H. Fujioka et al. / Tetrahedron Letters 52 (2011) 973–975
975
Supplementary data
Ph
R
O
R'
PIDA
R
AcO
I
R'
HO
Supplementary data (experimental procedures, characteriza-
tion data, and 1H and 13C NMR spectra for all compounds) associ-
ated with this article can be found, in the online version, at
O
i
R
O
R'
H2O
OH
R
References and notes
R'
ii
1. (a) Stang, P. J.; Zhdankin, V. V. Chem. Rev. 1996, 96, 1123; (b) Zhdankin, V. V.;
Stang, P. J. Chem. Rev. 2002, 102, 2523.
Scheme 4. Plausible reaction mechanism.
2. For reviews by our group, see: (a) Kita, Y.; Tohma, H.; Yakura, T. Trends Org.
Chem. 1992, 113; (b) Tohma, H.; Kita, Y. J. Synth. Org. Chem. Jpn. 2004, 62, 116; (c)
Dohi, T.; Kita, Y. Chem. Commun. 2009, 2073. and for reports about phenol
oxidations, see; (d) Tamura, Y.; Yakura, T.; Haruta, J.; Kita, Y. J. Org. Chem. 1987,
52, 3927; (e) Kita, Y.; Tohma, H.; Kikuchi, K.; Inagaki, M.; Yakura, T. J. Org. Chem.
1991, 56, 435; (f) Kita, Y.; Tohma, H.; Hatanaka, K.; Takada, T.; Fujita, S.; Mitoh,
S.; Sakurai, H.; Oka, S. J. Am. Chem. Soc. 1994, 116, 3684; (g) Kita, Y.; Takada, T.;
Tohma, H. Pure Appl. Chem. 1996, 68, 627; (h) Tohma, H.; Morioka, H.; Takizawa,
S.; Arisawa, M.; Kita, Y. Tetrahedron 2001, 57, 345; (i) Hata, K.; Hamamoto, H.;
Shiozaki, Y.; Cammerer, S. M.; Kita, Y. Tetrahedron 2007, 63, 4052; (j) Dohi, T.;
Minamitsuji, Y.; Maruyama, A.; Hirose, S.; Kita, Y. Org. Lett. 2008, 10, 3559.
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K.; Kita, Y. Chem. Commun. 2010, 46, 4133.
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Makhaev, V. D.; Petrova, L. A.; Nikishin, G. I. Russ. Chem. Bull. 1999, 48, 2080.
5. For transition metal induced bond cleavage, see: (a) Nishimura, T.; Ohe, K.;
Uemura, S. J. Am. Chem. Soc. 1999, 121, 2646; (b) Matsumura, S.; Maeda, Y.;
Nishimura, T.; Uemura, S. J. Am. Chem. Soc. 2003, 125, 8862; (c) Matsuda, T.;
Makino, M.; Murakami, M. Bull. Chem. Soc. Jpn. 2005, 78, 1528; For base induced
bond cleavage, see: (d) Thies, R. W.; Shih, H.-H. J. J. Org. Chem. 1977, 42, 280; (e)
Winkler, J. D.; Doherty, E. M. J. Am. Chem. Soc. 1999, 121, 7425; (f) Mislin, G. L.;
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Casey, B. M.; Eakin, C. A.; Flowers, R. A., II Tetrahedron Lett. 2009, 50, 1264.
6. (a) Moriarty, R. M.; Vaid, R. K.; Duncan, M. P.; Vaid, B. K. Tetrahedron Lett. 1987,
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proposed reaction mechanism could be very plausible for the
cyclobutanols bearing R0 substituents (R0 – H), the concerted
mechanism was not excluded in the case of
a-unsubstituted
cyclobutanols (R0 = H) because of instability of primary alkyl
cations.
In summary, we developed the PIDA mediated oxidative cleav-
age of cyclobutanols, which leads to efficient entry of c-hydroxy
ketones. This reaction proceeded under mild conditions and
showed a broad generality. When using 2-substituted cyclobuta-
nols, the C–C bond cleavage underwent regioselectively to give
c-substituted c-hydroxy ketones. The developed reaction using
environmentally benign hypervalent iodine reagents is very valu-
able, because the cleavages of cyclobutanols are one of the funda-
mental transformations in organic synthesis and the reported
oxidative cleavages of cyclobutanols use highly toxic heavy metals
under harsh conditions.5 A further extension of this method is now
underway.
Acknowledgments
This work was financially supported by Grant-in-Aid for Scien-
tific Research (A) and (B) from JSPS.