Barton D H, Csuhai E, Doller D, Ozbalik N, Balavoine G
Department of Chemistry, Texas A&M University, College Station 77843.
Proc Natl Acad Sci U S A. 1990 May;87(9):3401-4. 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 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.
在Gif型体系将饱和烃选择性氧化为酮的过程中，已鉴定出两种中间体A和B。中间体A被表征为一种具有与碳形成二级铁σ键的Fev物种；它能被四种不同的试剂捕获或转化为第二种中间体B，B水解形成仲醇。有人提出μ-氧代Fe2III二聚体是Gif型反应活性的基础。如果第一个铁参与中间体A的合成，那么第二个铁则用于将中间体B分子内氧化为缩酮，缩酮水解后生成酮。在选择性烃氧化方面，酶甲烷单加氧酶与Gif型体系表现出显著的相似性，尤其是在金刚烷的情况下。
