Vicinal Difunctionalization of Unactivated Alkenes Through Radical Addition/Remote (Hetero)Aryl Migration Cascade

Abstract Alkenes are ubiquitous in natural and synthetic molecules and constitute versatile building blocks. Remarkably, their radical 1,2‐difunctionalization offers a valuable synthetic tool for rapidly accessing multifunctional compounds through a step and atom‐ economy process. More particularly, the addition of (hetero)aromatic groups onto alkenes is of particular appeal given the numerous applications of aromatic compounds in various fields. However, such process becomes difficult when attempted on simple non‐conjugated aliphatic alkenes (unactivated alkenes). In this context, the (hetero)arylation of unactivated alkenes through the radical functionalization followed by remote (hetero)aryl migration has recently emerged as a powerful opportunity to address the lack of reactivity of such π systems. The advances in radical chemistry have led to a flood of synthetic methods to trigger the addition of a carbon‐ or heteroatom‐centered radical/(hetero)aryl migration sequence. Interestingly, the migration of the aromatic ring can take place from various atoms. This feature has spurred the design of several substrates allowing such a process to occur. This review intends to provide an overview of the contributions according to the type of substrates that have been employed. The reaction scope, limitations and mechanistic aspect will be discussed with the aim of stimulating efforts in this research area.