IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v13y2022i1d10.1038_s41467-022-28288-7.html
   My bibliography  Save this article

Enantioselective Cu(I)-catalyzed borylative cyclization of enone-tethered cyclohexadienones and mechanistic insights

Author

Listed:
  • Sandip B. Jadhav

    (CSIR-Indian Institute of Chemical Technology (CSIR-IICT)
    Academy of Scientific and Innovative Research (AcSIR))

  • Soumya Ranjan Dash

    (Academy of Scientific and Innovative Research (AcSIR)
    CSIR-National Chemical Laboratory)

  • Sundaram Maurya

    (CSIR-Indian Institute of Chemical Technology (CSIR-IICT)
    Academy of Scientific and Innovative Research (AcSIR))

  • Jagadeesh Babu Nanubolu

    (Academy of Scientific and Innovative Research (AcSIR)
    CSIR-Indian Institute of Chemical Technology (CSIR-IICT))

  • Kumar Vanka

    (Academy of Scientific and Innovative Research (AcSIR)
    CSIR-National Chemical Laboratory)

  • Rambabu Chegondi

    (CSIR-Indian Institute of Chemical Technology (CSIR-IICT)
    Academy of Scientific and Innovative Research (AcSIR))

Abstract

The catalytic asymmetric borylation of conjugated carbonyls followed by stereoselective intramolecular cascade cyclizations with in situ generated chiral enolates are extremely rare. Herein, we report the enantioselective Cu(I)-catalyzed β-borylation/Michael addition on prochiral enone-tethered 2,5-cyclohexadienones. This asymmetric desymmetrization strategy has a broad range of substrate scope to generate densely functionalized bicyclic enones bearing four contiguous stereocenters with excellent yield, enantioselectivity, and diastereoselectivity. One-pot borylation/cyclization/oxidation via the sequential addition of sodium perborate reagent affords the corresponding alcohols without affecting yield and enantioselectivity. The synthetic potential of this reaction is explored through gram-scale reactions and further chemoselective transformations on products. DFT calculations explain the requirement of the base in an equimolar ratio in the reaction, as it leads to the formation of a lithium-enolate complex to undergo C-C bond formation via a chair-like transition state, with a barrier that is 22.5 kcal/mol more favourable than that of the copper-enolate complex.

Suggested Citation

  • Sandip B. Jadhav & Soumya Ranjan Dash & Sundaram Maurya & Jagadeesh Babu Nanubolu & Kumar Vanka & Rambabu Chegondi, 2022. "Enantioselective Cu(I)-catalyzed borylative cyclization of enone-tethered cyclohexadienones and mechanistic insights," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-28288-7
    DOI: 10.1038/s41467-022-28288-7
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-022-28288-7
    File Function: Abstract
    Download Restriction: no
    File URL: https://libkey.io/10.1038/s41467-022-28288-7?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. Cathleen M. Crudden & Christopher Ziebenhaus & Jason P. G. Rygus & Kazem Ghozati & Phillip J. Unsworth & Masakazu Nambo & Samantha Voth & Marieke Hutchinson & Veronique S. Laberge & Yuuki Maekawa & Da, 2016. "Iterative protecting group-free cross-coupling leading to chiral multiply arylated structures," Nature Communications, Nature, vol. 7(1), pages 1-7, April.
    2. Fanke Meng & Kevin P. McGrath & Amir H. Hoveyda, 2014. "Multifunctional organoboron compounds for scalable natural product synthesis," Nature, Nature, vol. 513(7518), pages 367-374, September.
    3. Weijun Yao & Xiaowei Dou & Shan Wen & Ji’en Wu & Jagadese J. Vittal & Yixin Lu, 2016. "Enantioselective desymmetrization of cyclohexadienones via an intramolecular Rauhut–Currier reaction of allenoates," Nature Communications, Nature, vol. 7(1), pages 1-8, December.
    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.

      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:13:y:2022:i:1:d:10.1038_s41467-022-28288-7. 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.