Sligar S G, Gelb M H, Heimbrook D C
Xenobiotica. 1984 Jan-Feb;14(1-2):63-86. doi: 10.3109/00498258409151399.
This review presents current ideas, models and experimental data relating to the precise chemistry that links the transition metal active centre of cytochrome P-450 systems, the unactivated alkane substrate and the triplet atmospheric dioxygen molecule. Aspects considered include the hypervalent transition metal, the reductive activation of the dioxygen molecule by two electrons as an intermediate in the four-equivalent oxidase mechanism, and the details of carbon-hydrogen and carbon-carbon fragmentation. Studies of the microbial camphor 5-exo hydroxylase system are used to exemplify the principles discussed.
本综述介绍了与细胞色素P-450系统的过渡金属活性中心、未活化的烷烃底物和三线态大气双原子氧分子之间精确化学联系相关的当前观点、模型和实验数据。所考虑的方面包括高价过渡金属、作为四价氧化酶机制中间体的双原子氧分子通过两个电子的还原活化,以及碳-氢和碳-碳断裂的细节。对微生物樟脑5-exo羟化酶系统的研究被用于例证所讨论的原理。