α,β-Unsaturated (Bis)Enones as Valuable Precursors in Innovative Methodologies for the Preparation of Cyclic Molecules by Intramolecular Single-Electron Transfer

The synthesis of monocyclic and bicyclic compounds plays a fundamental role in organic chemistry, and the need for novel synthetic methodologies is still under investigation. In particular, α,β-unsaturated (bis)enones have emerged as valuable precursors for the formation of cyclic (both mono and bicyclic) structures through single-electron transfer (SET) processes. Single-electron transfer (SET) is a redox process where one electron moves from a donor species to an acceptor, generating radical ions or neutral radicals that drive unique reaction pathways. Thanks to the advent of radical chemistry, it was possible to discover an entirely new reactivity of α,β-unsaturated (bis)enones, which, after a SET event, undergo the formation of cyclic molecules, both in intra and inter-molecular reactions, under several possible pathways, including formal [2+2] cycloaddition reaction (22CA) and 5-exo-trig cyclization, for ring closure. Today, the generation of radical species can be broadly classified into three main approaches: <i>photochemical</i> and <i>photocatalytic</i>, <i>metal-driven</i> and <i>electrochemical</i> processes. In this review, we summarize the progress achieved to date in the synthesis of cyclic molecules from α,β-unsaturated (bis)enones via single-electron transfer events under these three main classes of processes. Whenever possible, the reaction pathway and fate of the radical species generated through SET is discussed.