IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v14y2023i1d10.1038_s41467-023-36103-0.html
   My bibliography  Save this article

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
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-023-36103-0
    File Function: Abstract
    Download Restriction: no

    File URL: https://libkey.io/10.1038/s41467-023-36103-0?utm_source=ideas
    LibKey link: if access is restricted and if your library uses this service, LibKey will redirect you to where you can use your library subscription to access this item
    ---><---

    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.
    Full references (including those not matched with items on IDEAS)

    Most related items

    These are the items that most often cite the same works as this one and are cited by the same works as this one.
    1. Ping-Fu Zhong & Jia-Lin Tu & Yating Zhao & Nan Zhong & Chao Yang & Lin Guo & Wujiong Xia, 2023. "Photoelectrochemical oxidative C(sp3)−H borylation of unactivated hydrocarbons," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    2. Zhenghui Wen & Diego Pintossi & Manuel Nuño & Timothy Noël, 2022. "Membrane-based TBADT recovery as a strategy to increase the sustainability of continuous-flow photocatalytic HAT transformations," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    3. Yue Wang & Suping Zhang & Ke Zeng & Pengli Zhang & Xiaorong Song & Tie-Gen Chen & Guoqin Xia, 2024. "Deoxygenative radical cross-coupling of C(sp3)−O/C(sp3)−H bonds promoted by hydrogen-bond interaction," Nature Communications, Nature, vol. 15(1), pages 1-8, December.
    4. Yujun Li & Shaopeng Guo & Qing-Han Li & Ke Zheng, 2023. "Metal-free photoinduced C(sp3)–H/C(sp3)–H cross-coupling to access α‑tertiary amino acid derivatives," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    5. Krishnamoorthy Muralirajan & Rajesh Kancherla & Bholanath Maity & Safakath Karuthedath & Frédéric Laquai & Luigi Cavallo & Magnus Rueping, 2023. "Mechanistic insights into excited-state palladium catalysis for C–S bond formations and dehydrogenative sulfonylation of amines," Nature Communications, Nature, vol. 14(1), pages 1-12, December.

    More about this item

    Statistics

    Access and download statistics

    Corrections

    All material on this site has been provided by the respective publishers and authors. You can help correct errors and omissions. When requesting a correction, please mention this item's handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-36103-0. See general information about how to correct material in RePEc.

    If you have authored this item and are not yet registered with RePEc, we encourage you to do it here. This allows to link your profile to this item. It also allows you to accept potential citations to this item that we are uncertain about.

    If CitEc recognized a bibliographic reference but did not link an item in RePEc to it, you can help with this form .

    If you know of missing items citing this one, you can help us creating those links by adding the relevant references in the same way as above, for each refering item. If you are a registered author of this item, you may also want to check the "citations" tab in your RePEc Author Service profile, as there may be some citations waiting for confirmation.

    For technical questions regarding this item, or to correct its authors, title, abstract, bibliographic or download information, contact: Sonal Shukla or Springer Nature Abstracting and Indexing (email available below). General contact details of provider: http://www.nature.com .

    Please note that corrections may take a couple of weeks to filter through the various RePEc services.

    IDEAS is a RePEc service. RePEc uses bibliographic data supplied by the respective publishers.