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Reversal of diastereoselectivity in palladium-arene interaction directed hydrogenative desymmetrization of 1,3-diketones

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Abstract

For the metal-catalyzed asymmetric hydrogenation of α-substituted ketones, cis reductive products are generally obtained due to steric hindrance of substituents. Herein, an unprecedented trans reductive products were observed in palladium-catalyzed hydrogenative desymmetrization of cyclic and acyclic 1,3-diketones, providing the chiral trans β-hydroxy ketones with two adjacent stereocenters including one α-tertiary or quaternary stereocenter with high enantioselectivity and diastereoselectivity. Mechanistic studies and DFT calculations suggested that the rarely observed diastereoselectivity reversal is ascribed to the charge-charge interaction between the palladium and aromatic ring of the substrate, which could not only result in the reversal of the diastereoselectivity, but also improve the reactivity.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21871255, 21532006, 21873096) and Chinese Academy of Sciences (XDB17020300, XDB17010200).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China

    Chang-Bin Yu, Heng-Ding Wang, Bo Song, Hong-Qiang Shen, Hong-Jun Fan & Yong-Gui Zhou

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Heng-Ding Wang

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  1. Chang-Bin Yu
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  2. Heng-Ding Wang
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  3. Bo Song
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  4. Hong-Qiang Shen
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  5. Hong-Jun Fan
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  6. Yong-Gui Zhou
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Correspondence to Hong-Jun Fan or Yong-Gui Zhou.

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Yu, CB., Wang, HD., Song, B. et al. Reversal of diastereoselectivity in palladium-arene interaction directed hydrogenative desymmetrization of 1,3-diketones. Sci. China Chem. 63, 215–221 (2020). https://doi.org/10.1007/s11426-019-9601-7

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  • DOI: https://doi.org/10.1007/s11426-019-9601-7

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