An electrochemical method for the green and practical synthesis of a broad range of substituted isoxazoline cores is presented. Both aryl and more challenging alkyl aldoximes are converted to the desired isoxazoline in an electrochemically enabled regio‐ and diastereoselective reaction with electron‐deficient alkenes. Additionally, in‐situ reaction monitoring methods compatible with electrochemistry equipment have been developed in order to probe the reaction pathway. Supporting analyses from kinetic (time‐course) modelling and density functional theory support a stepwise, radical‐mediated mechanism, and discounts hypothesised involvement of closed shell [3+2] cycloaddition pathways.

An electrochemical method for the green and practical synthesis of a broad range of substituted isoxazoline cores is presented. Both aryl and more challenging alkyl aldoximes are converted to the desired isoxazoline <i>via</i> an electrochemically enabled regio- and diastereoselective reaction with electron-deficient alkenes. Additionally, <i>in-situ</i> reaction monitoring methods compatible with electrochemistry equipment have also been developed in order to probe the reaction pathway. Supporting analyses from kinetic (time-course) modeling and density functional theory support a stepwise, radical-mediated mechanism, and discounts hypothesized involvement of closed shell [3+2] cycloaddition pathways.

An electrochemical method for the green and practical synthesis of a broad range of substituted isoxazoline cores is presented. Both aryl and more challenging alkyl aldoximes are converted to the desired isoxazoline <i>via</i> an electrochemically enabled regio- and diastereoselective reaction with electron-deficient alkenes. Additionally, <i>in-situ</i> reaction monitoring methods compatible with electrochemistry equipment have also been developed in order to probe the reaction pathway. Supporting analyses from kinetic (time-course) modeling and density functional theory support a stepwise, radical-mediated mechanism, and discounts hypothesized involvement of closed shell [3+2] cycloaddition pathways.