Programmable divergent electrochemical ring-opening multifunctionalization of strained rings

Abstract The ring-opening functionalization of strain rings is a highly valued transformation. However, existing strategies predominantly rely on ring-opening difunctionalization, as initial derivatization typically diminishes the reactivity of surrounding C–H bonds. Consequently, the control of site, regio, and oxidation state-selectivity among multiple inert C-H/C-C bonds remains a largely unmet challenge. Here we report a multi-site programmable, divergent ring-opening functionalization of strained rings via electrochemical oxidation of continuous C–C bond and multiple C(sp³)–H bonds. The key to this strategy is the generation of olefins through a controlled “Olefin Slow-Release Pool” (OSRP), which ensures sufficient selectivity oxidation and mitigates polymerization. Specifically, precise trioxygenation, tetraoxygenation, and trihalogenoxygenation have been realized, accompanied by controllable remote alkenylation via direct current (DC) electrolysis, rapid alternating polarity (rAP) electrolysis, and electrophotocatalysis. This method enables available strained rings to be readily converted into diverse multi-oxygenated scaffolds, including oxazolines, polyols, and polyhalogenated alcohols.