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Ruthenium-Catalyzed Asymmetric Hydrogenation of 3-Oxoglutaric Acid Derivatives: A Study of Unconventional Solvent and Substituent Effects

Authors

  • Wanfang Li,

    1. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (P.R. China), Fax: (+86) 21-5474-8925
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  • Xiaoming Tao,

    1. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (P.R. China), Fax: (+86) 21-5474-8925
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  • Xin Ma,

    1. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (P.R. China), Fax: (+86) 21-5474-8925
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  • Weizheng Fan,

    1. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (P.R. China), Fax: (+86) 21-5474-8925
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  • Xiaoming Li,

    1. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (P.R. China), Fax: (+86) 21-5474-8925
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  • Mengmeng Zhao,

    1. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (P.R. China), Fax: (+86) 21-5474-8925
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  • Xiaomin Xie,

    1. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (P.R. China), Fax: (+86) 21-5474-8925
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  • Prof. Zhaoguo Zhang

    Corresponding author
    1. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (P.R. China), Fax: (+86) 21-5474-8925
    2. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, 345 Lingling Road, Shanghai 200032 (P.R. China)
    • School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (P.R. China), Fax: (+86) 21-5474-8925===

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Abstract

A series of 3-oxoglutaric acid derivatives have been hydrogenated in different solvents in the presence of [RuCl(benzene)(S)-SunPhos]Cl (SunPhos=(2,2,2′,2′-tetramethyl-[4,4′-bibenzo[d][1,3]dioxole]-5,5′-diyl)bis(diphenylphosphine)). Unlike simple β-keto acid derivatives, these advanced analogues can be readily hydrogenated in uncommon solvents such as THF, CH2Cl2, acetone, and dioxane with high enantioselectivities. Two possible catalytic cycles have been proposed to explain the different reactivities of these 1,3,5-tricarbonyl substrates in the tested solvents. The C-2 and C-4 substituents had notable but irregular influence on the reactivity and enantioselectivity of the reactions. More pronounced solvent effects were observed: the ee values increased from around 20 % in EtOH or THF to 90 % in acetone. Inversion of the product configuration was observed when the solvent was changed from EtOH to THF or acetone, and a mixed solvent system can lead to better enantioselectivity than a single solvent.

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