Olefin cis‐Dihydroxylation and Aliphatic CH Bond Oxygenation by a Dioxygen‐Derived Electrophilic Iron–Oxygen Oxidant |
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Authors: | Sayanti Chatterjee Dr Tapan Kanti Paine |
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Institution: | Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata‐700032 (India) |
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Abstract: | Many iron‐containing enzymes involve metal–oxygen oxidants to carry out O2‐dependent transformation reactions. However, the selective oxidation of C? H and C?C bonds by biomimetic complexes using O2 remains a major challenge in bioinspired catalysis. The reactivity of iron–oxygen oxidants generated from an FeII–benzilate complex of a facial N3 ligand were thus investigated. The complex reacted with O2 to form a nucleophilic oxidant, whereas an electrophilic oxidant, intercepted by external substrates, was generated in the presence of a Lewis acid. Based on the mechanistic studies, a nucleophilic FeII–hydroperoxo species is proposed to form from the benzilate complex, which undergoes heterolytic O? O bond cleavage in the presence of a Lewis acid to generate an FeIV–oxo–hydroxo oxidant. The electrophilic iron–oxygen oxidant selectively oxidizes sulfides to sulfoxides, alkenes to cis‐diols, and it hydroxylates the C? H bonds of alkanes, including that of cyclohexane. |
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Keywords: | dioxygen electrophilic oxidants iron Lewis acids oxidation |
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