Electrolyte‐Controlled Regiodivergent Continuous Flow Electroselenocyclisations
Sagar Arepally, Hanaa Gieman, Thomas Wirth
Abstract
Supporting electrolytes, beyond traditionally serving as ionic conductors in electrochemistry, can influence regioselectivity in electrochemical synthesis by acting as base. We present a single-pass continuous flow electrolysis method enabling selective activation of diselenides and oximes to access seleno-substituted isoquinoline and isoindole derivatives. Mechanistic studies showed a radical pathway via iminoxyl radicals to isoindole N-oxides and an ionic mechanism leading to isoquinoline N-oxides. This process leverages N-activated neutral isoquinolinium products for diverse downstream modifications. Our findings highlight the untapped potential of supporting electrolytes in regiodivergent electrochemical transformations and provide a sustainable and scalable platform for continuous flow approaches for synthesising selenium-containing heterocycles with biological relevance.