PM3 SEMIEMPIRICAL STUDY OF STEREOELECTRONIC EFFECTS IN THE BAEYER-VILLIGER REACTION

The Baeyer-Villiger reaction of polymethoxybenzaldehydes with peroxysu ccinic acid (PSA) is studied theoretically. The semi-empirical SCF-MO/ PM3 method has been used to study the reaction and to calculate the en ergy profiles. In addition, heat of formation computations and bond or der analyses of the transition species along the reaction coordinates have been performed and are interpreted qualitatively in terms of elec tron flow through the system during aryl migration. Our results suppor t the hypothesis that the second step is a concerted reaction. Our dat a support a definite effect of the substituent on the aryl migration. The theoretical predictions are in good agreement with experimental re sults. (C) 1998 Elsevier Science B.V. All rights reserved.