通过第二个铁激活非血红素铁-氧氢以羟基化强碳氢键：对可溶性甲烷单加氧酶的可能影响
Activation of a Non-Heme Fe -OOH by a Second Fe to Hydroxylate Strong C-H Bonds: Possible Implications for Soluble Methane Monooxygenase.
作者信息
Kal Subhasree, Que Lawrence
机构信息
Department of Chemistry, University of Minnesota, Twin Cities, 207 Pleasant Street SE, Minneapolis, MN, 55455, USA.
出版信息
Angew Chem Int Ed Engl. 2019 Jun 17;58(25):8484-8488. doi: 10.1002/anie.201903465. Epub 2019 May 9.
Abstract
Non-heme iron oxygenases contain either monoiron or diiron active sites, and the role of the second iron in the latter enzymes is a topic of particular interest, especially for soluble methane monooxygenase (sMMO). Herein we report the activation of a non-heme Fe -OOH intermediate in a synthetic monoiron system using Fe (OTf) to form a high-valent oxidant capable of effecting cyclohexane and benzene hydroxylation within seconds at -40 °C. Our results show that the second iron acts as a Lewis acid to activate the iron-hydroperoxo intermediate, leading to the formation of a powerful Fe =O oxidant-a possible role for the second iron in sMMO.
摘要
非血红素铁氧化酶含有单铁或双铁活性位点，后一种酶中第二个铁的作用是一个特别受关注的话题，尤其是对于可溶性甲烷单加氧酶（sMMO）而言。在此我们报道了在一个合成单铁体系中使用Fe(OTf)激活非血红素Fe -OOH中间体，以形成一种高价态氧化剂，该氧化剂能够在-40°C下数秒内实现环己烷和苯的羟基化。我们的结果表明，第二个铁作为路易斯酸来激活铁-氢过氧中间体，导致形成一种强大的Fe =O氧化剂——这可能是第二个铁在sMMO中的作用。
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