An unusual decarboxylative benzannulation and biaryl formation during copper(I)-promoted halogen atom transfer radical cyclization of 2-allylaryl trichloroacetates

Abstract

CuCl/bpy-promoted halogen atom transfer radical cyclization of 2-allylaryl trichloroacetates in refluxing benzene gave benzannulated chloroarenes and benzannulated symmetrical biaryls along with reductive dehalogenation products. The unusual decarboxylative benzannulation and biaryl formation might be explained by a further intramolecular radical addition on the benzene ring of the eight-membered lactone intermediate, initially formed through 8- endo- trig halogen atom transfer radical cyclization, followed by decarboxylation, radical dimerization and dehydrochlorination reactions.