One‐pot multistep electrochemical strategy for the modular synthesis of epoxides, glycols, and aldehydes from alkenes

Abstract Oxidative functionalization of alkenes is a versatile strategy for the preparation of many oxygen‐containing scaffolds, such as epoxides, diols, or carbonyl‐containing compounds. In addition to conventional chemical methods, which rely on the utilization of stoichiometric amounts of oxidizing reagents, some electrochemical procedures have been developed to achieve these transformations. Typical electrochemical procedures employ tailored and often complex redox mediators to achieve the target transformation. Herein we present a modular approach for the synthesis of epoxides, diols, and aldehydes from a single set of reaction components. With sodium bromide as an inexpensive electrocatalyst and water as the oxygen donor, the outcome of the reaction (epoxide, 1,2‐diol, or aldehyde) can be selected by simply tuning the electrolysis conditions. This convenient platform has been accomplished by developing a selective one‐pot three‐step bromide‐electrocatalyzed epoxidation/ring opening/carbon‐carbon cleavage sequence. Its modularity permits the selection of the desired product, as the sequential reaction can be ended when the target compound has been formed. The method has been applied to a diversely functionalized terminal and non‐terminal olefins.