o-Sulfoperbenzoic Acid

[31652-18-3]  · C7H6O6S  · o-Sulfoperbenzoic Acid  · (MW 218.20)

(electrophilic reagent which delivers oxygen to alkenes1)

Solubility: sol water and aqueous acetone.

Form Supplied in: not available commercially.

Analysis of Reagent Purity: iodometry.2

Preparative Method: o-sulfobenzoic anhydride and Hydrogen Peroxide (30%; 1.3 equiv) react in acetone at -4 to 0 °C to furnish o-sulfoperbenzoic acid (1) in 65-75% yield (eq 1).

Handling, Storage, and Precautions: an aqueous acetone solution of the reagent is quite stable at rt and loss of active oxygen amounts to 1-2% per week. Since the reagent is a peroxide and potentially explosive, care is required in carrying out reactions with it. During workup, check for peroxides before solvent removal.

Anti Hydroxylation of Alkenes.

Reaction of a peroxycarboxylic acid (RCO3H) with an alkene (2) is syn stereospecific;3 the product is the epoxide (3) (eq 2). Under favorable conditions (pH of the reaction medium, temperature) the initially formed epoxide (3) undergoes trans ring opening due to reaction with RCO2H and furnishes the diol monoester (4) or (5) (or a mixture of 4 and 5); saponification of the diol monoester gives the diol (6). Peroxyformic acid (H2O2/Formic Acid) and Trifluoroperacetic Acid (TFPAA) are the peroxy acids which are normally used to effect the anti hydroxylation of alkenes (2 -> 6). Anti addition of hydroxyl groups to alkenes can also be effected by Prevost reaction, which involves treating an alkene with one equivalent of Iodine and two equivalents of the silver salt of a carboxylic acid; the monoester of the diol which is obtained is saponified.4

When an alkene is reacted with the peroxy acid (1) in aqueous acetone, the anti hydroxylation product is obtained directly. Cyclohexene (8) is converted to the trans-diol (9) (eq 3). Reagent (1) has been used for the synthesis of (±) g-rhodomycinone (11) via trans hydroxylation of the alkene (10) (eq 4).5

It is of interest to note that the electron-deficient alkene maleic acid has been hydroxylated to furnish tartaric acid in 80% yield. Phenylglyceric acid has been similarly prepared from cinnamic acid.

When one of the groups (R1,R2,R3,R4) attached to the epoxide ring in (3) is capable of stabilizing a positive charge on the neighboring carbon, the epoxide can undergo cis ring opening.6

Epoxidation of Alkenes.

Epoxides have been isolated by reacting alkenes with the peroxy acid (1) in the presence of a solid buffer such as Sodium Carbonate. Epoxides have been prepared from a-terpineol and cholesterol in 82% and 89% yields, respectively.

Baeyer-Villiger Reaction.

Baeyer-Villiger reaction of cyclohexanone takes place readily at 0 °C with (1) (4-6 h) to furnish hexanolide in 80% yield. Peracid (1) did not react with the ketone (12) and 4,4-dimethylcholestan-3-one. Reaction of (12) with Peracetic Acid-Boron Trifluoride Etherate furnished the lactone (13) in 36% yield.7

1. Bachhawat, J. M.; Mathur, N. K. TL 1971, 691.
2. Swern, D. In Organic Peroxides; Swern, D., Ed.; Wiley: New York, 1970; Vol. 1, Chapter 7.
3. Berti, G. Top. Stereochem. 1973, 7, 93.
4. (a) Haines, A. H. COS 1991, 7, 437. (b) Sonnet, P. E. T 1980, 36, 557.
5. (a) Kende, A. S.; Tsay, Y.-G. CC 1977, 140. (b) Braun, M. TL 1980, 21, 3871.
6. (a) Berti, G.; Bottari, F.; Ferrarini, P. L.; Macchia, B. JOC 1965, 30, 4091. (b) Rosen, W. E.; Dorfman, L.; Linfield, M. P. JOC 1964, 29, 1723.
7. Hase, T. A.; Huikko, R. ACS 1978, B32, 467.

A. Somasekar Rao & H. Rama Mohan

Indian Institute of Chemical Technology, Hyderabad, India

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