Baeyer-Villager

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 ... 

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... 

Cyclization of the ylide derived from phosphonium salt (141) gives the 3,4-dihydro-2iT-benzoxocin (142) in low yield as a mixture with the pyran (143) (74JOC3038). Hydrogenation of (142) leads to the benzoxocin (136). The bromobenzoxocin (145) is formed on Baeyer-Villager oxidation of the seven-membered ring ketone (144) (58JCS2797). 

It was first prepd hy Legler (Ref 2) as one of the products of incomplete combustion of ether. He erroneously called the product Hexaoxymethylenperoxyd . Nef (Ref 3) prepd di(methylol)-peroxide by treating formaldehyde with aq hydrogen peroxide and called the product "Diformal-peroxydhydhydrat . Baeyer Villager (Ref 4) confirmed the results of Nef and also showed that by treating Nef s product with ammonia, an extremely violent explosive was produced. They named it Hexamethylen-triperoxyd-diamin. Its structure was detd as ... 

The decomposition mode is somewhat similar to that previously shown in equation (28) for the Baeyer-Villager oxidation of ketones by Mo-peroxo complexes (c) a /3-hydride abstraction by rhodium followed by a nucleophilic attack at the coordinated alkene by the hydride (equation... 

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...

Example 4.33. Baeyer-Villager oxidation of cyclopentanone to 8-valerolactone. 

Baeyer - Villager oxidation of the heavily functionalized cyclopentanone PROBLEM 4.16 yields a mixture of products. Use a step-by-step mechanism to decide whether this result is unexpected. 

Successful Baeyer-Villager oxidations have been reported for 5-chloroacetyl and 6-chloroacetyl derivatives of methyl indole-3-carboxylate and the corresponding 1-methyl derivatives <87H(26)1471>. The yields were much better for the chloroacetyl compounds than for the acetyl derivatives (Equation... 

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... 

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... 

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