Stereodivergent 1,3-difunctionalization of alkenes by charge relocation

Alkenes are indispensable feedstocks in chemistry. Functionalization at both carbons of the alkene—difunctionalization—is part of chemistry curricula worldwide1. Although difunctionalization at distal positions has been reported, it typically relies on designer substrates featuring directing groups and/or stabilizing features, all of which determine the ultimate site of bond formation. 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 -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 ipomeanol and its derivatives.