Table 1 Isotope labeling results (%) for naphthalene oxidation catalysed by 1
Entry
Unlabeled
Singly labeled
Doubly labeled
1 (cis-diol from H218O2/H216O)a
2 (cis-diol from H216O2/H218O)b
3 (naphthols from H218O2/H216O)a
4 (naphthols from H216O2/H218O)b
6
3
27
72
93
96
72
26
o1
0
—
—
a
b
10 equiv. H218O2 (2% aqueous solution) relative to catalyst was used as oxidant. 10 equiv. H2O2 (0.5 M in CH3CN from 35% aqueous solution)
diluted with 1000 equiv. H218O was used as oxidant.
and L. P. Wackett, J. Bacteriol., 1997, 179, 3858; K. Lee and
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3 K. D. Koehntop, J. P. Emerson and L. Que, Jr, JBIC, J. Biol.
Inorg. Chem., 2005, 10, 87.
4 B. Kauppi, K. Lee, E. Carredano, R. E. Parales, D. T. Gibson,
H. Eklund and S. Ramaswamy, Structure, 1998, 6, 571;
A. Karlsson, J. V. Parales, R. E. Parales, D. T. Gibson,
H. Eklund and S. Ramaswamy, Science, 2003, 299, 1039.
5 R. E. J. Parales, J. Ind. Microbiol. Biotechnol., 2003, 30, 271.
6 H. C. Kolb, M. S. VanNieuwenhze and K. B. Sharpless, Chem.
Rev., 1994, 94, 2483; L. Que, Jr and W. B. Tolman, Nature, 2008,
455, 333.
7 K. Chen, M. Costas, J. Kim, A. K. Tipton and L. Que, Jr, J. Am.
Chem. Soc., 2002, 124, 3026.
8 M. Fujita, M. Costas and L. Que, Jr, J. Am. Chem. Soc., 2003, 125,
9912.
´
9 R. Mas-Balleste, M. Costas, T. van den Berg and L. Que, Jr,
Scheme 2 Proposed mechanism for the cis-dihydroxylation of
naphthalene catalysed by 1.
Chem.–Eur. J., 2006, 12, 7489.
10 P. D. Oldenburg, A. A. Shteinman and L. Que, Jr, J. Am. Chem.
Soc., 2005, 127, 15672.
11 M. Klopstra, G. Roelfes, R. Hage, R. M. Kellogg and
B. L. Feringa, Eur. J. Inorg. Chem., 2004, 2004, 846.
12 S. Gosiewska, M. Lutz, A. L. Spek and R. J. M. Klein Gebbink,
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13 M. D. Wolfe, J. V. Parales, D. T. Gibson and J. D. Lipscomb,
J. Biol. Chem., 2001, 276, 1945; M. D. Wolfe and J. D. Lipscomb,
J. Biol. Chem., 2003, 278, 829.
14 S. P. de Visser and S. Shaik, J. Am. Chem. Soc., 2003, 125, 7413;
M. P. Jensen, S. J. Lange, M. P. Mehn, E. L. Que and L. Que, Jr,
J. Am. Chem. Soc., 2003, 125, 2113; M. Kang, W. J. Song, A. Han,
Y. S. Choi, H. G. Jang and W. Nam, J. Org. Chem., 2007, 72, 6301;
S. P. de Visser, K. Oh, A.-R. Han and W. Nam, Inorg. Chem.,
2007, 46, 4632.
under ambient conditions with H2O2 as oxidant and
thus models the action of naphthalene dioxygenase, via the
peroxide shunt pathway.13 18O labeling experiments strongly
implicate a HO–FeVQO oxidant that is formed via a water-
assisted mechanism originally proposed for the 1-catalysed
hydroxylation of alkanes16 and cis-dihydroxylation of olefins.7
By extension, this work suggests that the crystallographically
characterized side-on peroxo intermediate of NDO4
could convert to a similar high-valent HO–FeVQO oxidant
that is responsible for the biological cis-dihydroxylation of
naphthalene.
This work was supported by the Department of Energy
15 Unfortunately, decreasing the naphthalene concentration below
0.5 M resulted in decreased turnover, showing that the high
concentration of naphthalene was required to intercept the oxidant
efficiently.
16 K. Chen and L. Que, Jr, J. Am. Chem. Soc., 2001, 123, 6327.
17 Polyhydroxylation of benzenes to inositols and conduritols has
been achieved by photo-induced charge transfer osmylation where
presumably an initial cis-dihydrodiol derivative must be formed.
W. B. Motherwell and A. S. Williams, Angew. Chem., Int. Ed.
Engl., 1995, 34, 2031; P. M. J. Jung, W. B. Motherwell and
A. S. Williams, Chem. Commun., 1997, 1283.
(DOE DE-FG02-03ER15455). We are grateful to Dr Rube
´
n
Mas-Balleste and Dr Paul Oldenburg for valuable discussions.
´
Notes and references
1 M. Costas, M. P. Mehn, M. P. Jensen and L. Que, Jr, Chem. Rev.,
2004, 104, 939; L. P. Wackett, Enzyme Microb. Technol., 2002, 31, 577;
D. T. Gibson and R. E. Parales, Curr. Opin. Biotechnol., 2000, 11, 236.
2 S. Ramaswamy, D. J. Ferraro and L. Gakhar, Biochem. Biophys.
Res. Commun., 2005, 338, 175; S. Beil, B. Happe, K. N. Timmis
and D. H. Pieper, Eur. J. Biochem., 1997, 247, 190; C. C. Lange
ꢀc
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52 | Chem. Commun., 2009, 50–52