A method for the direct stereodivergent 1,3-difunctionalization of unactivated alkenes is reported, based on a concept called 'charge relocation'. This approach enables the synthesis of 1,3-difunctionalized products with either syn- or anti-configuration without the need for directing groups or stabilizing features. The method is demonstrated in the synthesis of the pulmonary toxin 4-ipomeanol and its derivatives. The reaction involves electrophilic addition to alkenes, leading to the formation of 1,3-difunctionalized products through a series of hydride shifts. The success of the reaction relies on the use of a non-nucleophilic counter anion, hexafluoroantimonate, and the nature of the halophilic reagent. The reaction shows high selectivity for syn-products and can be modified to produce anti-products by using different nucleophiles. The method is shown to be applicable to a wide range of substrates, including linear alkenes and substituted cyclohexenes. The reaction mechanism is proposed to involve a rapid isomerization event, converting the β-keto cation into a cyclic oxocarbenium ion, which then undergoes hydrolytic or nucleophilic attack to form the final products. The method provides a general and efficient approach for the 1,3-difunctionalization of alkenes, with potential applications in the synthesis of biologically active molecules. The reaction is shown to be highly selective and efficient, with high yields and good stereocontrol. The method is compared to other approaches for alkene 1,3-difunctionalization, demonstrating its advantages in terms of simplicity and selectivity. The study highlights the importance of understanding the factors governing the selectivity and predictability of such transformations, and the direct and general 1,3-difunctionalization of unactivated and unfunctionalized alkenes remains an unmet challenge. The method offers a promising solution to this challenge, providing a new and efficient approach for the functionalization of alkenes.A method for the direct stereodivergent 1,3-difunctionalization of unactivated alkenes is reported, based on a concept called 'charge relocation'. This approach enables the synthesis of 1,3-difunctionalized products with either syn- or anti-configuration without the need for directing groups or stabilizing features. The method is demonstrated in the synthesis of the pulmonary toxin 4-ipomeanol and its derivatives. The reaction involves electrophilic addition to alkenes, leading to the formation of 1,3-difunctionalized products through a series of hydride shifts. The success of the reaction relies on the use of a non-nucleophilic counter anion, hexafluoroantimonate, and the nature of the halophilic reagent. The reaction shows high selectivity for syn-products and can be modified to produce anti-products by using different nucleophiles. The method is shown to be applicable to a wide range of substrates, including linear alkenes and substituted cyclohexenes. The reaction mechanism is proposed to involve a rapid isomerization event, converting the β-keto cation into a cyclic oxocarbenium ion, which then undergoes hydrolytic or nucleophilic attack to form the final products. The method provides a general and efficient approach for the 1,3-difunctionalization of alkenes, with potential applications in the synthesis of biologically active molecules. The reaction is shown to be highly selective and efficient, with high yields and good stereocontrol. The method is compared to other approaches for alkene 1,3-difunctionalization, demonstrating its advantages in terms of simplicity and selectivity. The study highlights the importance of understanding the factors governing the selectivity and predictability of such transformations, and the direct and general 1,3-difunctionalization of unactivated and unfunctionalized alkenes remains an unmet challenge. The method offers a promising solution to this challenge, providing a new and efficient approach for the functionalization of alkenes.