Enhanced Alkene Oxidative Cleavage in Water via Photoexcited FeIV Species within Covalent Organic Framework Thin Films

Abstract

AbstractThe oxidative cleavage of alkenes is a crucial step in synthesizing key organic molecules featuring carbonyl functional groups prevalent in natural products and pharmaceuticals. We introduce a photochemical method for heterogeneous C=C bond cleavage, employing photo‐catalytically generated [(bTAML)FeIV−O−FeIV(bTAML)]− species (where bTAML stands for biuret‐modified tetraamido macrocyclic ligand) in aqueous environments under gentle conditions. Leveraging the photosensitizing properties of Covalent Organic Frameworks (COFs) and their advantageous morphological traits as films, we enhance the reaction by closely associating the substrate with the catalyst. This study marks the inaugural demonstration of Fe2IV‐μ‐oxo radical cation and FeIV=O species facilitating alkene cleavage in water against a backdrop of a hydrophobic COF. Through comprehensive mechanistic studies, including control experiments, we confirm that these two high‐valent iron oxo species collaborate to cleave alkenes, forming an intermediate epoxide. Our approach yields moderate to high success across various alkenes, displaying diverse functional groups (achieving up to 75 % yield) with notable efficiency and selectivity towards aldehyde/ketone products. Moreover, the heterogeneous COF film, immobilizing (Et4N)2[FeIII(Cl)bTAML], exhibits exceptional recyclability, enduring up to four cycles.