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Olefin cis ‐Dihydroxylation and Aliphatic CH Bond Oxygenation by a Dioxygen‐Derived Electrophilic Iron–Oxygen Oxidant
Author(s) -
Chatterjee Sayanti,
Paine Tapan Kanti
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201502229
Subject(s) - heterolysis , chemistry , nucleophile , electrophile , bond cleavage , lewis acids and bases , medicinal chemistry , catalysis , ligand (biochemistry) , oxygen , reactivity (psychology) , photochemistry , stereochemistry , organic chemistry , medicine , biochemistry , receptor , alternative medicine , pathology
Many iron‐containing enzymes involve metal–oxygen oxidants to carry out O 2 ‐dependent transformation reactions. However, the selective oxidation of CH and CC bonds by biomimetic complexes using O 2 remains a major challenge in bioinspired catalysis. The reactivity of iron–oxygen oxidants generated from an Fe II –benzilate complex of a facial N 3 ligand were thus investigated. The complex reacted with O 2 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 Fe II –hydroperoxo species is proposed to form from the benzilate complex, which undergoes heterolytic OO bond cleavage in the presence of a Lewis acid to generate an Fe IV –oxo–hydroxo oxidant. The electrophilic iron–oxygen oxidant selectively oxidizes sulfides to sulfoxides, alkenes to cis‐diols, and it hydroxylates the CH bonds of alkanes, including that of cyclohexane.