Charge distribution and charge separation in radical rearrangement reactions

Abstract

Publisher Summary This chapter concentrates on the theoretical studies carried out for systems with acyloxy or phosphatoxy substituents, together with the relevant experimental results. Particular attention has been paid to quantitative aspects of the charge distribution in ground and transition states. Concerted rearrangement or stepwise heterolytic dissociation/recombination depends on the character of the migrating group, the substitution pattern, and the solvent polarity. It may also depend on the presence of a catalyst present in the reaction medium. There is not a single general mechanism for the 1, 2-migration reaction in β-substituted alkyl radicals that may easily be illustrated with sdq- and dsdq-plots of four selected systems. This selection includes transition states from chlorine, acyloxy, and phosphatoxy migration reactions as well as three-and five-membered ring transition states in order to illustrate, how broadly the charge density/spin density space is covered in 1, 2- migration reactions.