A simple and advantageous protocol for the oxidation of alcohols with o-iodoxybenzoic acid (IBX)

Organic Letters

Volumn 4, Issue 17, 2002, Pages 3001-3003

  More, Jesse D ^a   Finney, Nathaniel S ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

2 IODYLBENZOIC ACID; 2-IODOXYBENZOIC ACID; ALCOHOL DERIVATIVE; IODOBENZOIC ACID DERIVATIVE; KETONE; OXIDIZING AGENT; SOLVENT;

ARTICLE; CHEMISTRY; OXIDATION REDUCTION REACTION; POLLUTION; RECYCLING; SYNTHESIS;

ALCOHOLS; ENVIRONMENTAL POLLUTION; EQUIPMENT REUSE; IODOBENZOATES; KETONES; OXIDANTS; OXIDATION-REDUCTION; SOLVENTS;

EID: 0000234498     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol026427n     Document Type: Article

References (20)

1. (a) Frigerio, M.; Santagostino, M. Tetrahedron Lett. 1994, 35, 8019-8022.
2. (b) Frigerio, M.; Santagostino, M.; Sputore, S.; Palmisano, G. J. Org. Chem. 1995, 60, 7272-7276.
3. (c) De Munari, S.; Frigerio, M.; Santagostino, M. J. Org. Chem. 1996, 61, 9272-9279. See also ref 2a.
4. IBX has also found use in several other oxidative transformations. For an overview, see: (a) Wirth, T. Angew. Chem., Int. Ed. 2001, 40, 2812-2814. For more recent developments, see:
5. (b) Nicolaou, K. C.; Baran, P. S.; Zhong, Y.-L.; Barluenga, S.; Hunt, W. K.; Kranich, R.; Vega, J. A. J. Am. Chem. Soc. 2002, 124, 2233-2244.
6. (c) Nicolaou, K. C.; Montagnon, T.; Baran, P. S.; Zhong, Y.-L. J. Am. Chem. Soc. 2002, 124, 2245-2258.
7. IBX was first prepared over 100 years ago: Hartman, C.; Mayer, V. Chem. Ber. 1893, 26, 1727.
8. Prior to its use as a terminal oxidant in its own right, IBX was identified as a valuable precursor to the Dess-Martin periodinane: Dess, D. B.; Martin, J. C. J. Am. Chem. Soc. 1991, 113, 7277-7287, and references therein.
9. (a) Mülbaier, M.; Giannis, A. Angew. Chem., Int. Ed. 2001, 40, 4393-4394.
10. (b) Sorg, G.; Mengel, A.; Jung, G.; Rademan, J. Angew. Chem., Int. Ed. 2001, 39, 4395-4397.
11. Caution! IBX, like other hypervalent iodine oxidants, can explode on impact or heating. See: Plumb, J. B.; Harper, D. J. Chem. Eng. News 1990, 68 (29), 3.
12. The use of THF leads to solvent oxidation as the primary reaction, affording only small amounts of the desired aldehyde. The use of toluene leads to intractable dark-colored reactions; we suspect that both IBX decomposition and toluene oxidation are involved, although IBX does not oxidize toluene in EtOAc.
13. We cannot exclude the possibility that these oxidations occur at the interface of solvent and undissolved IBX. However, three points argue against this: the oxidation is independent of apparent IBX morphology, a solvent dependence is observed, and yields are reproducibly high.
14. An early report (ref 1b) describes a single instance in which IBX in THF oxidizes benzil to benzoin.
15. The alcohols in Table 2 are commercially available and were used as received, with the following exceptions. Entry 5: Prepared by Stille coupling of 2,5-bis(trimethylstannyl)furan with o-iodobenzyl alcohol (Fang, A. G., Finney, N. S., unpublished results). Entries 9, 10: Prepared by reaction of amino alcohol with 1 equiv of FmocOSu. Entry 12: Prepared according to Leonard, N. J.; Carraway, K. L. J. Heterocycl. Chem. 1966, 3, 485.
16. The alcohols in Table 2 are commercially available and were used as received, with the following exceptions. Entry 5: Prepared by Stille coupling of 2,5-bis(trimethylstannyl)furan with o-iodobenzyl alcohol (Fang, A. G., Finney, N. S., unpublished results). Entries 9, 10: Prepared by reaction of amino alcohol with 1 equiv of FmocOSu. Entry 12: Prepared according to Leonard, N. J.; Carraway, K. L. J. Heterocycl. Chem. 1966, 3, 485.
17. Benzaldehyde is also oxidized to benzoic acid under these conditions. We believe this is the first report of IBX allowing conversion of an alcohol or aldehyde to the corresponding carboxylic acid.
18. Frigerio, M.; Santogostino, M.; Sputore, S. J. Org. Chem. 1999, 64, 4537-4538.
19. 6).
20. 1H NMR) of piperonal as a waxy solid.