2904
M. Moghadam et al. / Bioorg. Med. Chem. 13 (2005) 2901–2905
Table 4. The results of [Mn(TPyP)-CMP] catalyst recovery and the
manganese leached in the oxidation of 4-chlorobenzyl alcohol with
sodium periodate
and secondary alcohols to carbonyl compounds with
NaIO . This catalytic system has some advantageous
4
18–21
over the previous reported systems
such as: (i) mild
a
Run
Conversion (%)
Mn leached (%)
reaction conditions (room temperature); (ii) simple
preparation of the catalyst from commercially available
materials (porphyrin and polystyrene resin) and it seems
binding of porphyrin pyridyl groups to polystyrene resin
is a good method to model the microenvironment of ac-
tive centre of cytochrome P-450; (iii) nontoxicity of the
catalyst; (iv) the use of supported metalloporphyrins
provides an easy way to recover and recycle the catalyst
from the reaction media and (v) the catalytic activity of
this catalyst in the oxidation of secondary alcohols has
been found to be higher compared with corresponding
1
2
3
4
100
100
98
0
0
0
0
97
a
GLC yield based on starting alcohol.
Blank experiments in the absence catalyst or in the ab-
sence of NaIO showed that only negligible amounts
of oxidation products were detected.
4
2
2
non-supported manganese(III)porphyrin.
Acknowledgements
3. Experimental
The partial support of this work by Yasouj and Isfahan
Universities Council Research is acknowledged.
All materials were commercial reagent grade. Alcohols
were obtained from Merck or Fluka. All of these tet-
ra(4-pyridyl)porphyrin was metalated and supported
1
6,17
according to the literature procedure.
References and notes
Reactions were quantified by GLC (Shimadzu 16 A)
using a 3 m Silicon DC-200 packed column with a
FID detector using decane as internal standard.
1
. (a) Coon, M. J.; White, R. E. In Dioxygen Binding and
Activation by Metal Centers; Spiro, T. G., Ed.; Wiley: New
York, 1980; p 73; (b) White, R. E.; Coon, M. J. Annu. Rev.
Biochem. 1980, 49, 315.
3.1. Typical procedure for oxidation of alcohols with
NaIO catalyzed by MnTPyP-CMP
2
3
4
. Groves, J. T.; Nemo, T. E. J. Am. Chem. Soc. 1983, 105,
4
5
786.
. Bortolini, O.; Meunier, B. J. Chem. Soc., Perkin Trans. 2
984, 1967.
. Meunier, B.; Cuilmel, E.; De Carvallho, M. E.; Poiblane,
R. J. Am. Chem. Soc. 1984, 106, 6668.
All of the reactions were carried out at room tempera-
ture under air in a 25 mL flask equipped with a magnetic
stirrer bar. A solution of NaIO4 (2 mmol) in H O
1
2
(
10 mL) was added to a mixture of alcohol (1 mmol),
5. (a) Mohajer, D.; Tangestaninejad, S. J. Chem. Soc., Chem.
Commun. 1993, 240; (b) Mohajer, D.; Tangestaninejad, S.
Tetrahedron Lett. 1994, 35, 945.
MnTPyP-CMP (20 lmol) and imidazole (0.2 mmol) in
CH CN (10 mL). The progress of reaction was moni-
3
6
. Wohler, D.; Gitzel, J. Makromol. Chem., Rapid Commun.
988, 9, 229.
tored by GLC. The reaction mixture was diluted with
CH Cl (20 mL) and filtered. The resin was thoroughly
washed with CH Cl and combined washings and fil-
trates were purified on silica-gel plates or silica-gel col-
umn. IR and H NMR spectral data confirmed the
identities of the products.
1
2
2
7
. (a) Leonard, D. R.; Lindsay Smith, J. R. J. Chem. Soc.,
Perkin Trans. 2 1990, 1917; (b) Leonard, D. R.; Lindsay
Smith, J. R. J. Chem. Soc., Perkin Trans. 2 1991, 25.
. Tangestaninejad, S.; Mirkhani, V. J. Chem. Res. (S) 1998,
788.
. Tangestaninejad, S.; Habibi, M. H.; Mirkhani, V.; Mogh-
2
2
1
8
9
adam, M. Molecules 2002, 7, 264.
3
.2. Catalyst reuse and stability
1
1
1
0. Tangestaninejad, S.; Moghadam, M. J. Chem. Res. (S)
998, 242.
1. Tangestaninejad, S.; Moghadam, M. Synth. Commun.
998, 28, 427.
2. Mirkhani, V.; Tangestaninejad, S.; Moghadam, M.
J. Chem. Res. (S) 1999, 722.
1
The stability of MnTPyP-CMP was studied in repeated
oxidation reactions. The oxidation of 4-chlorobenzyl
alcohol was chosen as a model substrate for studying
of catalyst reuse and stability. The reaction was carried
out as described above. At the end of reaction, the cat-
alyst was removed by filtration, washed with water and
acetonitrile and reused. After the use of catalyst for four
consecutive times, the aldehyde yield was 97%. No man-
ganese was detectable in the filtrates by atomic absorp-
tion spectrometry.
1
13. Tangestaninejad, S.; Habibi, M. H.; Mirkhani, V.; Mogh-
adam, M. J. Chem. Res. (S) 2001, 444.
14. Mirkhani, V.; Tangestaninejad, S.; Moghadam, M.;
Karimian, Z. Bioorg. Med. Chem. Lett. 2003, 13,
3
433.
1
1
1
5. Mirkhani, V.; Tangestaninejad, S.; Moghadam, M.;
Karimian, Z. J. Chem. Res. (S) 2003, 792.
6. Moghadam, M.; Tangestaninejad, S.; Habibi, M. H.;
Mirkhani, V. J. Mol. Catal. A: Chem. 2004, 217, 9.
7. Harriman, A.; Porter, G. J. Chem. Soc., Faraday II 1979,
4. Conclusions
75, 1532.
18. Linares, M. L.; Sanchez, N.; Alajarin, R.; Vaquero, J. J.;
Alvarez-Builla, J. Synthesis 2001, 3, 382.
In this paper we have demonstrated the utility of
Mn(TPyP)-CMP catalyst in the oxidation of primary