Chemoselective interaction of aromatic enynes with Bu3Sn radicals can be harnessed lot selective cascade transformations, yielding either Sn-substituted naphthalenes or Sn-indenes. Depending on the substitution at the alkene terminus, the initial regioselective 5-exo-trig cyclizations can be intercepted at the 5-exo stage via either hydrogen atom abstraction or C-S bond scission or allowed to proceed further to the formal 6-endo products via homoallylic ring expansion. Aromatization of the latter occurs via beta-C-C bond scission, which is facilitated by 2c,3e through-bond interactions, a new stereo electronic effect in radical chemistry. The combination of formal 6-endo-trig cyclization with stereoelectronically optimized fragmentation allows the use of alkenes as synthetic equivalents of alkynes and opens a convenient route to alpha-Sn-substituted naphthalenes, a unique launching platform for the preparation of extended polyaromatics.