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Proton-Promoted and Anion-Enhanced Epoxidation of Olefins by Hydrogen Peroxide in the Presence of Nonheme Manganese Catalysts
- Proton-Promoted and Anion-Enhanced Epoxidation of Olefins by Hydrogen Peroxide in the Presence of Nonheme Manganese Catalysts
- Miao, Chengxia; Wang, Bin; Yong, Yong; Xia, Chungu; Lee, Yong -Min; Nam, Wonwoo; Sun, Wei
- Ewha Authors
- 남원우; 이용민
- SCOPUS Author ID
- 남원우; 이용민
- Issue Date
- Journal Title
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
- vol. 138, no. 3, pp. 936 - 943
- AMER CHEMICAL SOC
- SCI; SCIE; SCOPUS
- We report a remarkable Bronsted acid effect in the epoxidation of olefins by nonheme manganese catalysts and aqueous hydrogen peroxide. More specifically, a mononuclear nonheme manganese complex bearing a tetradentate N4 ligand, Mn-II(Dbp-MCP)(OTf)(2) (Dbp-MCP = (1R,2R)-N,N'-dimethyl-N,N'-bis((R)-(3,5-di-tert-butyl-phenyl)-2-pyridinylmethyl)cyclohexane-1,2-diamine; OTf- = CF3SO3-), is a highly efficient catalyst in the epoxidation of olefins by aqueous H2O2 in the presence of H2SO4 (1-3 mol %). The yields of epoxide products as well as the chemo- and enantioselectivities increase dramatically in the presence of H2SO4; no formation of epoxides is observed in the absence of H2SO4. In addition, the product yields and enantioselectivities are dependent significantly on the manganese catalysts and Bronsted acids. The catalytic epoxidation of olefins by other oxidants, such as peracids, alkyl hydroperoxides, and iodosylbenzene, is also affected by the presence of H2SO4; product yields and enantioselectivities are high and similar irrespective of the oxidants in the presence of H2SO4, suggesting that a common epoxidizing intermediate is generated in the reactions of [Mn-II(Dbp-MCP)](2)(+) and the oxidants. Mechanistic studies, performed with O-18-labeled water ((H2O)-O-18) and cumyl hydroperoxide, reveal that a high-valent manganese-oxo species is formed as an epoxidizing intermediate via O-O bond heterolysis of Mn-OOH(R) species. The role of H2SO4 is proposed to facilitate the formation of a high-valent Mn-oxo species and to increase the oxidizing power and enantioselectivity of the Mn-oxo oxidant in olefin epoxidation reactions. Density functional theory (DFT) calculations support experimental results such as the formation of a Mn(V)-oxo species as an epoxidizing intermediate.
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