IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v13y2022i1d10.1038_s41467-022-33432-4.html
   My bibliography  Save this article

Stereodivergent dehydrative allylation of β-keto esters using a Ru/Pd synergistic catalyst

Author

Listed:
  • Thien Phuc Le

    (Nagoya University)

  • Shinji Tanaka

    (National Institute of Advanced Industrial Science and Technology (AIST))

  • Masahiro Yoshimura

    (Aichi Gakuin University)

  • Kazuhiko Sato

    (National Institute of Advanced Industrial Science and Technology (AIST))

  • Masato Kitamura

    (Nagoya University)

Abstract

α-Alkylation of a β-keto ester is a frequently used reaction for carbon–carbon bond formation. However, extension to a stereoselective reaction remains a significant challenge, because the product easily racemizes under acidic or basic conditions. Here, we report a hybrid system consisting of Pd and Ru complexes that catalyzes the asymmetric dehydrative condensation between cinnamyl-type allylic alcohols and β-keto esters. α-Non-substituted β-keto ester can be allylated to afford an α-mono-substituted product with high regio-, diastereo-, and enantioselectivity. No epimerization occurs owing to the nearly neutral conditions, which is achieved by a rapid proton transfer from Pd-enolate formation to Ru π-allyl complex formation. Four diastereomers can be synthesized on demand by changing the stereochemistry of the Pd or Ru complex. Eight stereoisomers with three adjacent stereogenic centers can be synthesized by employing diastereoselective reduction of the ketone in the products. The formal synthesis of (+)-pancratistatin demonstrates the utility of the reaction.

Suggested Citation

  • Thien Phuc Le & Shinji Tanaka & Masahiro Yoshimura & Kazuhiko Sato & Masato Kitamura, 2022. "Stereodivergent dehydrative allylation of β-keto esters using a Ru/Pd synergistic catalyst," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
  • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-33432-4
    DOI: 10.1038/s41467-022-33432-4
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-022-33432-4
    File Function: Abstract
    Download Restriction: no

    File URL: https://libkey.io/10.1038/s41467-022-33432-4?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
    ---><---

    Citations

    Citations are extracted by the CitEc Project, subscribe to its RSS feed for this item.
    as


    Cited by:

    1. Cong Fu & Ling He & Hui Xu & Zongpeng Zhang & Xin Chang & Yanfeng Dang & Xiu-Qin Dong & Chun-Jiang Wang, 2024. "Modular access to chiral bridged piperidine-γ-butyrolactones via catalytic asymmetric allylation/aza-Prins cyclization/lactonization sequences," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    2. Ruimin Lu & Qinglin Zhang & Chang Guo, 2023. "Catalytic stereodivergent allylic alkylation of 2-acylimidazoles for natural product synthesis," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    3. Chang You & Mingying Shi & Xueling Mi & Sanzhong Luo, 2023. "Asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysis," Nature Communications, Nature, vol. 14(1), pages 1-7, 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:13:y:2022:i:1:d:10.1038_s41467-022-33432-4. 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.

    We have no bibliographic references for this item. You can help adding them by using 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.