Electrochemical N‐hydroxyphthalimide Catalyzed Addition of α‐Alkoxy Radicals to Oxime Ethers

In this work, we describe how N‐hydroxyphthalimide (NHPI), also under catalytic amounts, promotes hydrogen atom transfer (HAT) from alcohols under electrochemical conditions through the generation of phthalimide‐N‐oxyl (PINO). In contrast with the well‐known electrochemical oxidation to their corresponding aldehydes or ketones, α‐alkoxy radicals were successfully coupled with oximes promoting a carbon–carbon bond‐forming event. This method allows the α‐functionalization of primary and secondary alcohols under simple, straightforward, and mild electrochemical reaction conditions in a single operation even in the presence of catalytic amounts of the HAT catalyst.