Reaction of t-butoxy radicals with cyclic alkenes studied by the nitroxide radical-trapping technique

The pattern of reactions occurring between t- butoxy radicals and a number of cyclic alkenes has been investigated by the nitroxide radical-trapping technique. The major reaction pathway is allylic abstraction unless this position is at a bridgehead as in norbornene where the major pathway is radical addition. The technique is sufficiently sensitive to identify minor reaction pathways of non-allylic substitution and radical addition when in the presence of extensive allylic substitution. Some stereoselective effects are also detected.