A Self‐Enhanced Tandem Catalytic System for Olefin‐to‐Diol Conversion Powered by Single‐Atom Fe Catalysts With In Situ Generated Acid

ABSTRACT

As important synthetic intermediates, 1,2‐diols are usually produced by dihydroxylation of olefins, which generally require noble metal‐based molecular catalysts that face recovery and reuse issues. Developing environmentally friendly and economical synthetic methodology to obtain 1,2‐diols is imperative. One‐pot tandem catalysis has attracted much attention due to the significant reduction of reaction time and the avoidance of intermediates separation of intermediates and waste production. Herein, we report a novel tandem catalytic system for the efficient conversion of terminal olefins to value‐added 1,2‐diols. This system employs a porous porphyrinic triazine framework‐stabilized iron single‐atom catalyst (FeSAs/PTFs) with well‐defined Fe–N ₄ sites, in conjunction with isobutyraldehyde (IBA) as a cocatalyst under an oxygen atmosphere. The tandem process begins with the epoxidation of the olefin catalyzed by FeSAs/PTFs using IBA and O ₂ , followed by hydrolysis of the epoxide intermediate mediated by in situ‐generated isobutyric acid—the oxidation product of IBA—in the presence of water. Notably, this non‐toxic and earth‐abundant iron‐based single‐atom catalyst exhibits broad substrate compatibility, encompassing both alkyl and cyclic olefins. Furthermore, the FeSAs/PTF‐400 catalyst demonstrates exceptional stability and can be recycled at least seven times without significant loss of catalytic activity.