Electrochemical selective divergent C-H chalcogenocyanation of N-heterocyclic scaffolds.

An electrochemical direct selective C-H chalcogenocyanation approach for indolizine derivatives under mild conditions has been described. Cyclic enone-fused, chromone-fused and 2-substituted indolizines possessing EDGs (electron donating groups) and EWGs (electron withdrawing groups) were successfully reacted with NH4SCN and KSeCN under electrochemical conditions to provide a wide array of mono and bis-chalcogenocyanate-indolizines in 75-94% yields. In addition, 1-substituted imidazo[1,5-a]quinolines were also successfully chalcogenocyanated under the optimized reaction conditions providing a platform for the synthesis of pharmaceutically privileged molecules. By switching the reaction conditions, the developed protocol offers selective synthesis of C-3 thiocyanate and 1,3 bis-thiocyanate indolizines in good to excellent yields under catalyst-free conditions. On the basis of control experiments and cyclic voltammetry data, a plausible reaction pathway is also presented.

Electrochemical direct C-H mono and bis-chalcogenation of indolizine frameworks under oxidant-free conditions.

Herein, we disclosed a sustainable electrochemical approach for site-selective C-H mono and bis-chalcogenation (sulfenylation or selenylation) of indolizine frameworks. Diversely functionalized disulfides and diselenides possessing EDGs and EWGs were successfully reacted with a variety of indolizines to directly access sulfenylated/selenylated indolizines in 40-96% yields. A mechanistic radical pathway was also validated with control experiments and cyclic voltammogram data.

Electrochemical site-selective direct C-H sulfenylation and selenylation of a chromone-fused-indolizine (CFI) skeleton.

Herein, for the first time, we report the transition metal-free electrochemical site-selective direct C-H sulfenylation/selenylation of chromone-fused indolizine compounds (CFIs) to afford the corresponding CFIs thioethers and selenoethers   in 58-96% yields. The developed protocol offers a transition metal-free, ligand-free, catalyst-free methodology and is suitable for a variety of chalcogenide molecules (S and Se) along with various electron-rich and electron-poor chromone-fused indolizine compounds. Cyclic voltammograms and control experiments also validated the plausible reaction pathway.

Electrochemical, Regioselective, and Stereoselective Synthesis of Allylic Thioethers and Selenoethers under Transition-Metal-Free and Oxidant-Free Conditions.

We disclose a mild, scalable, electricity-promoted cross coupling protocol between allylic iodides and disulfides/diselenides for the formation of C-S/Se bonds in the absence of transition metals, bases, and oxidants. The stereochemically different densely functionalized allylic iodides gave regio- and stereoselective diverse thioethers in good yields. This strategy demonstrates a sustainable promising approach for the synthesis of allylic thioethers in 38-80% yields. This protocol also provides a synthetic platform for the synthesis of allylic selenoethers. A single-electron transfer radical pathway was also validated with radical scavenger experiments and cyclic voltammetry data.