572
A. P. Thottumkara, T. K. Vinod / Tetrahedron Letters 43 (2002) 569–572
2000, 39, 622–625; (c) Nicolaou, K. C.; Zhong, Y.-L.;
Baran, P. S. Angew. Chem., Int. Ed. 2000, 39, 625–628; (d)
Nicolaou, K. C.; Baran, P. S.; Zhong, Y.-L.; Vega, J.
Angew. Chem., Int. Ed. 2000, 39, 2525–2529; (e) Nicolaou,
K. C.; Zhong, Y.-L.; Baran, P. S. J. Am. Chem. Soc. 2000,
122, 7596–7597; (f) Nicolaou, K. C.; Baran, P. S.; Zhong,
Y.-L. J. Am. Chem. Soc. 2001, 123, 3183–3185.
5. (a) Green Chemistry, Chemical & Engineering News, 2001,
July 16, 27–34; (b) Organic Synthesis in Water; Grieco, P.
A., Ed.; Blackie Academic: London, 1998; (c) Li, C.-J.
Chem. Rev. 1993, 93, 2023–2035.
6. (a) The conversion of 3-iodophthalic acid, 8 to mIBX, 3 is
carried out using KBrO3 in 0.73 M H2SO4 at 55–60°C as
follows: KBrO3 (5 g, 30 mmol) was added in portions to a
suspension of 8 (5 g, 17.1 mmol) in 70 mL of 0.73 M
H2SO4 over a period of 20 min. The mixture was then
maintained at 55–60°C for 12 h and the resulting clear
orange solution was evaporated to yield an off-white solid,
which was triturated with 30 mL of water at 0°C for 2 h
and filtered to obtain a white solid. This was further
triturated with hexanes (100 mL) for 6 h and filtered to
give 3 (3.9 g, 71%) as a white solid, mp: 258–260°C; (b) no
detonation of the sample was observed during the melting
point determination of mIBX, 3; (c) 3: Mp 258–260°C; IR
(KBr), 3503 3469, 3050, 1708, 1631, 1588, 1369, 730, 700
Scheme 2. Mechanism of oxidation of benzylic/allylic alco-
hols in water using mIBX.
References
1
cm−1; H NMR (D2O, 300 MHz): l 8.35 (dd, J=7.9, 1.0
Hz, 1H), 8.09 (t, J=7.9 Hz, 1H), 7.94 (dd, J=7.9, 1.0 Hz,
1H); 13C NMR (D2O, 75 MHz): l 125.5, 127.5, 132.5,
134.7, 137.0, 147.1 (ring carbons), 168.9, 172.9 (carbonyl
carbons)
1. (a) Varvoglis, A. Hypervalent Iodine in Organic Synthesis;
Academic Press: San Diego, 1997; (b) Tohma, H.; Tak-
izawa, S.; Maegawa, T.; Kita, Y. Angew. Chem., Intl. Ed.
2000, 39, 1306–1308; (c) Togo, H.; Nabana, T.;
Yamaguchi, K. J. Org. Chem. 2000, 65, 8391–8394; (d)
Ley, S. V.; Thomas, A. W.; Finch, H. J. Chem. Soc.,
Perkin Trans. 1 1999, 669–671; (e) De Mico, A.; Mar-
garita, R.; Parlanti, L.; Vescovi, A.; Piancatelli, G. J. Org.
Chem. 1997, 62, 6974–6977; (f) Corey, E. J.; Palani, A.
Tetrahedron Lett. 1995, 36, 7945–7948; (g) Frigerio, M.;
Santagostino, M.; Sputore, S.; Palmisano, G. J. Org.
Chem. 1995, 60, 7272–7276.
2. (a) Dess, D. B.; Martin, J. C. J. Am. Chem. Soc. 1991, 113,
7277–7287; (b) Dess, D. B.; Martin, J. C. J. Org. Chem.
1983, 48, 4155–4156; (c) Meyer, S. D.; Schrieber, S. L. J.
Org. Chem. 1994, 59, 7549–7552.
3. (a) For the first synthesis of IBX, see: Hartman, C.;
Meyer, V. Chem. Ber. 1893, 26, 1727; (b) For a superior
route to IBX, see: Friegerio, M.; Santagostino, M.; Supa-
tore, S. J. Org. Chem. 1999, 64, 4537–4538; (c) For use of
IBX as a selective oxidant for alacohols, see: Refs. 1f and
1g.
7. Corey, E. J.; Palani, A. Tetrahedron Lett. 1995, 36, 3485–
3488.
8. A typical oxidation procedure in the mixed solvent system
(oxidation of 4-nitrobenzyl alcohol, entry 5, Table 1, as an
example) is as follows: To a solution of of 4-nitrobenzyl
alcohol (100 mg, 0.65 mmol) in a mixture of water and
THF (5 mL, 3:2 v/v) was added 3 (315 mg, 0.98 mmol).
The homogeneous solution was left stirring at 55–60°C for
3 h and subsequently cooled and filtered to remove 12. The
filtrate after addition of H2O (15 mL) was extracted with
diethyl ether (2×10 mL). The organic extracts were com-
bined, dried (MgSO4), and evaporated to yield 79 mg of
4-nitrobenzaldehyde, identical in all respects with a com-
mercial sample.
9. Compound 12: Mp 261–262°C; IR (KBr), 3070, 2980,
1701, 1630, 1584, 1555, 1326, 820, 699 cm−1 1H NMR
;
(DMSO-d6, 300 MHz): l 8.24 (br s, 1H, D2O exchange-
able), 7.97–7.91 (m, 2H), 7.70 (dd, J=6.9, 1.5 Hz, 1H); 13
C
NMR (DMSO-d6, 75 MHz): l 121.8, 127.7, 127.9, 129.3,
134.9, 139.6 (ring carbons), 167.1, 169.3 (carbonyl car-
bons).
4. (a) Nicolaou, K. C.; Sugita, K.; Baran, P. S.; Zhong, Y.-L.
Angew. Chem., Int. Ed. 2001, 40, 207–210; (b) Nicolaou,
K. C.; Zhong, Y.-L.; Baran, P. S. Angew. Chem., Int. Ed.