This article introduces a novel method for the stereodivergent 1,3-difunctionalization of alkenes, a process that typically requires designer substrates with directing groups or stabilizing features. The method, termed 'charge relocation,' enables the direct and general 1,3-difunctionalization of unactivated alkenes without the need for such modifications. The approach is demonstrated through the synthesis of the pulmonary toxin 4-ipomeanol and its derivatives. The reaction involves the treatment of alkenes with an acylum cation carrying a non-nucleophilic hexafluorantimonate anion, leading to the selective formation of syn- or anti-configuration products. The mechanism involves the rapid isomerization of the β-keto cation into a rearranged, cyclic oxocarbocation ion, which is then intercepted by nucleophiles to form the desired products. This method offers a versatile and stereoselective alternative to traditional 1,3-difunctionalization techniques, providing a straightforward route to complex molecules.This article introduces a novel method for the stereodivergent 1,3-difunctionalization of alkenes, a process that typically requires designer substrates with directing groups or stabilizing features. The method, termed 'charge relocation,' enables the direct and general 1,3-difunctionalization of unactivated alkenes without the need for such modifications. The approach is demonstrated through the synthesis of the pulmonary toxin 4-ipomeanol and its derivatives. The reaction involves the treatment of alkenes with an acylum cation carrying a non-nucleophilic hexafluorantimonate anion, leading to the selective formation of syn- or anti-configuration products. The mechanism involves the rapid isomerization of the β-keto cation into a rearranged, cyclic oxocarbocation ion, which is then intercepted by nucleophiles to form the desired products. This method offers a versatile and stereoselective alternative to traditional 1,3-difunctionalization techniques, providing a straightforward route to complex molecules.