Photo‐Autocatalysis: Insights From Light‐Driven Self‐Catalyzed Organic Transformations

Autocatalysis refers to a synthetic transformation where products boost their own formation, while photochemistry enables innovative reaction pathways that can go beyond those by thermal activation. For the modern synthetic methodology development, the efficiency of autocatalysis and the versatility of photocatalysis have both played pivotal roles in this field and have recently merged into an emerging concept: photo-autocatalysis, which represents light-driven reactions featuring self-accelerated kinetics. From a mechanisticperspective, we systematically categorize these reactions based on the identity of key species responsible for photo-autocatalysis. These reactions can proceed with a single photo-autocatalyst that triggers photochemical transformation in an autocatalytic manner, or with a pair of photocatalyst and autocatalyst. For the former, it can be further categorized by whether the photo-autocatalyst is the product itself or an in situ generated complex, each offering distinct advantages. In this perspective, we present a classification framework and in-depth mechanistic discussion and offer insights into the design principles, key influencing factors, and future prospects of photo-autocatalysis, therefore contributing to the comprehension of this emerging topic.