I. R. Baxendale and S. V. Ley, J. Green Chem., 2000, 43; (c)
M. Calderelli, J. Habermann and S. V. Ley, J. Chem. Soc., Perkin
Trans. 1, 1999, 107; (d ) J. Habermann, S. V. Ley and R. Smits,
J. Chem. Soc., Perkin Trans. 1, 1999, 2421; (e) J. Habermann, S. V.
Ley, J. J. Scicinski, J. S. Scott, R. Smits and A. W. Thomas, J. Chem.
Soc., Perkin Trans. 1, 1999, 2425; ( f ) J. Habermann, S. V. Ley and
J. S. Scott, J. Chem. Soc., Perkin Trans. 1, 1998, 3127.
3 (a) I. R. Baxendale, G. Brusotti, M. Matsuoka and S. V. Ley,
J. Chem. Soc., Perkin Trans. 1, 2001, 143; (b) I. R. Baxendale, A.-L.
Lee and S. V. Ley, Synlett, 2001, 1482; (c) S. V. Ley, O. Schucht,
A. W. Thomas and P. J. Murray, J. Chem. Soc., Perkin Trans. 1, 1999,
1251.
4 For a comprehensive review see S. V. Ley, I. R. Baxendale, R. N.
Bream, P. S. Jackson, A. G. Leach, D. A. Longbottom, M. Nesi, J. S.
Scott, I. R. Storer and S. J. Taylor, J. Chem. Soc., Perkin Trans. 1,
2000, 3815.
5 For examples see (a) S. D. Rychnovsky and R. Vaidyanathan, J. Org.
Chem., 1999, 64, 310; (b) A. E. J. de. Nooy, A. C. Besemer and
H. Bekkum, Synthesis, 1996, 1153; (c) J. M. Bobbitt and M. C. L.
Flores, Heterocycles, 1988, 27, 509; (d ) P. L. Anelli, C. Biffi, F.
Montanari and S. Quici, J. Org. Chem., 1987, 52, 2559; (e) T.
Miyazawa, T. Endo, S. Shiihashi and M. Okawara, J. Org. Chem.,
1985, 50, 1332; ( f ) H. Bowers and L. Jones, J. Chem. Soc., 1953,
2548; (g) M. Zhao, J. Li, Z. Song, R. Desmond, D. M. Tschaen,
E. J. J. Grabowski and P. J. Reider, Tetrahedron Lett., 1998, 39,
5323.
Tschaen, E. J. J. Grabowski and P. J. Reider, J. Org. Chem., 1999, 64,
2564.
9 A typical procedure for the oxidation of an alcohol to a carboxylic
acid: prior to use PS-TEMPO (18.8 mg, 0.030 mmol) was washed
with acetonitrile (2 × 2 ml). To a suspension of washed PS-TEMPO,
PS-Chlorite (0.7 g, 1.5 mmol), PS-Dihydrogen phosphate (154 mg,
0.30 mmol) and potassium bromide (3.6 mg, 0.030 mmol) in
acetonitrile (1 ml) was added NaOCl (8.5 mg, 0.012 mmol) as an
aqueous solution in water (0.5 ml). After 10 min at room temper-
ature the alcohol (0.3 mmol) was added as a solution in acetonitrile
(1 ml). The mixture was stirred at room temperature (24–48 h) then
passed through a short pad of Celite (1 g). The precipitate was
washed with acetonitrile (30 ml) and the washings concentrated in
vacuo. The residue was dissolved in acetonitrile (0.5 ml) and passed
through a short pad of silica (0.3 g) eluting with 25% MeOH in
CHCl3 (10 ml). The filtrate was concentrated to give the desired
carboxylic acid derivative.
10 TEMPO polystyrene is available from the Novabiochem Polymer-
Supported Reagents catalogue (2001, p. 26).
11 Preparation of PS-chlorite: Polymer-supported chloride (Fluka,
4 mmol gϪ1, 10 g) was washed with water (500 ml). The resin was
added to sodium chlorite solution (2.0 M, 100 ml) and shaken at
25 ЊC for 24 h. The resin was collected by filtration, and washed with
water (50 ml × 2), THF (50 ml × 2) and Et2O (50 ml × 2) to obtain
18.6 g of PS-chlorite.
12 (a) B. J. Cohen, M. A. Kraus and A. Patchornik, J. Am. Chem. Soc.,
1977, 99, 4165; (b) G. Cainelli, M. Contento, F. Manescalchi and
R. Regnoli, J. Chem. Soc., Perkin Trans. 1, 1980, 2516; (c) D. E.
Bergbreiter and R. Chandran, J. Am. Chem. Soc., 1985, 107, 4792;
(d ) M. Bessodes and K. Antonakis, Tetrahedron Lett., 1985, 26,
1305; (e) S. L. Regen and M. Kodomari, J. Chem. Soc., Chem.
Commun., 1987, 1428; ( f ) J. J. Parlow, Tetrahedron Lett., 1995, 36,
1395; (g) L. Blackburn and R. J. K. Taylor, Org. Lett., 2001, 3, 1637.
6 For examples see (a) J. G. Deshmukh, M. H. Jagdale, R. B. Mane,
M. M. Salunkheanal and P. P. Wadgaonkar, Eur. Polym. J., 1987, 23,
577; (b) B. Tamami and M. A. Zarchi, Eur. Polym. J., 1955, 31, 715.
7 T. Takemoto, K. Yasuda and S. V. Ley, Synlett, 2001, 1555.
8 For a useful discussion of the oxidation of primary alcohols to
carboxylic acids in the solution phase with sodium chlorite catalysed
by TEMPO and bleach see M. Zhao, J. Li, E. Mano, Z. Song, D. M.
J. Chem. Soc., Perkin Trans. 1, 2002, 1024–1025
1025