A Demonstration of the Primary Stereoelectronic Effect in the Baeyer–Villiger Oxidation ofα-Fluorocyclohexanones

Since it was first reported in 1899 the Baeyer–Villiger reaction has become an important reaction in organic synthesis. The stereoelectronic components of this reaction have been difficult to observe because of the conformational mobility of the Criegee intermediate. Simply placing a fluorine substituent such that it interacts with the O−O bond of the peroxyester in this intermediate permits the observation of the primary stereoelectronic effect. Lactone 1 (see reaction scheme) is formed with 90 % selectivity, which demonstrates preferential migration of the equatorially substituted carbon and is in agreement with the primary stereoelectronic effect.