Supramolecular Modulation for Selective Mechanochemical Iron‐Catalyzed Olefin Oxidation

The development of a mechanochemical Fe‐catalyzed Wacker oxidation of olefins with a sustainable and benign procedure holds significant promise for industrial applications. However, navigating the intricate interactions inherent in ball‐milling conditions to fine‐tune reaction selectivity remains a formidable challenge. Herein, leveraging the dispersive and/or trapping properties of cyclodextrins, an innovative mechanochemical approach is developed through the integration of cyclodextrins into a Fe‐catalyzed system, enabling a streamlined Wacker oxidation process from simple and/or commercially available alkenes. Our efforts have yielded optimized mechanochemical conditions demonstrating exceptional reactivity and selectivity in generating a diverse array of ketone products, markedly enhancing catalytic efficiency compared to conventional batch methods. Mechanistic investigations have revealed a predominantly Markovnikov‐selective catalytic cycle, effectively minimizing undesired alcohol formation, hydrogenation, and the other competing pathways, boosting both reaction yield and selectivity. A mechanochemical strategy used for the iron‐catalyzed Wacker oxidation of aromatic and aliphatic olefins is developed. This combined catalytic system through the integration of Fe(III)/porphyrin and cyclodextrins under the optimal ball‐milling conditions enables a collaborative oxidation process and provides a wide range of Markovnikov‐selective ketone products with markedly enhanced catalytic efficiency compared to conventional batch procedures.