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20.5.1.3.2 Synthesis from Ketones via the Baeyer–Villiger Reaction

DOI: 10.1055/sos-SD-020-00673

Yan, L.; Lin, S.; Liu, P.Science of Synthesis, (200720750.

The BaeyerVilliger reaction, discovered in 1899,[‌99‌] is one of the most reliable and predictable of the classic transformations that are widely used in organic synthesis.[‌100‌] It is believed that the reaction proceeds through a Criegee intermediate 84, formed by nucleophilic attack of a peroxy acid at the carbonyl group of a ketone. One of the original carbonyl substituents then migrates preferentially to the partially positively charged oxygen atom generating an ester and an acid (Scheme 26). The rearrangement is concerted in nature and the substituent migrates with retention of its stereochemistry.[‌101‌] Substituents that can stabilize a positive charge are the most likely to migrate and the observed migratory preference is tertiary alkyl > cyclohexyl > secondary alkyl > benzyl > phenyl > primary alkyl > methyl. The BaeyerVilliger reaction is often employed to synthesize lactones from cyclic ketones, but for acyclic ketones it is mainly confined to the oxidation of methyl and phenyl ketones to afford the corresponding acetates and phenoxides.

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