Baeyer-Villager reaction

The mechanism of this degradation has received considerable attention, and for some species the reaction is equivalent to a nonenzymatic Baeyer-Villager reaction, producing first the 17j8-acetate. This functionality can then be hydrolyzed and oxidized to the ketone and may undergo a second Baeyer-Villager reaction to produce a lactone ... 

A complex of hexafluoroacetone and H20a exhibits properties similar to those of trifluoroperacetic acid. Using this reagent, the Baeyer-Villager reaction was executed in yields of 40-73%. The Lindlar catalyst has been used to obtain the dialdehyde from several ozonides resulting from treatment of the corresponding norbornadienes with ozone. The protected a-diketone 2 can be cleaved via the dithiane 2 way which... 

Baeyer-Villager oxidation, 10, 151, 433 Bamford-Stevens reaction, 402 Barton reaction, 253 Beckmann rearrangement, 140 Benzilic acid rearrangement, 418, 435 3 -Benzoyloxy-7-methylenecholest-5-ene, 60 Benzylmagnesium chloride, 64 3-Benzyloxycholesta-3,5-diene, 342... 

Figure 4 Chemistry of the oxygenation of cyclohexanone by cyclohexanone monooxygenase—a Baeyer-Villager rearrangement. In the first stage, NADPH binds and reduces the FAD to form E Flpgj-NADP. The NADP remains bound to the enzyme during the ensuing reactions. Oxygen reacts to form a C4a-peroxy-FAD (E FI HOO ). In the next phases, cyclohexanone binds and reacts with the peroxyflavin to form a Criegee adduct, which breaks down to form the lactone product and the C4a-hydroxy-FAD (E FI HOH-P). When the NADP dissociates, the hydroxy-flavin loses H2O to reform the oxidized FAD...

The reaction has the same characteristics as a Baeyer-Villager in that the more substituted carbon preferentially migrates (see Eq. 4) and migration occurs with retention of configuration at the migrating carbon (see Eq. 5). Thus, the overaU synthetic event is to convert any carbonyl partner... 

The following reaction is an example of the Baeyer-Villager oxidation (see Chapter 11 mCPBA = /-chloroperbenzoic acid). A heavy atom isotope effect for the carbon labeled was found tobeltia/ rM = 1.048. What does this tell you about the mechanism (do not write the entire mechanism) ... 

---