Baeyer-Villiger Rearrangement

The acid-catalyzed reaction of ketones with hydroperoxide derivatives is known as the Baeyer-Villiger reaction. A general equation illustrating this oxidation reaction is shown below, and it may be noted that the rearrangement step is similar to that of a pinacol rearrangement. Esters or lactones are the chief products from ketone reactants. In this equation a discrete oxacation is drawn as an intermediate, but it is more likely that the rearrangement is concerted, as will be shown  on the below equation. Once the peracid has added to the carbonyl group, the rearrangement may be facilitated by an intramolecular hydrogen bond, in the manner depicted in brackets on the right.
The migratory aptitude of various substituent groups (e.g. ¹R & ²R) is generally: 3º-alkyl > 2º-alkyl ~ benzyl ~ phenyl > 1º-alkyl > methyl. Stereoelectronic factors favor an anti-periplanar orientation of the migrating group to the leaving moiety, and will control the rearrangement in some cases. An example will be displayed below .

Peracid exchange with peracetic acid leads to an intramolecular Baeyer-Villiger reaction by way of the bicyclic acylperoxide drawn in brackets. Here stereoelectronics favor migration of the less substituted α-carbon. The lactone product was identified by esterification and ester exchange with methanol to give methyl 2-carbomethoxy-7-hydroxyheptanoate.
Aldehydes are usually oxidized to carboxylic acids under the conditions used for the Baeyer-Villiger reaction.

Although hydrogen peroxide itself may be used in the Bayer-Villiger reaction, it may add at both ends to reactive carbonyl groups, producing cyclic dimeric, trimeric and higher addition compounds. Consequently, derivatives such as peracids (Z = RCO & ArCO above) are the preferred reagents for this reaction. Among the most common peracids used in this respect are: peracetic acid, perbenzoic acid & meta-chloroperbenzoic acid (MCPBA). Four examples of this oxidative rearrangement are given in the following diagram. In most of these examples the migrating group retains its configuration in the course of the rearrangement, as expected for a concerted process. In example #3 it is interesting that migration of the bridgehead 3º-alkyl group is preferred over a possible phenyl shift.

مواضيع ذات صلة

تفاعلات البروبان الحلقي

تفاعلات المركبات الحلقية

تحضير الهكسان الحلقي

تحضير البنتان الحلقي ومشتقاته

تحضير البيوتان الحلقي ومشتقاته

تحضير البروبان الحلقي ومشتقاته

Curtius Rearrangement

Hofmann Elimination

Hofmann rearrangement

Preparation of acyl chlorides

Synthesis of banana oil

Preparation of esters by Fischer esterification