; Dehaen, W.; Jacobs, P. A. J. Mol. Catal.
A 1999, 144, 373–377.
10. Mirkhani, V.; Tangestaninejad, S.; Moghadam, M.;
Yadollahi, B. J. Chem. Res. (S) 2000, 515–517.
11. You, J.-S.; Xiao, Y.-F.; Yu, X.-Q.; Cheng, A.-X.; Lan,
Z.-W. Chinese J. Chem. 1996, 14, 303–309.
12. Tangestaninejad, S.; Mirkhani, V. J. Chem. Res. (S) 1998,
788–789.
13. Zhang, J.-L.; Che, C.-M. Org. Lett. 2002, 11, 1911–1914.
14. Stamp, L. M.; Mang, S. A.; Holmes, A. B.; Knights, K.
A.; de Miguel, Y. R.; McConvey, I. F. Chem. Commun.
2001, 2502–2503.
In conclusion, we have developed a new efficient route
to supported manganese porphyrins, and demonstrated
the effectiveness of Argogel and Merrifield-bound cata-
lysts 7 and 8 as alkene epoxidation catalysts. Detailed
studies have shown that Merrifield resin is a superior
support for this catalyst, as it can be recycled with
minimum loss of activity.
15. Yu, X.-Q.; Wei, T.-X.; Lan, Z.-W.; You, J.-S.; Zhao,
H.-M. J. Mol. Catal. (Chinese) 1995, 9, 244–250.
16. Uno, H.; Takata, K.; Mitzuni, Y. React. Funct. Polym.
1991, 15, 121–129.
Acknowledgements
17. The resins, Argogel chloride 2 (0.44 mmol g−1) or Mer-
rifield 3 (0.84 mmol g−1), potassium carbonate (1.1
mmol), potassium iodide (0.44 mmol) and 5-(4-hydroxy-
phenyl)-10,15,20-triphenylporphyrin 116 (0.33 mmol) were
placed under N2 in a flask equipped with an overhead
stirrer. Anhydrous DMF (100 mL) was then added. The
flask was warmed to 80°C and stirred at 60 rpm for 3
days. After cooling to room temperature, the beads were
washed with acetone, water, methanol, ethyl acetate,
dichloromethane and HPLC-grade pentane and then
dried under vacuum at 50°C for 2 h to give dark purple
beads. After three treatments, nitrogen microanalysis for
AG-TPP 4 was 1.57%, which corresponded to a calcu-
lated yield of 75% (loading of 0.28 mmol g−1). MR-TPP
5 was obtained in 93% after one single treatment, yield
based on the nitrogen microanalysis result of 2.90%
(loading of 0.52 mmol g−1). Furthermore, no Cl was
detected in either of the compounds.
18. AG-TPP 4 or MR-TPP 5 was placed in a flask equipped
with an overhead stirrer under N2. Anhydrous DMF was
added and the reaction mixture was refluxed at 158°C for
5 min and manganese dichloride (100 equiv.) was added
under N2. The mixture was then stirred at 60 rpm in
refluxing DMF for 2.5 h. After cooling to room tempera-
ture, the beads were washed with water, acetone, DCM
and HPLC-grade pentane and dried under vacuum. Man-
ganese analysis (ICP-AES) showed 100% metallation in
both cases (1.54% Mn, loading of 0.28 mmol g−1 for
AG-TPPMnCl 7 and 2.86% Mn, loading of 0.52 mmol
g−1 for MR-TPPMnCl 8).
We thank King’s College London for financial support
(E. Brule´), and the Royal Society (Dorothy Hodgkin
Fellowship to Y. R. de Miguel).
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