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Asymmetric α-C(sp3)−H allylic alkylation of primary alkylamines by synergistic Ir/ketone catalysis

Author

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  • Jianyu Li

    (Shanghai Frontiers Science Center of Biomimetic Catalysis and Shanghai Normal University)

  • Sheng Gong

    (Shanghai Frontiers Science Center of Biomimetic Catalysis and Shanghai Normal University)

  • Shaolun Gao

    (Shanghai Frontiers Science Center of Biomimetic Catalysis and Shanghai Normal University)

  • Jianfeng Chen

    (Shanghai Frontiers Science Center of Biomimetic Catalysis and Shanghai Normal University)

  • Wen-Wen Chen

    (Shanghai Frontiers Science Center of Biomimetic Catalysis and Shanghai Normal University)

  • Baoguo Zhao

    (Shanghai Frontiers Science Center of Biomimetic Catalysis and Shanghai Normal University)

Abstract

Primary alkyl amines are highly reactive in N-nucleophilic reactions with electrophiles. However, their α-C−H bonds are unreactive towards electrophiles due to their extremely low acidity (pKa ~57). Nonetheless, 1,8-diazafluoren-9-one (DFO) can activate primary alkyl amines by increasing the acidity of the α-amino C−H bonds by up to 1044 times. This makes the α-amino C−H bonds acidic enough to be deprotonated under mild conditions. By combining DFO with an iridium catalyst, direct asymmetric α-C−H alkylation of NH2-unprotected primary alkyl amines with allylic carbonates has been achieved. This reaction produces a wide range of chiral homoallylic amines with high enantiopurities. The approach has successfully switched the reactivity between primary alkyl amines and allylic carbonates from intrinsic allylic amination to the α-C−H alkylation, enabling the construction of pharmaceutically significant chiral homoallylic amines from readily available primary alkyl amines in a single step.

Suggested Citation

  • Jianyu Li & Sheng Gong & Shaolun Gao & Jianfeng Chen & Wen-Wen Chen & Baoguo Zhao, 2024. "Asymmetric α-C(sp3)−H allylic alkylation of primary alkylamines by synergistic Ir/ketone catalysis," Nature Communications, Nature, vol. 15(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-45131-3
    DOI: 10.1038/s41467-024-45131-3
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