Baeyer-Villiger oxidation

The Baeyer-Villiger oxidation (also called Baeyer-Villiger rearrangement) is an organic reaction that forms an ester from a ketone or a lactone from a cyclic ketone.Peroxyacids or peroxides are used as the oxidant. The reaction is named after Adolf Baeyer and Victor Villiger who first reported the reaction in 1899.

In the first step of the reaction mechanism, the peroxyacid protonates the oxygen of the carbonyl group. This makes the carbonyl group more susceptible to attack by the peroxyacid. In the next step of the reaction mechanism, the peroxyacid attacks the carbon of the carbonyl group forming what is known as the Criegee intermediate. Through a concerted mechanism, one of the substituents on the ketone migrates to the oxygen of the peroxide group while a carboxylic acid leaves. This migration step is thought to be the rate determining step. Finally, deprotonation of the oxygen of the carbonyl group produces the ester.

The products of the Baeyer-Villiger oxidation are believed to be controlled through both primary and secondary stereoelectronic effects. The primary stereoelectronic effect in the Baeyer-Villiger oxidation refers to the necessity of the oxygen-oxygen bond in the peroxide group to be antiperiplanar to the group that migrates. This orientation facilitates optimum overlap of the ...
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