Shedding Light on Synthetic Autocatalysis: From Conventional Closed‐Shell Chemistries to Overlooked Open‐Shell Occurrences

Autocatalysis is a kinetic phenomenon where a reaction product catalyzes its own formation, often leading to sigmoidal reaction profiles and exponential rate acceleration. This process plays a fundamental role in biological systems, for example, in chemistry of the origins of life. Although synthetic reactions are not as widely reported as the biological studies, autocatalysis offers a unique mechanism and high efficiency to organic synthesis. This review highlights diverse synthetic examples in various autocatalytic mechanistic paradigms, including well‐studied examples such as the Soai reaction. We also explore emerging examples in radical‐ and photochemistry‐based systems, emphasizing recent advances in auto‐photocatalysis. By exploring examples from different fields, this review aims to highlight the variety and potential of autocatalytic reactions for synthesis. We aim to encourage further research into autocatalysis as a powerful strategy for improving reaction efficiency, revealing new reaction pathways, and inspiring innovative catalytic methodologies.