Baeyer-Villiger reaction mechanism

Density functional theory has been used to model the Baeyer-Villiger reaction mechanism for Ti(IV)-H202 and Sn(IV)-H202 systems. These calculations have shown... 

Quantum, by contrast, converted an ethylene—carbon monoxide polymer into a polyester-containing terpolymer by treatment with acidic hydrogen peroxide, the Baeyer-Villiger reaction (eq. 11). Depending on the degree of conversion to polyester, the polymer is totally or partially degraded by a biological mechanism. 

The Dakin reaction proceeds by a mechanism analogous to that of the Baeyer-Villiger reaction. An aromatic aldehyde or ketone that is activated by a hydroxy group in the ortho or para position, e.g. salicylic aldehyde 12 (2-hydroxybenzaldehyde), reacts with hydroperoxides or alkaline hydrogen peroxide. Upon hydrolysis of the rearrangement product 13 a dihydroxybenzene, e.g. catechol 14, is obtained ... 

In another kind of reaction, an aromatic aldehyde ArCHO or ketone ArCOR is converted to a phenol ArOH on treatment with alkaline H202, but there must be an OH or NH2 group in the ortho or para position. This is called the Dakin reac-The mechanism may be similar to that of the Baeyer-Villiger reaction (18-19) ... 

Fig. 23. Mechanism of CHMO-catalyzed Baeyer-Villiger reaction (173,177,178,182).

Ab initio and semiempirical studies on the transition structure of the Baeyer-Villiger rearrangement of acetone with performic acid have been undertaken,510 and a theoretical investigation has been made511 of the mechanism of the Baeyer-Villiger reaction in non-polar solvents. The effect of fluoromethyl groups on the Baeyer-... 

A new transition state (7) of the addition step in the Baeyer-Villiger reaction was found by B3LYP calculations. The role of proton acceptor is played by the carbonyl-oxygen atom, and the free energy barrier is lower than that previously estimated. This finding changes the mechanism for the acid catalysis.231... 

Fig. 5. Mechanism of CHMO-catalysed Baeyer-Villiger reaction...

The accepted two-step mechanism (Scheme 1) for the Baeyer-Villiger reaction is based upon kinetic, isotopic substitution, stereochemical and substituent effect studies. In step 1 of the reaction, addition of... 

Problem 2.16. The Baeyer-Villiger reaction can also be carried out under basic conditions. Draw a reasonable mechanism. 

Enzymes that catalyze the Baeyer-Villiger reaction are a subset of the flavin monooxygenases. In the mechanism of oxidation catalyzed by such enzymes one atom of molecular oxygen is incorporated into the substrate, whereas the other is reduced to H20. Two cofactors are required for catalytic activity. The first is a reduced flavin (FAD or FMN) bound non-covalently in the active site. The riboflavin moiety of flavin monooxygenase holoproteins is shown in Fig. 16.5-15 the second is a reduced nicotinamide cofactor (NADPH or NADH), which is required to furnish the enzyme with electrons to reduce the flavin. 

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