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

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Abstract

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
Number of pages9
JournalAdvanced Synthesis and Catalysis
Early online date14 Apr 2020
DOIs
Publication statusE-pub ahead of print - 14 Apr 2020

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Keywords

  • radical
  • Truce-Smiles rearrangement
  • silane
  • KOtBu

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