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Regioselective and asymmetric allylic alkylation of vinyl epoxides for the construction of allylic alcohols via synergistic catalysis

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Abstract

A highly efficient asymmetric allylic alkylation of cyclic and acyclic carbon nucleophiles with vinyl epoxides has been developed, which exhibits good functional group compatibility, high atomic and step economy. This protocol utilizes a strategy of synergistic catalysis with a chiral N,N′-dioxide/NiII complex and an achiral Pd0 catalyst, generating a series of multi-substituted allylic alcohols with a quaternary carbon stereocenter in high yield and excellent regio-, Z/E- and enantioselectivity under mild conditions. Further transformations of the product demonstrate the potential utility of this protocol in the synthesis of allyl alcohol derivatives and natural product analogues. Experimental studies revealed that the N,N′-dioxide/metal complexes play an important role in controlling the Z/E- and enantioselectivity. The density functional theory (DFT) calculations further demonstrated that multiple C-H···π interactions between the aromatic rings of the two substrates and the amide moiety in the ligand stabilized the dominant transition state.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (U19A2014) and Sichuan University (2020SCUNL204). We are grateful to Dr Yuqiao Zhou (Sichuan University) for the X-ray single crystal diffraction analysis.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, China

    Min Chen, Longqing Yang, Yuzhen Li, Yinhe Qu, Guihua Pan, Xiaoming Feng & Xiaohua Liu

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  1. Min Chen
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  2. Longqing Yang
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  3. Yuzhen Li
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Correspondence to Xiaoming Feng or Xiaohua Liu.

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Supporting information The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Chen, M., Yang, L., Li, Y. et al. Regioselective and asymmetric allylic alkylation of vinyl epoxides for the construction of allylic alcohols via synergistic catalysis. Sci. China Chem. 67, 542–550 (2024). https://doi.org/10.1007/s11426-023-1794-2

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