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Bobbitt, Chem. Commun., 1996, 1043.
Fig. 1 Yields [hatched (%)] and conversions [black (%)] in consecutive
oxidation reactions of nonan-1-ol when using silica-supported catalyst 3.
secondary substrates. Optically active starting materials can be
used without racemisation. Finally, the catalyst was shown to be
stable under the reaction conditions, thus allowing it to be
recycled without significant loss of activity.
11 R. Siedlecka, J. Skarzewski and J. Mlochowski, Tetrahedron Lett.,
1990, 31, 2177; M. R. Leanna, T. J. Sowin and H. E. Morton,
Tetrahedron Lett., 1992, 33, 5029; T. S. Straub, J. Chem. Educ., 1991,
68, 1048; N. J. Davis and S. L. Flitsch, Tetrahedron Lett., 1993, 34,
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Linden, J. Org. Chem., 1996, 61, 4400; G. Tong, J. W. Perich and R. B.
Johns, Tetrahedron Lett., 1990, 31, 3759.
This research was supported by the Katalyseverbund NRW
and the Fonds der Chemischen Industrie.
Notes and references
† CAS nomenclature = nitroxyl.
‡ Aminopropyl-functionalised silica was purchased from Aldrich. Accord-
ing to the distributor’s information the degree of functionalisation is
12 For a review on that topic: D. P. Curran, Angew. Chem., Int. Ed., 1998,
37, 1174.
approximately 1.0 mmol g21
.
13 (a) T. Miyazawa and T. Endo, J. Polym. Sci., Polym. Chem. Ed., 1985,
23, 2487; (b) T. Miyazawa and T. Endo, J. Mol. Catal., 1988, 49, L31;
(c) A. Deronzier, D. Lìmosin and J.-C. Moutet, Electrochim. Acta, 1987,
32, 1643; (d) T. Osa, U. Akiba, I. Segawa and J. M. Bobbitt, Chem. Lett.,
1988, 1423; (e) F. MacCorquodale, J. A. Crayston, J. C. Walton and
D. J. Worsfold, Tetrahedron Lett., 1990, 31, 771; (f) C. Amiel, B.
Sebille, H. Hommel and A. P. Legrand, J. Colloid Interface Sci., 1994,
165, 236; (g) A. W. Bosman, R. A. J. Janssen and E. W. Meijer,
Macromolecules, 1997, 30, 3606.
14 Selected recent examples of oxidations with polymer-supported re-
agents and catalysts: (a) J. A. Elings, R. Ait-Meddour, J. H. Clark and
D. J. Macquarrie, Chem. Commun., 1998, 2707; (b) B. Hinzen and S. V.
Ley, J. Chem. Soc., Perkin Trans. 1, 1997, 1907; (c) B. Hinzen, R. Lenz
and S. V. Ley, Synthesis, 1998, 977; (d) L. Canali, E. Cowan, H.
Deleuze, C. L. Gibson and D. C. Sherrington, Chem. Commun., 1998,
2561; (e) J. K. Karjaleinen, O. E. O. Hormi and D. C. Sherrington,
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therein.
15 C. Bolm, A. Maischak and A. Gerlach, Chem. Commun., 1997, 2353.
16 Compound 2 was synthesised as described in C. M. Paleos and P. Dais,
J. Chem. Soc., Chem. Commun., 1977, 345.
17 The reductive amination was carried out with an excess of the carbonyl
compound analogously to the synthesis of 4-amino-TEMPO from
4-oxo-TEMPO: G. M. Rosen, J. Med. Chem., 1974, 17, 358.
18 The ee of the product was determined by GC [Lipodex-A (Macherey-
Nagel), 50 m 3 0.25 mm, 100 kPa H2, 30 °C] after its reduction to the
corresponding alcohol.
§ General procedure for the oxidation of alcohols with SG-TMP-OH 3 as
catalyst: The reaction was performed in a glass tube with a cooling mantle.
The bottom of the tube was equipped with a ceramic filter plate and a
stopcock allowing easy separation of the supported catalyst from the
reaction mixture by filtration. In this vessel was placed 9.2 mg of SG-TMP-
OH 3 (8 mmol based on complete functionalisation; degree of functionalisa-
tion = 0.87 mmol g21). Then a CH2Cl2 solution (2 ml) of the alcohol (0.4
M) and decane or dodecane (0.12 M; as internal standard) was added
followed by an aqueous solution (0.16 ml) of KBr (0.5 M). After the cooling
of the reaction mixture to 0 °C, 2.7 ml of aq. NaOCl (diluted to a final
concentration of 0.37 M and buffered by the addition of NaHCO3 to a pH
of 9.1) was added. Then, the reaction mixture was vigorously shaken for 30
min. After filtration, the organic phase was separated, dried over MgSO4,
and the product composition was analysed by means of GC [ultra-2-column
(Hewlett Packard)]. The filtered solid was washed five times with water,
MeOH and CH2Cl2 (2 ml each), air-dried, and reused as such. Preparative
runs were carried out on a five-fold scale, and the reaction time was
extended to 1 h. After filtration the organic layer was separated, and the
aqueous phase was extracted with CH2Cl2 once. The combined organic
phases were dried over MgSO4, the solvent was removed in vacuo, and the
crude product purified by column chromatography on silica gel with
CH2Cl2 as eluent.
1 For reviews see: A. E. J. de Nooy, A. C. Besemer and H. van Bekkum,
Synthesis, 1996, 1153; J. M. Bobbitt and M. C. L. Flores, Heterocycles,
1988, 27, 509; early observations: E. G. Rozantsev and V. D. Sholle,
Synthesis, 1971, 401.
2 (a) P. L. Anelli, C. Biffi, F. Montanari and S. Quici, J. Org. Chem.,
1987, 52, 2559; (b) P. L. Anelli, S. Banfi, F. Montanari and S. Quici,
J. Org. Chem., 1989, 54, 2970; (c) P. L. Anelli, F. Montanari and S.
Quici, Org. Synth., 1990, 69, 212.
19 Some mechanistic aspects concerning this phenomenon are discussed in
A. E. J. de Nooy, A. C. Besemer and H. van Bekkum, Tetrahedron,
1995, 51, 8023.
3 M. Zhao, J. Li, E. Mano, Z. Song, D. M. Tschaen, E. J. J. Grabowski and
P. J. Reider, J. Org. Chem., 1999, 64, 2564.
4 T. Inokuchi, S. Matsumoto, T. Nishiyama and S. Torii, J. Org. Chem.,
1990, 55, 462.
Communication 9/05683A
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Chem. Commun., 1999, 1795–1796