Abstract
Oxidative free-radical cyclizations of γ,γ-(bis)allylic acetoacetates demonstrate that 1,1-disubstituted double bonds are much more reactive than mono- or chloroalkyl-substituted double bonds. The product isolated suggests that bicyclo[3.2.1]octanes 25, 33 and 36 are formed from boat cyclohexyl radical 42 and tandem cyclization products 30, 37 and 38 are obtained from boat cyclohexyl radical 41.
Oxidative free-radical cyclization of λ-λ-bis(allylic)acetoacetates give monocyclic radicals that cyclize through a transition state with a boat cyclohexane to the allyl group attached to the α-carbon.