Formal Aza-Wacker Cyclization by Tandem Electrochemical Oxidation and Copper Catalysis.

In oxidative electrochemical organic synthesis, radical intermediates are often oxidized to cations on the way to final product formation. Herein, we describe an approach to transform electrochemically generated organic radical intermediates into neutral products by reaction with a metal catalyst. This approach combines electrochemical oxidation with Cu catalysis to effect formal aza-Wacker cyclization of internal alkenes. The Cu catalyst is essential for transforming secondary and primary alkyl radical intermediates into alkenes. A wide range of 5-membered N-heterocycles including oxazolidinone, imidazolidinone, thiazolidinone, pyrrolidinone, and isoindolinone can be prepared under mild conditions.