Substrate‐Dependent Electrochemical Dimethoxylation of Olefins

Abstract A general and direct electrochemical dimethoxylation of olefins is reported, which enables a divergent route to different products depending on the structure of olefins. The present protocol features mild conditions and broad substrate scope (49 examples) obviating the usage of transtion‐metals and external oxidants. More importantly, to rationalize the divergent route of the transformation, an ionic‐like pathway involving carbocation intermediate is proposed and the diverse products is attributed to the different stability of carbocations. magnified image