Noncovalent Interaction Effects on the Acyl Radical Reaction of Bicyclo[2.2.2]octanone: Selective Formation of Rearrangement and Cyclization Products

The influence of allylic substituent orientation on the six-membered fused ring, as well as the steric hindrance at the alkene bridge (R(1) and R(2)) and bridgehead (R(3)), on the thiol-mediated acyl radical rearrangement/cyclization of bicyclo[2.2.2]octenone was investigated. A combined analysis using density functional theory calculations and interaction region indicator analysis suggests that reaction selectivity is driven by functional group noncovalent interactions.