Mechanochemical Radical Transformations in Organic Synthesis

Abstract Organic synthesis has historically relied on solution‐phase, polar transformations to forge new bonds. However, this paradigm is evolving, propelled by the rapid evolution of radical chemistry. Additionally, organic synthesis is witnessing a simultaneous resurgence in mechanochemistry, the formation of new bonds in the solid‐state, further contributing to this shift in the status quo. The aforementioned advances in radical chemistry have predominantly occurred in the solution phase, while the majority of mechanochemical synthesis advances feature polar transformations. Herein, we discuss a rapidly advancing area of organic synthesis: mechanochemical radical reactions. Solid‐state radical reactions offer improved green chemistry metrics, better reaction outcomes, and access to intermediates and products that are difficult or impossible to reach in solution. This review explores these reactions in the context of small molecule synthesis, from early findings to the current state‐of‐the‐art, underscoring the pivotal role solid‐state radical reactions are likely to play in advancing sustainable chemical synthesis.