Direct insertion into the C–C bond of unactivated ketones with NaH-mediated aryne chemistry

Fan Luo, Chen Long Li, Peng Ji, Yuxin Zhou, Jingjing Gui, Lingyun Chen, Yuejia Yin, Xinyu Zhang, Yanwei Hu, Xiaobei Chen, Xuejun Liu, Xiaodong Chen, Zhi Xiang Yu, Wei Wang, Shi Lei Zhang

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

Here, we document the reinvention of aryne chemistry with “old” o-diiodoarenes as aryne progenitors. We have established a NaH-mediated activation strategy for the generation of highly reactive aryne species in a controlled manner. The resulting arynes can efficiently participate in a C–C σ-bond-insertion reaction with unactivated ketones, which is difficult to achieve by existing methods. Density functional theory (DFT) calculations reveal that the two adjacent iodines in o-diiodoarenes play critical roles in the formation of aryne. The nucleophilic attack of hydride to the electrophilic iodine requires that the adjacent iodine act as a directing group to accelerate this process, whereas mono-substituted iodobenzene lacking the neighboring-group participation makes it difficult. The in-situ-formed enolates from ketones are proposed to adopt tetrameric aggregates to react with arynes, which accounts for the high regiochemistry for substrates with bulky substituents.

Original languageEnglish (US)
Pages (from-to)2620-2636
Number of pages17
JournalChem
Volume9
Issue number9
DOIs
StatePublished - Sep 14 2023

Keywords

  • SDG12: Responsible consumption and production
  • SDG3: Good health and well-being
  • SDG9: Industry, innovation, and infrastructure
  • aryne chemistry
  • insertion reaction
  • o-diiodoarenes
  • sodium hydride
  • unactivated ketones

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry
  • Environmental Chemistry
  • General Chemical Engineering
  • Biochemistry, medical
  • Materials Chemistry

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