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Published on: June 23, 2019
Non-Heme Iron Catalysts for Olefin Epoxidation: Conformationally Rigid Aryl-Aryl Junction To Support Amine/Imine
Hyunchang Park1, Hye Mi Ahn2, Ha Young Jeong2
1Department of Chemistry, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul, 08826, Korea.
Abstract:
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.
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