In this paper we report a simple synthetic route to obtain functionalized allyltin derivatives from 1-ethynylcyclohexene (1), through a "one pot" procedure. Radical addition of trineophyltin hydride to 1 leads quantitatively to (Z,E)-1-(2-trineophylstannylvinyl)-cyclohexene (3), a conjugated dienylstannane that, through a [4+2] cycloaddition reaction (Diels -Alder) with activated dienophiles, allows to obtain substituted bicyclic unsaturated products with specific stereochemistry and a trialkylstannyl group in allylic position.