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<p>Discovery and application of reactive intermediates has prominently expedited the development of organic chemistry. In this respect, while ketene has been well recognized as a versatile intermediate for a wide range of transformations, practical application of difluoroketene remained virtually unrealized because of its highly reactive nature. Herein, we present a transition-metal-free approach for in situ generation of difluoroketene using difluorobromoacetylsilane as a precursor. The controlled release of chemically labile difluoroketene under mild conditions, achieved through desilylative β-elimination, establishes a foundation for successful development of its Belluš-Claisen rearrangement with allylic amines, Staudinger [2 + 2] cycloaddition with imines, [4 + 2] cycloaddition, as well as insertion into alcohols, amines, and thiols for their difluoroacetylation. A series of mechanistic experiments provide concrete support for the involvement of difluoroketene in these transformations.</p>

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Unlocking the reactivity of difluoroketene and its synthetic applications

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年3月28日

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  • Sheng Xi,
  • Chi Zhang,
  • Liying Fu,
  • Hai-Xiang Gao,
  • Wenjing Jia,
  • Hongrui Zhang,
  • Yuting Liu,
  • Xue-Qiang Chu,
  • Yu Zhang,
  • Kai Guo,
  • Chao Feng

摘要

Discovery and application of reactive intermediates has prominently expedited the development of organic chemistry. In this respect, while ketene has been well recognized as a versatile intermediate for a wide range of transformations, practical application of difluoroketene remained virtually unrealized because of its highly reactive nature. Herein, we present a transition-metal-free approach for in situ generation of difluoroketene using difluorobromoacetylsilane as a precursor. The controlled release of chemically labile difluoroketene under mild conditions, achieved through desilylative β-elimination, establishes a foundation for successful development of its Belluš-Claisen rearrangement with allylic amines, Staudinger [2 + 2] cycloaddition with imines, [4 + 2] cycloaddition, as well as insertion into alcohols, amines, and thiols for their difluoroacetylation. A series of mechanistic experiments provide concrete support for the involvement of difluoroketene in these transformations.