Alkene difunctionalization represents one of the most efficient methods for the construction of highly functionalized products from simple and readily available starting materials. These transformations are usually promoted by a highly reactive electrophilic reagent (e.g., peracid, metal oxide, and hypervalent iodine), which engages the unactivated π electrons of the alkene to form two new vicinal chemical bonds in either a concerted or a stepwise fashion. The requirement for these highly reactive electrophiles can often lead to functional group compatibility issues, which may limit their broad use in late-stage synthesis. In addition, many of these reagents generate substantial amounts of byproducts upon reaction.

Herein, we describe the development of alkene difunctionalization reactions via electrochemical generation of radical intermediates. Electrochemistry allows for the generation of highly reactive intermediates in situ from simple and readily available feedstocks and with high atom economy. The heteroatom-based radical can be produced directly from the corresponding anion via anodic oxidation, and will add across a C=C bond in the alkene substrate to yield a carbon based radical. Due to the high reactivity and promiscuity of this carbon radical species, a variety of undesired pathways, including polymerization, dimerization, elimination, and over-oxidation, could follow. In order to realize difunctionalization with high selectivity in addition to high stereochemical control, we introduce a metal catalyst that could associate with the second heteroatom-based radical and deliver it to the carbon radical via a catalyst-controlled mechanism. The therefore reduced catalyst could then also be oxidized on the anode to complete the catalytic cycle. Judicious choice of catalyst and careful control of the applied electrochemical bias allow for the regulation of the reactivity and selectivity of the alkene difunctionalization process.