金属酵素作用機序に触発された精密設計金属錯体触媒の開発

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Direct aromatic ring hydroxylation is an important and desirable chemical reaction in various chemical processes such as drug synthesis. This reaction is hard to be achieved, but is carried out by some dioxygen-activating metalloenzymes such as cytochrome P450, pterin-dependent dioxygenases, and tyrosinase. In the pterin-dependent dioxygenases, dioxygen is activated at the mononuclear nonheme iron(II) ion in cooperation with reduced pterin cofactor to generate an iron(II)-alkylperoxo species. The heterolysis of the O−O bond in the iron(II)-alkylperoxo species results in the generation of an iron(IV)-oxo species. The high-valent iron oxo species is capable of performing aromatic ring hydroxylation due to its electrophilicity. This elegant chemical mechanism has stimulated many researchers to develop functional model complexes for aromatic ring hydroxylases, which can catalytically perform the direct aromatic ring hydroxylation reaction via a hypervalent iron-oxo species. The active species can be generated through the reaction of iron complexes with hydrogen peroxide, but often produce undesirable hydroxyl radicals via homolytic cleavage of the O−O bond in iron(III)-hydroperoxo species, which results in unselective oxidation of substrates and/or decomposition of the iron complex itself. Thus, the O−O bond in the iron(III)-hydroperoxo species must be cleaved heterolytically, but not homolytically. In this paper, recent progress is reviewed in the development of mononuclear nonheme iron complexes that catalyze direct hydroxylation of aromatic rings using hydrogen peroxide as an oxidant.

金属酵素作用機序に触発された精密設計金属錯体触媒の開発

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