Mechanism of the Selective Functionalization of Saturated Hydrocarbons by Gif Systems: Relationship with Methane Monooxygenase

• Published in: Proceedings of the National Academy of Sciences - PNAS Vol. 87; no. 9; pp. 3401 - 3404
• Main Authors: Derek H. R. Barton, Csuhai, Eva, Doller, Dario, Ozbalik, Nubar, Balavoine, Gilbert
• Format: Journal Article
• Language: English
• Published: Washington, DC National Academy of Sciences of the United States of America 01-05-1990; National Acad Sciences
• Subjects: Adamantane - metabolism; Alcohols; Aldehydes - analysis; Analytical, structural and metabolic biochemistry; Biological and medical sciences; Enzymes; Enzymes and enzyme inhibitors; Fundamental and applied biological sciences. Psychology; Hydrocarbons; Hydrocarbons - metabolism; Ketones; Ketones - analysis; Ligands; Methane; methane monooxygenase; Molecular Structure; Oxidation; Oxidation-Reduction; Oxidoreductases; Oxygen; Oxygenases - metabolism; Pyridines; Reagents; Structure-Activity Relationship; Oxidation; Hydrocarbon; Mechanism of action; Enzyme
• ISSN: 0027-8424; 1091-6490
• DOI: 10.1073/pnas.87.9.3401

Two intermediates, A and B, have been identified in the selective oxidation of saturated hydrocarbons to ketones by Gif-type systems. Intermediate A has been characterized as an Fevspecies with a secondary iron σ-bond to carbon; it is captured by four different reagents or transformed into the second intermidiate, B, which hydrolyzes to form a secondary alcohol. A μ-oxo Fe2
IIIdimer is proposed as a basis for Gif-type reactivity. If the first iron is involved in the synthesis of intermediate A, the second is used to oxidize intermediate B intramolecularly to a ketal, which on hydrolysis yields a ketone. The enzyme methane monooxygenase shows a remarkable similarity to Gif-type systems in its selective hydrocarbon oxidation, particularly in the case of adamantane.