Alkenes are indispensable feedstocks in chemistry. Functionalization at both carbons of the alkene—1, 2-difunctionalization—is part of chemistry curricula worldwide 1. Although difunctionalization at distal positions has been reported 2, 3, 4, it typically relies on designer substrates featuring directing groups and/or stabilizing features, all of which determine the ultimate site of bond formation 5, 6, 7. Here we introduce a method for the direct 1, 3-difunctionalization of alkenes, based on a concept termed ‘charge relocation’, which enables stereodivergent access to 1, 3-difunctionalized products of either syn-or anti-configuration from unactivated alkenes, without the need for directing groups or stabilizing features. The usefulness of the approach is demonstrated in the synthesis of the pulmonary toxin 4-ipomeanol and its derivatives.