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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
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    References listed on IDEAS

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    1. 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.
    2. Manwika Charaschanya & Jeffrey Aubé, 2018. "Reagent-controlled regiodivergent ring expansions of steroids," Nature Communications, Nature, vol. 9(1), pages 1-8, December.
    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.
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