Department of Chemistry and Nano Science, Ewha Womans University, Seoul 03760, Korea.
Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States.
J Am Chem Soc. 2023 Mar 1;145(8):4389-4393. doi: 10.1021/jacs.2c13551. Epub 2023 Feb 16.
The nature of reactive intermediates and the mechanism of the -dihydroxylation of arenes and olefins by Rieske dioxygenases and synthetic nonheme iron catalysts have been the topic of intense research over the past several decades. In this study, we report that a spectroscopically well characterized mononuclear nonheme iron(III)-peroxo complex reacts with olefins and naphthalene derivatives, yielding iron(III) cycloadducts that are isolated and characterized structurally and spectroscopically. Kinetics and product analysis reveal that the nonheme iron(III)-peroxo complex is a nucleophile that reacts with olefins and naphthalenes to yield -diol products. The present study reports the first example of the -dihydroxylation of substrates by a nonheme iron(III)-peroxo complex that yields -diol products.
过去几十年中， Rieske 双加氧酶和合成非血红素铁催化剂催化芳烃和烯烃的 -二羟化的反应中间体的本质和反应机理一直是研究的热点。在这项研究中，我们报告了一种光谱性质良好的单核非血红素铁（III）-过氧配合物与烯烃和萘衍生物反应，生成了铁（III）环加成产物，这些产物通过结构和光谱学进行了分离和表征。动力学和产物分析表明，非血红素铁（III）-过氧配合物是亲核试剂，它与烯烃和萘反应生成 -二醇产物。本研究报告了首例非血红素铁（III）-过氧配合物催化底物 -二羟化生成 -二醇产物的例子。
