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Rhodium-catalyzed enantioselective and diastereodivergent access to diaxially chiral heterocycles

Author

Listed:
  • Yishou Wang

    (Shandong University)

  • Xiaohan Zhu

    (Shaanxi Normal University)

  • Deng Pan

    (Tianjin University)

  • Jierui Jing

    (Shaanxi Normal University)

  • Fen Wang

    (Shaanxi Normal University)

  • Ruijie Mi

    (Shandong University)

  • Genping Huang

    (Tianjin University)

  • Xingwei Li

    (Shandong University
    Shaanxi Normal University)

Abstract

N-N axially chiral biaryls represent a rarely explored class of atropisomers. Reported herein is construction of diverse classes of diaxially chiral biaryls containing N-N and C-N/C-C diaxes in distal positions in excellent enantioselectivity and diastereoselectivity. The N-N chiral axis in the products provides a handle toward solvent-driven diastereodivergence, as has been realized in the coupling of a large scope of benzamides and sterically hindered alkynes, affording diaxes in complementary diastereoselectivity. The diastereodivergence has been elucidated by computational studies which revealed that the hexafluoroisopropanol (HFIP) solvent molecule participated in an unusual manner as a solvent as well as a ligand and switched the sequence of two competing elementary steps, resulting in switch of the stereoselectivity of the alkyne insertion and inversion of the configuration of the C-C axis. Further cleavage of the N-directing group in the diaxial chiral products transforms the diastereodivergence to enantiodivergence.

Suggested Citation

  • Yishou Wang & Xiaohan Zhu & Deng Pan & Jierui Jing & Fen Wang & Ruijie Mi & Genping Huang & Xingwei Li, 2023. "Rhodium-catalyzed enantioselective and diastereodivergent access to diaxially chiral heterocycles," Nature Communications, Nature, vol. 14(1), pages 1-12, December.
    • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-39968-3
    DOI: 10.1038/s41467-023-39968-3
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    References listed on IDEAS

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    1. Jiawen Wang & Sujuan Zheng & Subramani Rajkumar & Jinglei Xie & Na Yu & Qian Peng & Xiaoyu Yang, 2020. "Chiral phosphoric acid-catalyzed stereodivergent synthesis of trisubstituted allenes and computational mechanistic studies," Nature Communications, Nature, vol. 11(1), pages 1-12, December.
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    Cited by:

    1. Chaochao Yao & Dan-Ran Li & Hua-Ming Xiang & Si-Jia Li & Yuepeng Lu & Zihao Wang & Tingrui Yin & Jiaqiang Wang & Kongling Feng & Cuiju Zhu & Hao Xu, 2024. "Copper-catalysed asymmetric annulation of yne-allylic esters with amines to access axially chiral arylpyrroles," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    2. Tong Li & Yanbo Zhang & Cong Du & Dandan Yang & Mao-Ping Song & Jun-Long Niu, 2024. "Simultaneous construction of inherent and axial chirality by cobalt-catalyzed enantioselective C-H activation of calix[4]arenes," Nature Communications, Nature, vol. 15(1), pages 1-10, December.

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