Mild and efficient alkene epoxidation and alkane hydroxylation by manganese(III) porphyrin supported on IRA-400 ion-exchange resin

Article abstract of DOI:10.1039/a906303j

Sulfonated manganese(III) tetraphenylporphyrin supported on Amberlite IRA-400 ion-exchange resin (MnTPPS-Ad), can act as an efficient heterogeneous catalyst for alkene epoxidation and alkane hydroxylation by sodium periodate in the presence of imadazole.

Full text of DOI:10.1039/a906303j

View Article Online / Journal Homepage / Table of Contents for this issue
7
22 J. CHEM. RESEARCH (S), 1999
J. Chem. Research (S),
Mild and Efficient Alkene Epoxidation and
Alkane Hydroxylation by Manganese(III)
Porphyrin Supported on IRA-400 Ion-exchange
Resin�
1
999, 722^723y
Valiollah Mirkhani,* Shahram Tangestaninejad and
Majid Moghadam
Chemistry Department, Esfahan University, Esfahan 81744, Iran
Sulfonated manganese(III
)
tetraphenylporphyrin supported on Amberlite IRA-400 ion-exchange resin
(
MnTPPS-Ad), can act as an efficient heterogeneous catalyst for alkene epoxidation and alkane hydroxylation
by sodium periodate in the presence of imadazole.
Recently, there has been considerable interest in the syn-
thesis and use of polymer supported catalysts. The high
remained almost unchanged by NaIO4 in CH3CN/H2O
after 24 h.
1
e¤ciency of some of these catalytic systems makes them
2;3
potentially useful for large scale oxidation.
Numerous
studies have been carried out employing metalloporphyrins
in association with various single oxygen donors for the
O
4
5
6
7
catalytic oxidation of alkenes, alkanes, amines, phenols,
8
9
mercaptans and sul¢des. Immobilization of expensive
metalloporphyrin catalysts on insoluble organic and
inorganic supports appears to be a good way to render them
practicable and improve their stability, selectivity and show
O
8,9-Epoxide 34%
1
,2-Epoxide 44%
9
� 16
other advantages with respect to recovery and reuse.
This report describes new periodate-heterogenized
a
metalloporphyrin system for alkene epoxidation and alkane
hydroxylation in CH3CN/H2O mixture at room tem-
perature.
Scheme 2
Table
1 Epoxidation of alkenes with NaIO4 catalysed by
O
MnIIITPPS-Ad/Imidazole
MnTPPS-Ad in the presence of imidazole at room temperature
+
NaIO4
CH3CN/H2O
Entry
1
Alkene Conversion(%)a Epoxide yield(%)a Reaction time/h
or
or
OH
O
C
1
2
R CH2R
R1 CH R2 and R1
R2
100
96
3.5
Scheme 1
2
3
98
82
95
3.5
3.5
The e¡ect of di¡erent axial ligands upon the epoxidation
rate of cyclooctene was also investigated. The epoxidation
rates decrease in the order: imidazole ˆ 1-methyl-
imidazole > tert-butylpyridine > pyridine. Reactions were
performed at room temperature under air in CH3CN/H2O
containing the alkene, oxidant, imidazole and MnTPPS-Ad
in 1 : 2 : 0.2 : 0.0145 ratio, respectively. This catalytic system
led to the epoxidation of various alkenes (Table 1, Scheme
100
4
5
100
100
89
90
3.5
3.5
CH3O
1
) with good yields (51^100%). Epoxidation of trans-
stilbene proceeds in a stereospeci¢c manner with complete
retention of con¢guration. In contrast, epoxidation of
cis-stilbene is associated with some loss of stereochemistry
and a¡ords 63% cis and 8% trans-stilbene oxides,
respectively.
The MnTPPS-Ad/NaIO4 system exhibits regioselectivity
for epoxidation of (R)-(‡)-limonene. The ratio among 1,2-
and 8,9-epoxides was found to be 1.29 : 1 (Scheme 2).
Selective partial alkane oxidation is a particularly chal-
lenging problem in the organic chemistry. Alkanes were
oxidized with sodium periodate by MnTPPS-Ad to the cor-
responding alcohols and ketones only in the presence of imi-
dazole (Table 2). In the absence of the supported
metalloporphyrin catalyst, cyclooctene and cyclooctane
6
7
96
78
81
4
4
44 (1,2-epoxide)b
4 (8,9-epoxide)b
3
8
9
51
71
51 (trans-epoxide)b
63 (cis-epoxide)b
4
4
8
(trans-epoxide)b
*
To receive any correspondence.
�
This is a Short Paper as de¢ned in the Instructions for Authors,
aGLC yield based on starting alkene. bBoth 1H NMR and GLC data
gave reported yields.
Section 5.0 [see J. Chem. Research (S), 1999, Issue 1]; there is
therefore no corresponding material in J. Chem. Research (M).

View Article Online
J. CHEM. RESEARCH (S), 1999 723
Table 2 Hydroxylation of alkanes with NaIO4 catalysed by
MnTPPS-Ad in the presence of imidazole at room temperature
General Procedure for Alkene Epoxidation Catalysed by
MnTPPS-Ad.öAll of the reactions were carried out at room tempera-
ture under air in a 25 mL £ask equipped with a magnetic stirring bar.
A solution of NaIO4 (2 mmol) in H2O (5 mL) was added to a mixture
of alkene (1 mmol), MnTPPS-Ad (14 mmol) and imidazole (0.2 mmol)
in CH3CN (10 mL). The progress of the reaction was monitored by
GLC. The reaction mixture was diluted with CH2Cl2 (20 mL) and
Entry
1
Alkane
Ketone(%)a
Alcohol(%)a
Reaction time/h
8
22
36
¢
ltered. The resin was thoroughly washed with CH2Cl2 and the com-
bined washings and ¢ltrates were puri¢ed on silica gel plates or a silica
2
3
30
—
14
45
8
8
1
gel column. IR and H NMR spectra data con¢rmed the identities of
the products.
General Procedure for Alkane Hydroxylation Catalysed by
MnTPPS-Ad.öA 25 mL £ask was charged with alkane (1 mmol),
MnTPPS-Ad (14 mmol), imidazole (0.2 mmol) and CH3CN (10 mL).
After addition of sodium periodate solution (2 mmol in 5 mL H2O),
the mixture was stirred magnetically at room temperature. The pro-
gress of the reaction was monitored by GLC. After the reaction
was completed, the resin was ¢ltered o¡ and the ¢ltrate was extracted
with CH2Cl2 and puri¢ed on a silica gel plate or silica gel column. IR
4
5
51
61
35
—
8
8
1
and H NMR spectral data con¢rmed the identities of the products.
6
7
8
34
48
40
—
—
—
8
8
8
We thank the Esfahan University Research Council for
support of this work.
Received, 3rd August 1999; Accepted, 2nd September, 1999
Paper E/9/06303J
aGLC yield based on starting alkane.
References
1
2
3
D. C. Sherrington, Pure. Appl. Chem., 1988, 60, 401.
B. Meunier, Coord. Chem., 1991, 92, 1411.
M. Sono, M. P. Roach, E. D. Coulter and J. H. Dawson,
Chem. Rev., 1996, 96, 2841.
P. Ho¡mann, A. Robert and B. Meunier, Bull. Soc. Chim. Fr.,
The activity of this catalyst (MnTPPS-Ad) was compared
to that of unsupported catalyst in epoxidation of
cyclooctene and cyclohexene. The results showed that the
homogeneous oxidations are faster but less selective.
Normally, side reactions such as double bond cleavage
and allylic oxidation are minimized with the heterogeneous
catalysts.
The solutions remained colorless during the course of
epoxidations and there was no evidence for leaching of
the catalyst into solution. The attachment of metallo-
porphyrin to the Amberlite made it possible to remove
the stable catalyst by simple ¢ltration at the end of reaction.
The stability of MnTPPS-Ad was studied in repeated
epoxidation reactions of styrene (5 times) by sodium per-
iodate. The catalyst was removed after, each reaction by
simple ¢ltration and washing with acetonitrile. The reused
catalyst displayed consistent reactivity and selectivity.
4
5
6
7
8
9
0
1
992, 129, 85.
J. R. Lindsay Smith and D. N. Mortimer, J. Chem. Soc., Per-
kin Trans. 2, 1986, 1743.
M. H. Habibi, S. Tangestaninejad and V. Mirkhani, J. Chem.
Res. (S), 1998, 648.
T. Buck, H. Bohlen, D. Wohrle, G. Schulz-Eklo¡ and A.
Andreev, J Mol. Catal., 1993, 80, 253.
E. Baciocchi, O. Lanzalunga and F. Marconi, Tetrahedron
Lett., 1994, 35, 9771.
D. R. Leonard and J. R. Lindsay Smith, J. Chem. Soc., Perkin
Trans. 2, 1991, 25.
T. Mori, T. Santa and M. Hirobe, Tetrahedron Lett., 1985, 26,
5555.
1
11 I. Mochida, K. Tsuji, K. Suetsugu, H. Fujitsu and K.
Takeshita, J. Phys. Chem., 1980, 84, 3159.
1
1
1
1
2
3
4
5
M. Nakamura, T. Tatsumi and H. Tominage, Bull. Chem. Soc.
Jpn., 1990, 63, 3334.
S. Tangestaninejad and V. Mirkhani, J. Chem. Res. (S), 1998,
7
88.
S. Tangestaninejad and M. Moghadam, J. Chem. Res. (S),
998, 242.
H. Turk and W. T. Ford, J. Org. Chem., 1991, 56, 1253.
1
Experimental
Alkene, alkane and alkylaromatic compounds were obtained from
Merck or Fluka. All were passed through a column containing active
alumina to remove peroxidic impurities. The porphyrin ligand
16 F. Pautet and M. Daudon, Tetrahedron Lett., 1991, 32, 1457.
17 E. B. Fleischer, J. M. Palmer, T. S. Srinivastava and A.
Chatterjee, J. Am. Chem. Soc., 1971, 93, 3162.
18 A. Harriman and G. Porter, J. Chem. Soc., Faraday Trans. 2,
1979, 75, 1532.
19 Y. Saito, M. Mifume, S. Nakashima, H. Nakayama, J. Odo, Y.
Tanaka, M. Ohikama and H. Tanaka, Chem. Pharm. Bull.,
1987, 34, 2885.
5
,10,15,20-tetrakis(4-sulfonophenyl)porphyrin was prepared and
1
7;18
metallated according to the literature procedures.
MnTPPS
immobilized on Amberlite IRA-400) was prepared according to
the reported procedure (9 mmol of MnTPPS were immobilized on
00 mg of the resin).
1
9
1