SHORT PAPER
TEMPO-Mediated Oxidation of Alcohols
23
night. Et2O was then added to the solution for precipitation and the
product (ca. 9 g) was collected by filtration.
M.; Sputore, S.; Palmisano, G. J. Org. Chem. 1995, 60,
7272. (f) See also: Corey, E. J.; Palani, A. Tetrahedron Lett.
1995, 36, 7945. (g) See also: Corey, E. J.; Palani, A.
Tetrahedron Lett. 1995, 36, 3485. (h) See also: Friegerio,
M.; Santagostino, M.; Supatore, S. J. Org. Chem. 1999, 64,
4537. (i) See also: Nicolaou, K. C.; Zhong, Y.-L.; Baran, P.
S. Angew. Chem., Int. Ed. 2000, 39, 622. (j) See also:
Nicolaou, K. C.; Zhong, Y.-L.; Baran, P. S. Angew. Chem.,
Int. Ed. 2000, 39, 625. (k) See also: Thottumkara, A. P.;
Thottumkara, K. V. Tetrahedron Lett. 2002, 43, 569. (l)
See also: Moore, J. D.; Finney, N. S. Org. Lett. 2002, 4,
3001.
IR (KBr): 1630 (br), 1560 (br), 1480, 1450, 1410, 1260, 1180, 1000,
770 (br) cm–1.
Anal. Found: C, 38.86; H, 3.51; I, 37.17.
Loading rate of (diacetoxyiodo)phenyl group was estimated by ele-
mental analysis and iodometry analysis; loading rate was 2.0–2.6
mmol/g.
Oxidation of Alcohols with Poly[4-(diacetoxyiodo)styrene]
(PSDIB); General Procedure
(4) (a) (Dichloroiodo)benzene/Pyridine: Wicha, J.; Zarecki, A.;
Kocor, M. Tetrahedron Lett. 1973, 3635. (b)
PSDIB (600 mg, 1.2 mmol) was added to a solution of the appropri-
ate alcohol (1 mmol) and TEMPO (31 mg, 0.2 mmol) in acetone (2
mL) and the mixture was stirred at r.t. for the time given in Table 1.
At end of the reaction, Et2O (10 ml) was added and the mixture was
filtered to remove the polymer. After removal of the solvent from
the filtrate, the corresponding carbonyl compound was obtained in
over 95% purity. If necessary, the filtrate was poured into H2O and
extracted with Et2O (3 10 mL). The combined organic layers were
dried (Na2SO4), filtered, and the solvent was removed in vacuo. The
residue was chromatographed on silica gel to give the pure carbonyl
product (Table 1). The polymer reagent can be regenerated by treat-
ing poly(4-iodostyrene) with peracetic acid to give PSDIB and re-
used for the same reaction.
[Bis(trifluoroacetoxy)iodo]benzene/Pyridine: Spyroudis, S.;
Varvoglis, A. Synthesis 1975, 445. (c) i-PrMgBr/tBuOH/
(Diacetoxyiodo)benzene: Narasaka, K.; Morikawa, A.;
Saigo, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1977, 50,
2773. (d) Iodosylbenzene or (Diacetoxyiodo)benzene/
RuCl2(PPh3)3: Muller, P.; Godoy, J. Tetrahedron Lett. 1981,
22, 2361. (e) See also: Muller, P.; Godoy, J. Helv. Chem.
Acta 1983, 66, 1790. (f) (Diacetoxyiodo)benzene on
Alumina/Microwave Irradiation: Varma, R. S.; Dahiya, R.;
Saini, R. K. Tetrahedron Lett. 1997, 38, 7029. (g)
Iodosylbenzene/KBr/H2O: Tohma, H.; Takizawa, S.;
Maegawa, T.; Kita, Y. Angew. Chem., Int. Ed. 2000, 39,
1306. (h) [(Hydroxy)(tosyloxy)iodo]benzene and Poly{4-
[(hydroxy)(tosyloxy)iodo]styrene}: Abe, S.; Sakuratani, K.;
Togo, H. Synlett 2001, 22. (i) See also: Abe, S.; Sakuratani,
K.; Togo, H. J. Org. Chem. 2001, 66, 6174.
All aldehydes and ketones mentioned in this work are commercially
available. Thus, all compounds were identified by comparison with
the authentic samples.
Regeneration of Poly[4-(diacetoxyiodo)styrene]
(5) (a) Ganem, B. J. Org. Chem. 1975, 40, 1998.
(b) Miyazawa, T.; Endo, T.; Siihashi, S.; Okawara, M. J.
Org. Chem. 1985, 50, 1332. (c) Miyazawa, T.; Endo, T. J.
Org. Chem. 1985, 50, 3939. (d) Anelli, P. L.; Biffi, C.;
Montanari, F.; Quici, S. J. Org. Chem. 1987, 52, 2559.
(e) Leanna, M. R.; Sowin, T. J.; Morton, H. E. Tetrahedron
Lett. 1992, 33, 5029. (f) De Nooy, A. E. J.; Besemer, A. C.;
van Bekkum, H. Synthesis 1996, 1153. (g) Weik, S.;
Nicholson, G.; Jung, G.; Rademann, J. Angew. Chem., Int.
Ed. 2001, 40, 1436. (h) Dijksman, A.; Arends, I. W. C. E.;
Sheldon, R. A. Synlett 2001, 102.
Recovered polymer species [poly(4-iodostyrene)] was treated with
peracetic acid under the same conditions as mentioned above, to
form poly[4-(diacetoxyiodo)styrene].
Acknowledgement
Financial support from a Grant-in-Aid for Developmental Scientific
Research (No. 13554028) from the Ministry of Education, Science,
Sports and Culture of Japan is gratefully acknowledged.
(6) (a) De Mico, A.; Margarita, R.; Parlanti, L.; Vescovi, A.;
Piancatelli, G. J. Org. Chem. 1997, 62, 6974. (b) Pozzi, G.;
Quici, S.; Shepperson, I. Tetrahedron Lett. 2002, 43, 6141.
(7) Togo, H.; Nabana, T.; Yamaguchi, K. J. Org. Chem. 2000,
65, 8391.
(8) (a) Togo, H.; Nogami, G.; Yokoyama, M. Synlett 1998, 534.
(b) Togo, H.; Abe, S.; Nogami, G.; Yokoyama, M. Bull.
Chem. Soc. Jpn. 1999, 72, 2351.
(9) Sorg, G.; Mengel, A.; Jung, G.; Rademann, J. Angew.
Chem., Int. Ed. 2001, 40, 4395.
(10) Mülbair, M.; Giannis, A. Angew. Chem., Int. Ed. 2001, 40,
4393.
(11) (a) Varvoglis, A. Synthesis 1984, 709. (b) Moriarty, R. M.;
Vaid, R. K. Synthesis 1990, 431. (c) Prakash, O.; Saini, N.;
Sharma, P. K. Synlett 1994, 221. (d) Stang, P. J.; Zhdankin,
V. V. Chem. Rev. 1996, 96, 1123. (e) Varvoglis, A.
Tetrahedron 1997, 53, 1179. (f) Togo, H.; Katohgi, M.
Synlett 2001, 565. (g) Zhdankin, V. V.; Stang, P. J. Chem.
Rev. 2002, 102, 2523.
References
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Synthesis 2003, No. 1, 21–23 ISSN 0039-7881 © Thieme Stuttgart · New York