Sodium Periodate-Potassium Permanganate

NaIO4-KMnO4
(NaIO4)

[7790-28-5]  · INaO4  · Sodium Periodate-Potassium Permanganate  · (MW 213.89) (KMnO4)

[7722-64-7]  · KMnO4  · Sodium Periodate-Potassium Permanganate  · (MW 158.04)

(oxidant for the cleavage of carbon-carbon double bonds1)

Physical Data: NaIO4: mp 300 °C (dec); specific gravity 3.865. KMnO4: mp 240 °C (dec); specific gravity 2.703.

Solubility: NaIO4: sol H2SO4, HNO3, MeCO2H, hot water; slightly sol cold water. KMnO4: sol MeOH, acetone, hot water; slightly sol cold water.

Form Supplied in: NaIO4: white to colorless efflorescent solid. KMnO4: dark purple crystals. Both reagents are widely available and can be used as supplied.

Handling, Storage, and Precautions: gloves and safety goggles must be worn during handling; avoid inhalation of dust and contact with combustible matter.

Introduction.

The oxidative cleavage of carbon-carbon double bonds to give carboxylic acids using a catalytic amount of Potassium Permanganate in the presence of Sodium Periodate was first reported by Lemieux and von Rudloff.2 The reaction is usually carried out under buffered reaction conditions and, depending on the pH of the solution, either a 1,2-diol (at pH 9-10) or a 1,2-ketol (at pH 7-8) is initially formed. Oxidative cleavage of either of these intermediates by periodate yields the corresponding aldehyde, which is oxidized by permanganate to give the carboxylic acid. Permanganate is continually being regenerated from its reduced state (manganate) by the periodate. The reaction can be carried out in an aqueous medium or in mixed solvents (e.g. t-BuOH-H2O, pyridine-H2O) and proceeds optimally in the pH range between 7 and 10. Ketones and esters are not oxidized by NaIO4-KMnO4, whereas alcohols are oxidized slowly to carboxylic acids. Acyclic and cyclic alkenes are efficiently oxidized by NaIO4-KMnO4 to the carboxylic acids (eqs 1 and 2).1,3 a,b-Unsaturated ketones are oxidized smoothly to give keto acids with loss of one carbon atom (eq 3).4

Double bonds located in the side chain of a ring are more easily oxidized than those situated in the ring (eq 4).5 Also, double bonds in hydroxy alkenes can be selectively cleaved in the presence of a hydroxyl group.5b,c Thus (R)-(+)-citronellol is oxidized with NaIO4-KMnO4 to give (R)-(+)-6-hydroxy-4-methylhexanoic acid (eq 5).5c The oxidation of cyclic conjugated dienes6 with NaIO4-KMnO4 can lead to products arising from hydroxylation7 and epoxidation5a of the double bonds, as well as the expected oxidative cleavage of the double bonds (eq 6).7a


1. Suga, T.; von Rudloff, E. CJC 1969, 47, 3682.
2. (a) Lemieux, R. U.; von Rudloff, E. CJC 1955, 33, 1701. (b) von Rudloff, E. CJC 1965, 43, 1784. (c) von Rudloff, E. CJC 1956, 34, 1413.
3. von Rudloff, E. CJC 1965, 43, 2660.
4. Back, T. G. JOC 1981, 46, 1442.
5. (a) ApSimon, J. W.; Chau, A. S. Y.; Craig, W. G.; Krehm, H. CJC 1967, 45, 1439. (b) Bernassau, J.-M.; Fetizon, M. S 1975, 795. (c) Overberger, C. G.; Kaye, H. JACS 1967, 89, 5640.
6. von Rudloff, E. TL 1966, 993.
7. (a) Boncza-Tomaszewski, Z. CJC 1987, 65, 656. (b) Nace, H. R.; Rieger, A. L. JOC 1970, 35, 3846.

Andrew G. Wee & Baosheng Liu

University of Regina, Saskatchewan, Canada



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