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Also known as: Baeyer-Villiger Reaction
Discovered by Adolf von Baeyer, Victor Villiger (1899)
Oxidation of a ketone to an ester (or lactone) using a peracid. An oxygen atom is inserted between the carbonyl and the adjacent carbon. The migratory aptitude determines which group migrates: 3° > 2° > 1° > methyl (also aryl migrates well).
The peracid attacks the ketone carbonyl to form a tetrahedral intermediate (Criegee intermediate).
The group with highest migratory aptitude migrates from carbon to oxygen as the carboxylate leaves. This is a concerted 1,2-shift.
Migratory aptitude: 3° > 2° > aryl ≈ vinyl > 1° > methyl
Cyclohexanone
mCPBA, CH₂Cl₂
ε-Caprolactone
3-Methylcyclobutanone
mCPBA
4-Methylbutyrolactone
Acetophenone
mCPBA (aryl migrates)
Phenyl acetate
Clean method to convert ketones to esters/lactones. Lactones from cyclic ketones are especially valuable in polymer and natural product chemistry.