Journal of the American Chemical Society
Communication
temperature, the reaction products were analyzed by GC-MS.
The products and their yields are shown in Figure 2. The
chlorination products are the same as the products from 1. The
ratio of the p- and o-chloroanisoles is different from the ratio
formed from 1, but close to the ratio obtained in chlorination
(2) (a) Murakami, T.; Yamaguchi, K.; Watanabe, Y.; Morishima, I.
Bull. Chem. Soc. Jpn. 1998, 71, 1343−1353. (b) Nanthankumar, A.;
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8
17
reactions using chlorine as reported previously. These results
(
1
(
indicate that 1 can react with excess chloride ion to form a
III
chlorine molecule and (TPFP)Fe Cl.
The chlorination reactions induced by iron(III) meso-chloro-
isoporphyrin complex could be expanded in the development
of a catalytic chlorination reaction. When ozone gas is bubbled
1984, 23, 2932−2935. (b) Abhilash, G. J.; Bhuyan, J.; Singh, P.; Maji,
S.; Pal, K.; Sarkar, S. Inorg. Chem. 2009, 48, 1790−1792.
(c) Rachlewicz, K.; Latos-Grazy
̇
́
nski, L. Inorg. Chem. 1995, 34, 718−
III
−4
7
27.
into a mixture of (TPFP)Fe Cl (5.0 × 10 M, 1 mol %), TFA
(
(
6) Woodward, R. B. Pure Appl. Chem. 1961, 2, 383−404.
(
0.1 M), TBACl (0.05 M), and 1,3,5-trimethoxybenzene (0.05
7) Dophin, D.; Felton, R. H.; Borg, D. C.; Fajer, J. J. Am. Chem. Soc.
M) in DCM at room temperature for 1.5 h, 1-chloro-2,4,6-
1
(
1
(
970, 92, 743−745.
8) Dinello, R. K.; Rousseau, K.; Dolphin, D. Ann. N.Y. Acad. Sci.
975, 244, 94−106.
9) (a) Davydov, R.; Matsui, T.; Fujii, H.; Ikeda-Saito, M.; Hoffman,
trimethoxybenzene is produced in 16% yield (turnover number
2
4
=
16). Moreover, the same product is also produced in 85%
yield (turnover number = 85) when an aqueous solution of
hydrogen peroxide is vigorously stirred with a mixture of
B. M. J. Am. Chem. Soc. 2003, 125, 16340−16346. (b) Evans, J. P.;
Niemevz, F.; Buldain, G.; Oritz de Montellano, P. J. Biol. Chem. 2008,
283, 19530−19539.
III
−4
(
(
TPFP)Fe Cl (5.0 × 10 M, 1 mol %), TFA (0.1 M), TBACl
0.05 M), and 1,3,5-trimethoxybenzene (0.05 M) in DCM at
room temperature for 1 h. Similar catalytic chlorination
reactions with a heme thiolate complex have been reported by
Woggon et al., who proposed the formation of hypochlorite
as a chlorinating agent in a haloperoxidase reaction. This
process seems not to be involved under our conditions because
the formation of 1 is much faster than the reaction of
24
(10) (a) Wiseman, J. S.; Nichols, J. S.; Kolpak, M. X. J. Biol. Chem.
1
982, 257, 6328−6332. (b) Ator, M. A.; David, S. K.; Ortiz de
Montellano, P. J. Biol. Chem. 1989, 264, 9250−9257.
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623−8530.
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2
0
(
8
(
E.; Johnston, E. R. Biochemistry 2002, 41, 9601−9610.
(13) Takahashi, A.; Kurahashi, T.; Fujii, H. Inorg. Chem. 2009, 48,
+
•
IV
17
(
TPFP )Fe O(NO ) with TBACl. In addition, isoporphyr-
3
in could not be formed under their conditions because acetic
acid was used as proton source. Further studies are needed to
optimize the reaction conditions and to clarify the mechanism
of the catalytic reactions.
In summary, this study demonstrates the conversion of
oxoiron(IV) porphyrin π-cation radical to iron(III) meso-
chloro-isoporphyrin in the presence of chloride ion and TFA.
The iron(III) meso-chloro-isoporphyrin complex formed in this
reaction is a reactive agent capable of chlorination of aromatic
compounds and olefins.
2
614−2615.
(14) (a) Schmidt, E. S.; Bruice, T. C.; Brown, R. S.; Wilkins, C. L.
Inorg. Chem. 1986, 25, 4799−4780. (b) Lee, W. A.; Bruice, T. Inorg.
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K. M. Chem. Commun. 2007, 2258−2260. (d) Bhuyan, J.; Sarkar, S.
Chem.Eur. J. 2010, 16, 10649−10652.
(
(
(
15) Fujii, H. Chem. Lett. 1994, 1491−1494.
16) Brown, F. S.; Hager, L. P. J. Am. Chem. Soc. 1967, 89, 719−720.
17) Cong, Z.; Kurahashi, T.; Fujii, H. Angew. Chem., Int. Ed. 2011,
5
(
1
0, 9935−9939.
18) Kaustov, L.; Tal, M. E.; Shames, A. I.; Gross, Z. Inorg. Chem.
997, 36, 3503−3511.
ASSOCIATED CONTENT
(19) (a) Umile, T. P.; Wang, D.; Groves, J. T. Inorg. Chem. 2011, 50,
0353−10362. (b) Liu, W.; Groves, J. T. J. Am. Chem. Soc. 2010, 132,
2847−12849.
■
1
1
(
*
S
Supporting Information
20) (a) Wagenknecht, H.-A.; Woggon, W.-D. Angew. Chem., Int. Ed.
997, 36, 390−392. (b) Wagenknecht, H.-A.; Claude, C.; Woggon,
1
W.-D. Helv. Chim. Acta 1998, 81, 1506−1520. (c) Woggon, W.-D. Acc.
Chem. Res. 2005, 38, 127−136.
(21) Zweig, A.; Hodgson, W. G.; Jura, W. H. J. Am. Chem. Soc. 1964,
8
(
AUTHOR INFORMATION
6, 4124−29.
22) Nakagaki, T.; Shin-ichiro, K.; Harano, A.; Shinmyozu, T.
Tetrahedron 2010, 66, 976−985.
Notes
(23) Faita, G.; Fleischmann, M.; Pletcher, D. J. Electroanal. Chem.
1970, 25, 455−459.
The authors declare no competing financial interest.
III
−3
(
24) The blank experiments, (TPFP)Fe Cl (1.0 × 10 M) in the
presence of TBACl (0.05 M), TFA (0.1 M), and 1,3,5-trimethox-
ybenzene (0.05 M), formed 1-chloro-2,4,6-trimethoxybenzene in 0.1%
yield (turnover number = 0.1).
ACKNOWLEDGMENTS
■
This study was supported by grants from JSPS (Grant-in-Aid
for Science Research, Grant No. 22350030) and MEXT
(Global COE Program).
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