Mechanism of the selective functionalization of saturated hydrocarbons by Gif systems: relationship with methane monooxygenase.
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 Fev species with a secondary iron sigma-bond to carbon; it is captured by four different reagents or transformed into the second intermediate, B, which hydrolyzes to form a secondary alcohol. A mu-oxo Fe2III dimer 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.
Barton
D H
DH
Department of Chemistry, Texas A&M University, College Station 77843.
Csuhai
E
E
Doller
D
D
Ozbalik
N
N
Balavoine
G
G
D000218:Adamantane / Q000378:metabolism*; D000447:Aldehydes / Q000032:analysis; D006838:Hydrocarbons / Q000378:metabolism*; D007659:Ketones / Q000032:analysis; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010105:Oxygenases / Q000378:metabolism*; D013329:Structure-Activity Relationship
D000447:Aldehydes; D006838:Hydrocarbons; D007659:Ketones; D010105:Oxygenases; C021555:methane monooxygenase; D000218:Adamantane