Kinetic Analysis of the Rearrangement of a Conformationally Constrained α-Cyclopropylbenzyl Radical

Article abstract of DOI:10.1021/jo00092a003

Modulation of the cyclopropylmethyl (CPM)/homoallyl radical equilibrium by phenyl substitution at the radical center is exploited in determining the kinetic versus thermodynamic preference for bond scission in a bicyclic CPM radical.Exocyclic ring opening is determined to be 28.7 times faster than the respective endocyclic process.This method will be of general use for determining the regioselectivity of radical rearrangements.