M. Toganoh et al. / Tetrahedron Letters 49 (2008) 1488–1491
1491
L = pyridine or PPh3
O=PPh3
Re(VII)−(NFP)O3
N
PPh3
L
Re(V)−(NFP)O2
Re(V)−(NFP)O2L
O=PPh3
PPh3
Re(V)−(NFP)O2
O
N
Re(III)−(NFP)OL
O
N
decompose
Scheme 2. A plausible mechanism of Re(VII)–(NFP)O
3
-catalyzed oxygen atom transfer reactions.
in the case of Re(NFTPP)O , TON reached 340,000. On
11. Yoo, B. W.; Choi, J. W.; Yoon, C. M. Tetrahedron Lett. 2006, 47,
25–126.
12. Saini, A.; Kumar, S.; Sandhu, J. S. Synlett 2006, 395–398.
3
1
the basis of recent advances in the chemistry of the rhenium
2
6
oxo complexes and the rich heritage of porphyrinoid
chemistry, further development in the field of catalysis as
well as coordination chemistry will be expected.
1
3. Wang, Y.; Espenson, J. H. Org. Lett. 2000, 2, 3525–3526.
4. Sanz, R.; Escribano, J.; Fern a´ ndez, Y.; Aguado, R.; Pedrosa, M. R.;
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1
1
5. Nakagawa, H.; Higuchi, T.; Kikuchi, K.; Urano, Y.; Nagano, Y.
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Acknowledgments
1
1
6. Higuchi, T.; Hirobe, M. J. Mol. Catal. A 1996, 113, 403–422.
7. (a) Furuta, H.; Ishizuka, T.; Osuka, A.; Ogawa, T. J. Am. Chem. Soc.
The present work was supported by the Grant-in-Aid
for Scientific Research (16350024 and 19750036) and the
Global COE Program ‘Science for Future Molecular Sys-
tems’ from the Ministry of Education, Culture, Science,
Sports and Technology of Japan, and PRESTO from
JST, Japan.
1
999, 121, 2945–2946; (b) Furuta, H.; Ishizuka, T.; Osuka, A.;
Ogawa, T. J. Am. Chem. Soc. 2000, 122, 5748–5757.
18. (a) Toganoh, M.; Ishizuka, T.; Furuta, H. Chem. Commun. 2004,
2
2
2
464–2465; (b) Toganoh, M.; Ikeda, S.; Furuta, H. Chem. Commun.
005, 4589–4591; (c) Toganoh, M.; Ikeda, S.; Furuta, H. Inorg. Chem.
007, 46, 10003–10015.
1
2
9. Preliminary experimental result was reported in Ref. 18b.
0. At higher temperature (>230 °C) the reaction proceeded Howard, E.,
Jr.; Olszewski, W. F. J. Am. Chem. Soc. 1959, 81, 1483–1484.
1. General procedures. Method A: Triphenylphosphine (315 mg,
Supplementary data
2
1
.0 equiv) was added to a solution of pyridine N-oxide (1.0 equiv)
and Re(NFTPP)O (5.0 mg, 0.5 mol %) in 10 mL of CH Cl . The
mixture was stirred until no change was observed by TLC analysis.
The resulting solution was poured onto a silica gel column. Column
3
2
2
2 2
chromatography was performed with MeOH/CH Cl to give the
product. Method B: Triphenylphosphine (315 mg, 1.0 equiv) was
References and notes
added to
a
solution of pyridine N-oxide (1.0 equiv) and
Re(NFTPP)O
3
(5.0 mg, 0.5 mol %) in 10 mL of toluene at 23 °C.
1
2
3
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TLC analysis. The resulting solution was poured onto a silica gel
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2 2
CH Cl to give the product.
4
5
6
2
2
2
2. Isolation or further analysis on a tentative Re(V) species was so far
difficult due to its instability.
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