Annamaria Deagostino

Achieving high molecular complexity can be not trivial, but the exploitation of domino reactions provides an atom‐ and step‐economical method to reach this target. Over the past decades, a lot of efforts have been put on the development of photocatalytic cascades employing both metal‐based and purely organic catalysts. Despite the effectiveness of these protocols, catalyst‐ and additive‐free light‐induced domino reactions are gaining momentum thank to their efficiency, operational simplicity and sustainability. The increasing number of papers published on this field in the last years is a proof of the appeal of these transformations. In this Review, we discuss domino and multicomponent reactions mediated by light with a focus on photocatalyst‐ and additive‐free processes. The most recent advances in the synthesis of complex nitrogen‐, oxygen‐, sulphur‐ and selenium‐heterocycles together with multicomponent cascades are analysed with an emphasis on both experimental and mechanistic studies.