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Enantioselective remote meta-C–H arylation and alkylation via a chiral transient mediator

Author

Listed:
  • Hang Shi

    (The Scripps Research Institute)

  • Alastair N. Herron

    (The Scripps Research Institute)

  • Ying Shao

    (The Scripps Research Institute)

  • Qian Shao

    (The Scripps Research Institute)

  • Jin-Quan Yu

    (The Scripps Research Institute)

Abstract

Enantioselective carbon–hydrogen (C–H) activation reactions by asymmetric metallation could provide new routes for the construction of chiral molecules1,2. However, current methods are typically limited to the formation of five- or six-membered metallacycles, thereby preventing the asymmetric functionalization of C–H bonds at positions remote to existing functional groups. Here we report enantioselective remote C–H activation using a catalytic amount of a chiral norbornene as a transient mediator, which relays initial ortho-C–H activation to the meta position. This was used in the enantioselective meta-C–H arylation of benzylamines, as well as the arylation and alkylation of homobenzylamines. The enantioselectivities obtained using the chiral transient mediator are comparable across different classes of substrates containing either neutral σ-donor or anionic coordinating groups. This relay strategy could provide an alternative means to remote chiral induction, one of the most challenging problems in asymmetric catalysis3,4.

Suggested Citation

  • Hang Shi & Alastair N. Herron & Ying Shao & Qian Shao & Jin-Quan Yu, 2018. "Enantioselective remote meta-C–H arylation and alkylation via a chiral transient mediator," Nature, Nature, vol. 558(7711), pages 581-585, June.
    • Handle: RePEc:nat:nature:v:558:y:2018:i:7711:d:10.1038_s41586-018-0220-1
    DOI: 10.1038/s41586-018-0220-1
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    Cited by:

    1. Liang Jin & Ya Li & Yihui Mao & Xiao-Bao He & Zhan Lu & Qi Zhang & Bing-Feng Shi, 2024. "Chiral dinitrogen ligand enabled asymmetric Pd/norbornene cooperative catalysis toward the assembly of C–N axially chiral scaffolds," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    2. Peng-Bo Bai & Alastair Durie & Gang-Wei Wang & Igor Larrosa, 2024. "Unlocking regioselective meta-alkylation with epoxides and oxetanes via dynamic kinetic catalyst control," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    3. Jagrit Grover & Gaurav Prakash & Nupur Goswami & Debabrata Maiti, 2022. "Traditional and sustainable approaches for the construction of C–C bonds by harnessing C–H arylation," Nature Communications, Nature, vol. 13(1), pages 1-17, December.
    4. Zi-An Shen & Jiami Guo & Yixin Lu, 2024. "Facile enantioselective synthesis of multi-substituted norbornanes/norbornenes using a latent synthon strategy," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    5. Saikat Guria & Mirja Md Mahamudul Hassan & Jiawei Ma & Sayan Dey & Yong Liang & Buddhadeb Chattopadhyay, 2023. "A tautomerized ligand enabled meta selective C–H borylation of phenol," Nature Communications, Nature, vol. 14(1), pages 1-11, December.

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