Baeyer-Villiger reaction conformation

The study to predict the migrating group in the Baeyer-Villiger reaction has been scrutinized by several authors. As previously stated, conformational, steric, and... 

A detailed examination of OSO4 reactions with A -steroids has been reported." The A-ring conformation of the reactant or derived complex is important in determining the stereoselectivity of these reactions, and the major role of the proximate substituents is to anchor the appropriate conformation favouring a- or /3-attack. Studies on the stereochemistry of electrophilic attack on cholest-5-en-3-one continue." As with bromine chloride," appreciable /3-attack occurs and the 5/3,6j8-epoxide was isolated along with the previously reported 5a,6a-epoxide and the Baeyer-Villiger product, the A-homo-enol lactone (58). Base-catalysed... 

RB3LYP calculations indicate that the s-cis conformer of peroxy acids is more stable than the s-trans conformer. Calculations on the reaction of prop-2-enol with some peroxy acids showed that trans-transition states collapse to the epoxide via a 1,2-shift, whereas a 1,4-shift is operable for cis-transition states.195 Quantum mechanical calculations have been performed on the migration step of the Baeyer-Villiger rearrangements of some substituted acetophenones with m-chloroperbenzoic acid (m-CPBA). The energy barriers, charge distributions and frontier molecular orbitals, determined for the aryl migration step, have been used to explain the effects of substituents on the reactivity of the ketones.196... 

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