Proton-Promoted and Anion-Enhanced Epoxidation of Olefins by Hydrogen Peroxide in the Presence of Nonheme Manganese Catalysts | |
Department | OSSO国家重点实验室 |
Miao CX(苗成霞)1; Wang B(王斌)2; Wang Y(王永)1; Xia CG(夏春谷)1; Lee, Yong -Min2; Wonwoo Nam2; Sun W(孙伟)1; Sun W(孙伟) | |
2016 | |
Source Publication | Journal of the American Chemical Society |
ISSN | 0002-7863 |
Volume | 138Issue:3Pages:936-943 |
Abstract | We report a remarkable Brønsted 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, MnII(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 Brønsted 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 [MnII(Dbp-MCP)]2+ and the oxidants. Mechanistic studies, performed with 18O-labeled water (H218O) 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. |
Subject Area | 物理化学与绿色催化 |
DOI | 10.1021/jacs.5b11579 |
Funding Organization | the National Natural Science Foundation of China (21473226;21133011;21173211);the NRF of Korea through CRI (NRF-2012R1A3A2048842);GRL (NRF-2010-00353) |
Indexed By | SCI |
If | 13.858 |
Language | 英语 |
Funding Project | 生物与仿生催化课题组;均相催化课题组 |
compositor | 第一作者单位 |
Citation statistics | |
Document Type | 期刊论文 |
Identifier | http://ir.licp.cn/handle/362003/19474 |
Collection | 羰基合成与选择氧化国家重点实验室(OSSO) |
Corresponding Author | Wonwoo Nam; Sun W(孙伟) |
Affiliation | 1.Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China 2.Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea |
Recommended Citation GB/T 7714 | Miao CX,Wang B,Wang Y,et al. Proton-Promoted and Anion-Enhanced Epoxidation of Olefins by Hydrogen Peroxide in the Presence of Nonheme Manganese Catalysts[J]. Journal of the American Chemical Society,2016,138(3):936-943. |
APA | Miao CX.,Wang B.,Wang Y.,Xia CG.,Lee, Yong -Min.,...&孙伟.(2016).Proton-Promoted and Anion-Enhanced Epoxidation of Olefins by Hydrogen Peroxide in the Presence of Nonheme Manganese Catalysts.Journal of the American Chemical Society,138(3),936-943. |
MLA | Miao CX,et al."Proton-Promoted and Anion-Enhanced Epoxidation of Olefins by Hydrogen Peroxide in the Presence of Nonheme Manganese Catalysts".Journal of the American Chemical Society 138.3(2016):936-943. |
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