Molecular Iodine as Efficient Co-Catalyst for Facile Oxidation of Alcohols with Hypervalent(III) Iodine

Abstract

A simple and mild procedure for the facile oxidation of alcohols to ketones and acids using a catalytic quantity of molecular iodine in combination with (diacetoxyiodo)benzene in acetonitrile is described. Direct oxidative methyl esterification of alcohols is also reported in methanol as solvent. Oxidation of alcohols is induced by iodonium ion generated in situ by the chemical oxidation of molecular iodine with (diacetoxyiodo)benzene.

Key words

alcohols - hypervalent elements - iodine - oxidation

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12

Experimental Procedure. To a magnetically stirred solution of alcohol (1 mmol), iodine (0.1 mmol) in MeCN (15 mL) was added(diacetoxyiodo)benzene (1.1 mmol). The resulting red brown solution was stirred in an open vessel for the time as mentioned in Table [1] . The progress of the reaction was monitored by TLC. After completion of reaction, the mixture was washed with Na₂S₂O₃ and extracted with CH₂Cl₂ (2 × 10 mL). The organic extract was dried over anhyd Na₂SO₄. Removal of the solvent and subsequent silica gel chromatography (petroleum ether and EtOAc) afforded the corresponding carbonyl compounds in the pure form.

13

The experimental procedure for the oxidative esterification is similar to that mentioned above except the use of alcohol as solvent in place of acetonitrile.