Citation: JIANG He-Yan, WU Zhi-Feng, CHEN Hua. Asymmetric Hydrogenation of Aromatic Ketones Catalyzed by Cinchona-Modified Ir/SiO₂[J]. Acta Physico-Chimica Sinica, ;2013, 29(07): 1572-1581. doi: 10.3866/PKU.WHXB201304243 shu

Asymmetric Hydrogenation of Aromatic Ketones Catalyzed by Cinchona-Modified Ir/SiO₂

1.
1 Key Laboratory of Catalysis Science and Technology of Chongqing Education Commission, College of Environmental and Biological Engineering, Research Center of Pharmaceutical Chemistry and Chemical Biology, Chongqing Technology and Business University, Chongqing 400067;
2 Key Laboratory of Green Chemistry and Technology, Ministry of Education, The Institute of Homogeneous Catalysis, College of Chemistry, Sichuan University, Chengdu 610064

Received Date: 4 February 2013
Available Online: 24 April 2013
Fund Project: 国家自然科学基金(21201184) (21201184) 重庆市科委自然科学基金计划(CSTC, 2011BA5025) (CSTC, 2011BA5025) 重庆工商大学科研启动基金(2010-56-14) (2010-56-14) 重庆市百名学术学科领军人才培养计划和重庆市科技创新团队(KJTD201020)资助项目 (KJTD201020)

The asymmetric hydrogenation of aromatic ketones catalyzed by cinchona- and triphenylphosphine (tpp)-modified Ir/SiO₂ was studied. The heterogeneous enantioselective hydrogenation of heterocyclic ketones using a supported iridium catalyst was also investigated. Different analytical techniques, including inductively coupled plasma-atomic emission spectroscopy (ICP-AES), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), the Brunauer- Emmett-Teller (BET) method, infrared (IR) spectroscopy, ³¹P solid state nuclear magnetic resonance (NMR) spectroscopy, homogeneous- heterogeneous comparison experiment, conventional filtering test, and mercury poisoning experiment, were used to characterize the catalytic system. HRTEM, XPS, and the BET method clearly characterized the catalytic system. IR and ³¹P solid state NMR spectra provided useful information about the interactions between modifier, metal, and stabilizer. The homogeneous-heterogeneous comparison experiment, conventional filtering test, and mercury poisoning experiment clearly showed the differences between supported, and homogeneous catalysts. In addition, the effects of different stabilizers, modifiers, iridium content, solvents, and base additives on the asymmetric hydrogenation of aromatic ketones were investigated in detail. The results showed that cinchona alkaloids positively modified the Ir/ SiO₂ catalyst. Under the optimum conditions, the hydrogenation enantioselectivities of acetophenone and its derivatives were 52%-96%. The enantioselectivities of the hydrogenation products of 4-acetopyridine, 2-acetothiophene, and 2-acetofuran reached 74%, 75%, and 63%, respectively.
- Iridium,
- Cinchona alkaloid,
- Aromatic ketone,
- Asymmetric hydrogenation,
- Supported catalyst
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沈阳化工大学材料科学与工程学院沈阳 110142

Asymmetric Hydrogenation of Aromatic Ketones Catalyzed by Cinchona-Modified Ir/SiO2

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通讯作者: 陈斌, bchen63@163.com

Asymmetric Hydrogenation of Aromatic Ketones Catalyzed by Cinchona-Modified Ir/SiO₂