Unexpected radical substitution of the dichlorine-containing iron(II) clathrochelate with 1,4-dioxane derivatives: Novel approach to functionalization of its macrobicyclic framework

► The iron(II) clathrochelate undergoes a radical addition-elimination reactions. ► The reaction radical 1,4-dioxane derivatives yield C-alkylated macrobicycles. ► Radical substitution as a novel approach to functionalization of the clathrochelates. ► The free-radical addition-elimination reaction results in substitution. ► The reaction is first example of alkylation of a coordinated ligand with cyclic ether.