A Novel Catalytic Hypervalent Iodine Oxidation of p-Alkoxyphenols to p-Quinones Using 4-Iodophenoxyacetic Acid and Oxone^®

Abstract

A novel catalytic hypervalent iodine oxidation of phenol derivatives using 4-iodophenoxyacetic acid and Oxone^® was developed. Reaction of p-alkoxyphenols with a catalytic amount of 4-iodophenoxyacetic acid in the presence of Oxone^® as a co-oxidant in acetonitrile-water (2:1) gave the corresponding p-quinones in ­excellent yields without purification.

Key words

p-alkoxyphenol - p-quinone - catalysis - hypervalent ­iodine oxidation - 4-iodophenoxyacetic acid - Oxone^®

References and Notes

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19

It is possible that iodine(III) species may be oxidized by Oxone^® to regenerate iodine(V) species before the reaction of iodine(III) with phenol.

20

Typical Reaction Procedure: To a solution of 2 (1 mmol) in MeCN-H₂O (2:1, 6 mL) was added 1a (0.2 mmol) followed by Oxone^® (1 mmol) at r.t. and the resulting mixture was stirred at the same temperature. After 2 was completely consumed indicated by TLC, the mixture was diluted with EtOAc and washed with H₂O. The organic layer was then washed with aq sat. NaHCO₃ solution and dried, concentrated to give pure 3. If necessary, the product was purified by column chromatography on silica gel to give pure quinone.
The alkaline solution was acidified by 10% HCl solution and extracted with EtOAc. The organic layer was washed with aq Na₂S₂O₃ solution and dried, then concentrated to give recovered 1a which was purified by recrystallization from Et₂O-hexane.
All new compounds gave satisfactory spectroscopic data.