Department of Chemistry, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul, 08826, Korea.
Department of Fine Chemistry, Seoul National University of Science and Technology, 232 Gongneung-ro, Nowon-gu, Seoul, 01811, Korea.
Chemistry. 2018 Jun 18;24(34):8632-8638. doi: 10.1002/chem.201800447. Epub 2018 May 22.
Atom-transfer chemistry represents an important class of reactions catalyzed by metalloenzymes. As a functional mimic of non-heme iron enzymes that deliver oxygen atoms to olefins, we have designed monoiron complexes supported by new N-donor chelates. These ligands take advantage of heme-like conformational rigidity of the π-conjugated molecular backbone, and synthetic flexibility of tethering non-heme donor groups for additional steric and electronic control. Iron complexes generated in situ can be used to carry out catalytic epoxidation of a wide range of olefin substrates by using mCPBA as a terminal oxidant. The fate of initial iron-peracid adduct and the involvement of iron-oxo species in this process were investigated further by mechanistic probes and isotope exchange studies. Our findings suggest that anilidopyridyl-derived [N,N]-bidentate motif could serve as a versatile structural platform to build non-heme ligands for catalytic oxidation chemistry.
原子转移化学代表了一类由金属酶催化的重要反应。作为非血红素铁酶向烯烃提供氧原子的功能模拟物，我们设计了由新型 N-供体螯合物支撑的单核铁配合物。这些配体利用了共轭分子骨架的类血红素构象刚性，以及连接非血红素给体基团的合成灵活性，以实现额外的空间和电子控制。通过原位生成的铁配合物可以使用 mCPBA 作为末端氧化剂，对广泛的烯烃底物进行催化环氧化反应。通过机理探针和同位素交换研究进一步研究了初始铁过酸加合物的命运以及铁-氧物种在该过程中的参与。我们的研究结果表明，苯胺基吡啶衍生的[N,N]-双齿基序可以作为构建催化氧化化学非血红素配体的多功能结构平台。
