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.