IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v13y2022i1d10.1038_s41467-022-35141-4.html
   My bibliography  Save this article

Azoarene activation for Schmidt-type reaction and mechanistic insights

Author

Listed:
  • Fan-Tao Meng

    (Jiangsu Normal University)

  • Ya-Nan Wang

    (Zhengzhou University)

  • Xiao-Yan Qin

    (Jiangsu Normal University)

  • Shi-Jun Li

    (Zhengzhou University)

  • Jing Li

    (Jiangsu Normal University)

  • Wen-Juan Hao

    (Jiangsu Normal University)

  • Shu-Jiang Tu

    (Jiangsu Normal University)

  • Yu Lan

    (Zhengzhou University)

  • Bo Jiang

    (Jiangsu Normal University)

Abstract

The Schmidt rearrangement, a reaction that enables C-C or C-H σ bond cleavage and nitrogen insertion across an aldehyde or ketone substrate, is one of the most important and widely used synthetic tools for the installation of amides and nitriles. However, such a reaction frequently requires volatile, potentially explosive, and highly toxic azide reagents as the nitrogen donor, thus limiting its application to some extent. Here, we show a Schmidt-type reaction where aryldiazonium salts act as the nitrogen precursor and in-situ-generated cyclopenta-1,4-dien-1-yl acetates serve as pronucleophiles from gold-catalyzed Nazarov cyclization of 1,3-enyne acetates. Noteworthy is that cycloketone-derived 1,3-enyne acetates enabled ring-expansion relay to access a series of 2-pyridone-containing fused heterocycles, in which nonsymmetric cycloketone-derived counterparts demonstrated high regioselectivity. Aside from investigating the scope of this Schmidt-type reaction, mechanistic details of this transformation are provided by performing systematic theoretical calculations.

Suggested Citation

  • Fan-Tao Meng & Ya-Nan Wang & Xiao-Yan Qin & Shi-Jun Li & Jing Li & Wen-Juan Hao & Shu-Jiang Tu & Yu Lan & Bo Jiang, 2022. "Azoarene activation for Schmidt-type reaction and mechanistic insights," Nature Communications, Nature, vol. 13(1), pages 1-12, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-35141-4
    DOI: 10.1038/s41467-022-35141-4
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-022-35141-4
    File Function: Abstract
    Download Restriction: no
    File URL: https://libkey.io/10.1038/s41467-022-35141-4?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
    ---><---

    References listed on IDEAS

    as
    1. Manwika Charaschanya & Jeffrey Aubé, 2018. "Reagent-controlled regiodivergent ring expansions of steroids," Nature Communications, Nature, vol. 9(1), pages 1-8, December.
    2. Francisco Juliá-Hernández & Toni Moragas & Josep Cornella & Ruben Martin, 2017. "Remote carboxylation of halogenated aliphatic hydrocarbons with carbon dioxide," Nature, Nature, vol. 545(7652), pages 84-88, May.
    3. Zachary C. Litman & Yajie Wang & Huimin Zhao & John F. Hartwig, 2018. "Cooperative asymmetric reactions combining photocatalysis and enzymatic catalysis," Nature, Nature, vol. 560(7718), pages 355-359, 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. Qingyun Wang & Shuquan Wu & Juan Zou & Xuyang Liang & Chengli Mou & Pengcheng Zheng & Yonggui Robin Chi, 2023. "NHC-catalyzed enantioselective access to β-cyano carboxylic esters via in situ substrate alternation and release," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    2. Yunting Liu & Teng Ma & Zhongxu Guo & Liya Zhou & Guanhua Liu & Ying He & Li Ma & Jing Gao & Jing Bai & Frank Hollmann & Yanjun Jiang, 2024. "Asymmetric α-benzylation of cyclic ketones enabled by concurrent chemical aldol condensation and biocatalytic reduction," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    3. Zhiyong Sun & René Hübner & Jian Li & Changzhu Wu, 2022. "Artificially sporulated Escherichia coli cells as a robust cell factory for interfacial biocatalysis," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    4. Sergio Sanz-Navarro & Marta Mon & Antonio Doménech-Carbó & Rossella Greco & Jorge Sánchez-Quesada & Estela Espinós-Ferri & Antonio Leyva-Pérez, 2022. "Parts–per–million of ruthenium catalyze the selective chain–walking reaction of terminal alkenes," Nature Communications, Nature, vol. 13(1), pages 1-9, 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_s41467-022-35141-4. 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.

    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.