Peroxide Induced Baeyer-Villiger Oxidation

Stated by Lewis, however, this rate difference is not large with isolated carbon-carbon double bonds and Baeyer-Villiger oxidation can be competitive with epoxidation. 416 Lewis illustrated this by oxidation of 296 

Although most peroxyacids can be used in the Baeyer-Villiger reaction, trifluoroperoxyacetic acid is one of the more efficient reagents for this rearrangement. House gave an example in which 301 was selectively 

Another point learned from the transformation of 301 to 302 is that the cyclopropyl group is selectively transferred in preference to the methyl group. When unsymmetrical ketone 303 is treated with a peroxyacid, 

This migratory preference is clear in Chang s oxidation of 308 to 309 in 75% yield, taken from a synthesis of sarracenin. 24 Although there may be some correlation between migratory ability and the ability of that 

Simple dialkyl ketones are not easily oxidized by less reactive peroxyacids and usually require the more powerful trifluoroperoxyacetic acid. Since most groups migrate in preference to methyl, the Baeyer-Villiger reaction of methyl ketones serves as a stereo specific source of optically active alcohols by way of the acetate , 28 seen in the conversion of 310 to 311 in 85% yield. 29 example also illustrates that the stereochemical integrity of the migratory group is retained, which appears to be a general phenomenon.  

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