Thanks are due to the Universidade de Aveiro and Fundação para
a Ciência e a Tecnologia (FCT) for funding the Organic Chemistry
Research Unit. S. L. H. R. also thanks FCT for a PhD grant.
Notes and references
1 D. L. Lanza, E. Code, C. L. Crespi, F. G. Gonzalez and G. S. Yost, Drug
Metab. Dispos, 1999, 27, 798; S. P. de Visser and S. Shaik, J. Am. Chem.
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2 H. B. Bode, B. Wegner and A. Zeek, J. Antibiot., 2000, 53, 153.
3 ‘Chemistry of Arene Oxides’, G. S. Shirwaiker and M. V. Bhatt, in
Advances in Heterocyclic Chemistry, A. R. Katritzky, ed., Academic
Press, New York, 1984, vol. 37, p. 67; W. Adam and M. Balci,
Tetrahedron, 1980, 36, 833.
Scheme 1
4 W.-S. Tsang, G. W. Griffin, M. G. Horning and W. G. Stillwell, J. Org.
Chem., 1982, 47, 5339.
5 D. R. Boyd, N. D. Sharma, C. R. O’Dowd and F. Hempenstall, Chem.
Commun., 2000, 2151; S. K. Balani, I. N. Brannigan, D. R. Boyd, N. D.
Sharma, F. Hempenstall and A. Smith, J. Chem. Soc., Perkin Trans 1,
2001, 1091.
isation of the products was made by NMR techniques, namely 1H,
13C, COSY, NOESY, HSQC and HMBC and mass spectrometry.
The conversion percentages and products selectivity were deter-
mined directly from the 1H NMR spectra of the reaction
mixtures.
In the presence of Mn(TDCPP)Cl (I), naphthalene and anthra-
cene were oxidised with high selectivity to the corresponding anti-
1,2:3,4-arene oxides 1 (81%) and 2 (74%), at 91 and 100% of
conversion, respectively. Keeping in mind that the formation of a
diepoxide requires two cycles, the turnover numbers obtained with
catalyst I were 442 for diepoxide 1 and 444 for diepoxide 2. These
results demonstrate that we are in the presence of a very useful
procedure for the synthesis of 119 and 2.20 Quinones 6 (12%) and
7 (7%) were detected only as minor products, as well as the syn-
isomers of the dioxides 1 (7%) and 2 (9%).21 In the case of
anthracene oxidation reactions, small quantities of anti-9,9a:4a,10-
anthracene dioxide 9 (3%)22 and 1,2:3,4:5,6:7,8-anthracene tetra-
oxide 10 (5%)22 were also observed. Compound 10 was observed in
26% yield after 3 h of reaction with catalyst I. Mn(bNO2TDCPP)Cl
(II) gave rise to similar results on the oxidation of naphthalene and
anthracene. The tetraoxide 10 was observed as the main product in
42% yield after 6 h of reaction with catalyst II.
The oxidation of phenanthrene by porphyrin I showed high
selectivity for epoxidation of the 9,10-bond,3,14 affording 91% of
the epoxide 3. With both catalysts I and II complete phenanthrene
conversions were obtained. Catalyst II afforded compound 4 as the
major product (58 %) and 8 as the minor one (42%).
With Mn(TPFPP)Cl (III) the aromatic hydroxylation of the
substrates and the transformation of the phenols to the correspond-
ing quinones were always the main transformations observed.
These results are in agreement with our previous studies with
catalyst III, which showed high chemoselectivity for aromatic
hydroxylation.12 With this catalyst, naphthalene was mainly
transformed into 1-naphthol 5 (62%) and 1,4-naphthoquinone 6
(15%), whereas the dioxide 1 was obtained with 20% selectivity.
Anthracene gave 100% selectivity for the anthraquinone 7.
The oxidation of phenanthrene in the presence of catalyst III
afforded only compounds 4 and 8 with 41 and 59% selectivity,
respectively.
6 E. Vogel, H.-H. Klug and M. Schäfer-Ridder, Angew. Chem., Int. Ed.
Engl., 1976, 15, 229; K. Tshikawa and G. W. Griffin, Angew. Chem.,
Int. Ed. Engl., 1977, 16, 171.
7 R. Jeyaraman and R. W. Murray, J. Am. Chem. Soc., 1984, 106,
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8 Cytochrome P450: Structure, Mechanism and Biochemistry, P. Ortiz de
Montellano, ed., Plenum Press, New York, 1995.
9 J. Mc Lain, J. Lee and J. T. Groves, in Biomimetic Oxidations Catalysed
by Transition Metal Complexes, B. Meunier, ed., Imperial College
Press, London, 2000, p. 91.
10 B. Meunier, A. Robert, G. Pratviel and J. Bernadou, in The Porphyrin
Handbook, K. M. Kadish, K. M. Smith and R. Guilard, ed., Academic
Press, New York, 2000, vol. 4, p. 119.
11 A. Thellend, P. Battioni and D. Mansuy, J. Chem. Soc., Chem.
Commun., 1994, 1035.
12 S. L. H. Rebelo, M. M. Q. Simões, M. G. P. M. S. Neves and J. A. S.
Cavaleiro, J. Mol. Catal. A: Chem., 2003, 201, 9.
13 R. R. L. Martins, M. G. P. M. S. Neves, A. J. D. Silvestre, A. M. S. Silva
and J. A. S. Cavaleiro, J. Mol. Catal. A: Chem., 1999, 137, 41.
14 M. N. Carrier, C. Sheer, P. Gouvine, J. F. Bartoli, P. Battioni and D.
Mansuy, Tetrahedron Lett., 1990, 31, 6645.
15 J. F. Bartoli, V. Mouries-Mansuy, K. Le Barch-Ozette, M. Palacio, P.
Battioni and D. Mansuy, Chem. Commun., 2000, 827; T. Higuchi, C.
Satake and M. Hirobe, J. Am. Chem. Soc., 1995, 117, 8879; H. R.
Khavasi, S. S. H. Davarani and N. Safari, J. Mol. Catal. A: Chem., 2002,
188, 115.
16 A. M. A. R. Gonsalves, J. M. T. B. Varejão and M. M. Pereira, J.
Heterocycl. Chem., 1991, 28, 635.
17 J. W. Buchler, in The Porphyrins, D. Dolphin, ed., Academic Press,
New York, 1978, vol. 1, p. 398 and refs. cited therein.
18 A. D. Adler, F. R. Longo, F. Kampes and J. J. Kim, Inorg. Nucl. Chem.,
1970, 32, 2443.
19 Spectroscopic data for 1: 1H NMR: d 3.73–3.74 (m, 2H, H-1,4),
4.01–4.02 (m, 2H, H-2,3), 7.35–7.37 (m, 2H, H-6,7), 7.43–7.46 (m, 2H,
H-5,8); 13C NMR: d 52.0 (C-1,4), 54.7 (C-2,3), 129.4 (C-6,7), 131.47
(C-4a,8a), 131.50 (C-5,8). MS (EI) m/z (rel. int. %): 160 (M+·, 23). The
melting point (96–98 °C) compares favourably with that described
(99–100 °C) in ref. 6.
We also tried to oxidise benzene under the above oxidative
conditions, but after 14 h of reaction only a very small product peak
( < 5%, m/z M+· 94) was detected by GC–MS. The total amount of
this compound did not allow its identification.
Knowing that one of the main applications of the oxygenation
reactions using biomimetic models of cytochrome P450 is the
preparation of xenobiotic metabolites, it can be concluded that the
reactions described in this work open a potential and fascinating
way to the synthesis of polycyclic aromatic hydrocarbon metabo-
lites or corresponding precursors. These catalytic reactions can also
become new and efficient ways for a researcher to transform
polycyclic aromatic hydrocarbons into other functionalised com-
pounds.
20 Spectroscopic data for 2: 1H NMR: d 3.94–3.95 (m, 2H, H-1,4),
4.07–4.09 (m, 2H, H-2,3), 7.51–7.54 (m, 2H, H-5,8), 7.81–7.84 (m, 2H,
H-6,7), 7.91 (s, 2H, H-9,10); 13C NMR: d 52.6 (C-1,4), 54.8 (C-2,3),
127.2 (C-6,7), 127.7 (C-5,8), 128.4 (C-9a,9b), 131.7 (C-9,10), 133.3 (C-
8a,10a). MS (EI) m/z (rel. int. %): 210 (M+·, 32).
1
21 Spectroscopic data for the syn-isomer of 1: H NMR: d 3.93–3.95 (m,
2H, H-2,3), 4.01–4.02 (m, 2H, H-1,4), 7.41–7.44, 7.65–7.68 (m, 4H, H-
5,6,7,8). Spectroscopic data for the syn-isomer of 2: 1H NMR: d
3.98–4.00 (m, 2H, H-2,3), 4.16–4.18 (m, 2H, H-1,4), 7.55–7.57,
7.88–7.90 (m, 4H, H-5,6,7,8), 8.15 (s, 2H, H-9,10).
22 Spectroscopic data for 9: 1H NMR: d 4.78 (s, 2H, H-9,10), 6.86–6.88
(m, 4H, H-1,2,3,4), 7.41–7.44 (m, 4H, H-5,6,7,8). Spectroscopic data
for 10: 1H NMR: d 3.70–3.72 (m, 4H, H-1,4,5,8), 4.00–4.02 (m, 4H, H-
2,3,6,7), 7.50 (s, 2H, H-9,10).
C h e m . C o m m u n . , 2 0 0 4 , 6 0 8 – 6 0 9
609