Lee Jung Yoon, Karlin Kenneth D
Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, USA.
Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, USA.
Curr Opin Chem Biol. 2015 Apr;25:184-93. doi: 10.1016/j.cbpa.2015.02.014. Epub 2015 Mar 8.
To contribute solutions to current energy concerns, improvements in the efficiency of dioxygen mediated C-H bond cleavage chemistry, for example, selective oxidation of methane to methanol, could minimize losses in natural gas usage or produce feedstocks for fuels. Oxidative C-H activation is also a component of polysaccharide degradation, potentially affording alternative biofuels from abundant biomass. Thus, an understanding of active-site chemistry in copper monooxygenases, those activating strong C-H bonds is briefly reviewed. Then, recent advances in the synthesis-generation and study of various copper-oxygen intermediates are highlighted. Of special interest are cupric-superoxide, Cu-hydroperoxo and Cu-oxy complexes. Such investigations can contribute to an enhanced future application of C-H oxidation or oxygenation processes using air, as concerning societal energy goals.
为解决当前的能源问题，提高双分子氧介导的C-H键裂解化学的效率，例如将甲烷选择性氧化为甲醇，可以减少天然气使用中的损失或生产燃料的原料。氧化C-H活化也是多糖降解的一个组成部分，有可能从丰富的生物质中获得替代生物燃料。因此，本文简要综述了对激活强C-H键的铜单加氧酶活性位点化学的理解。然后，重点介绍了各种铜-氧中间体的合成、生成和研究的最新进展。特别感兴趣的是铜超氧化物、氢过氧化铜和铜-氧络合物。这些研究有助于在未来增强使用空气进行C-H氧化或氧合过程的应用，以实现社会能源目标。
