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Modulating stereoselectivity in allylic C(sp3)-H bond arylations via nickel and photoredox catalysis

Author

Listed:
  • Long Huang

    (RWTH Aachen University)

  • Marcin Szewczyk

    (RWTH Aachen University)

  • Rajesh Kancherla

    (King Abdullah University of Science and Technology (KAUST))

  • Bholanath Maity

    (King Abdullah University of Science and Technology (KAUST))

  • Chen Zhu

    (King Abdullah University of Science and Technology (KAUST))

  • Luigi Cavallo

    (King Abdullah University of Science and Technology (KAUST))

  • Magnus Rueping

    (King Abdullah University of Science and Technology (KAUST)
    RWTH Aachen University)

Abstract

While significant progress has been made in developing selective C-H bond cross-couplings in the field of radical chemistry, the site and stereoselectivity remain a long-standing challenge. Here, we present the successful development of stereodivergent allylic C(sp3)-H bond arylations through a systematic investigation of the direction and degree of stereoselectivity in the cross-coupling process. In contrast to the signature photosensitized geometrical isomerization of alkenes, the catalytic reaction demonstrates the feasibility of switching the C-C double bond stereoselectivity by means of ligand control as well as steric and electronic effects. Computational studies explain the stereochemical outcome and indicate that excitation of a Ni-allyl complex from singlet to a triplet state results in a spontaneous change of the allyl group coordination and that the subsequent isomerization can be directed by the choice of the ligand to achieve E/Z selectivity.

Suggested Citation

  • Long Huang & Marcin Szewczyk & Rajesh Kancherla & Bholanath Maity & Chen Zhu & Luigi Cavallo & Magnus Rueping, 2023. "Modulating stereoselectivity in allylic C(sp3)-H bond arylations via nickel and photoredox catalysis," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
  • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-36103-0
    DOI: 10.1038/s41467-023-36103-0
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    References listed on IDEAS

    as
    1. Rajesh Kancherla & Krishnamoorthy Muralirajan & Bholanath Maity & Safakath Karuthedath & Gadde Sathish Kumar & Frédéric Laquai & Luigi Cavallo & Magnus Rueping, 2022. "Mechanistic insights into photochemical nickel-catalyzed cross-couplings enabled by energy transfer," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    2. Ian B. Perry & Thomas F. Brewer & Patrick J. Sarver & Danielle M. Schultz & Daniel A. DiRocco & David W. C. MacMillan, 2018. "Direct arylation of strong aliphatic C–H bonds," Nature, Nature, vol. 560(7716), pages 70-75, August.
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