(a) Classical approach for the selective interconversion of a functional group. (b) Chemoselective interaction between a metal and a specific moiety allowing the creation of functionalized organometallic species, leading to a variety of electrophilic substitution reactions. (c) Remote functionalization through metal migration strategy enabling a transformation away from a functional group at a distant position (FG2); located further away from (FG1). Despite many inherent advantages, this approach does not allow the presence of the highly regarded quaternary carbon stereocentre. (d) Proposed sequence where a strategically stereodefined polysubstituted cyclopropane vault is used assuming that the ring-strain release may drive the chain-walking process towards the formation of acyclic products and allowing the introduction of an internal substitution on the carbon skeleton. (e) Illustration of this sequence was reported for the addition of stoichiometric amount of low-valent zirconocene derivatives to ω-alkenyl cyclopropanes generating a cascade of events composed by successive allylic C–H bond activations, selective C–C bond cleavage and finally reaction with two different electrophiles (E1X and E2X).