Benzylic C-H functionalisation by [Et3SiH + KOtBu] leads to radical rearrangements in o-tolylaryl ethers, amines

Jude N. Arokianathar, Krystian Kolodziejczak, Frances E. Bugden, Kenneth F. Clark, Tell Tuttle, John A. Murphy

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Reaction of Et 3SiH+KO tBu with diaryl ethers, sulfides and amines that feature an ortho alkyl group leads to rearrangement products. The rearrangements arise from formation of benzyl radicals, likely formed through hydrogen atom abstraction by triethylsilyl radicals. The rearrangements involve cyclisation of the benzyl radical onto the partner arene, which, from computation, is the rate determining step. In the case of diaryl ethers, Truce-Smiles rearrangements arise from radical cyclisations to form 5-membered rings, but for diarylamines, cyclisations to form dihydroacridines are observed. (Figure presented.).

Original languageEnglish
Pages (from-to)2260-2267
Number of pages8
JournalAdvanced Synthesis and Catalysis
Issue number11
Early online date14 Apr 2020
Publication statusPublished - 26 May 2020


  • radical
  • Truce-Smiles rearrangement
  • silane
  • KOtBu

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