Electrolyte-Controlled Regiodivergent Continuous Flow Electroselenocyclisations

Supporting electrolytes, beyond traditionally serving as ionic conductors in electrochemistry, can influence regioselectivity in electrochemical synthesis by acting as base. In the research we studied 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 <i>via</i> iminoxyl radicals to isoindole <i>N</i>-oxides and an ionic mechanism leading to isoquinoline <i>N</i>-oxides. This process leverages <i>N</i>-activated neutral isoquinolinium products for diverse downstream modifications. In this project, All compounds (Scheme 2; compounds 3 to 34), (Scheme 4; compounds 36 to 48), (Scheme 7; compounds 50 to 55) were characterised by NMR, (HRMS only for unknown compounds), and (Crystallography data for compounds 28 and 35), reaction kinetics was studied for one compound S1 by cyclic voltammetry. All NMR data were processed by MestReNova software, and HRMS data were provided in .pdf file.