N to C aryl migration in lithiated carbamates: α-arylation of benzylic alcohols

Jonathan Clayden (Lead / Corresponding author), William Farnaby, Damian M. Grainger, Ulrich Hennecke, Michele Mancinelli, Daniel J. Tetlow, Ian H. Hillier, Mark A. Vincent

Research output: Contribution to journalArticlepeer-review

46 Citations (Scopus)


We report a new mode of reactivity displayed by lithiated O-benzyl carbamates carrying an N-aryl substituent: upon lithiation, the N-aryl group is transferred cleanly from N to C. An arylation of the carbamate results, providing a route to @,@-arylated secondary or tertiary alcohols. We also report density functional theory calculations supporting the proposal that arylation proceeds through a dearomatizing attack on the aromatic ring, a significantly lower energy pathway than the 1,2-acyl transfer observed with related N-alkyl carbamates.

Original languageEnglish
Pages (from-to)3410-3411
Number of pages2
JournalJournal of the American Chemical Society
Issue number10
Early online date18 Feb 2009
Publication statusPublished - 18 Mar 2009


  • Solvents
  • Additives
  • Alcohols
  • Organic compounds
  • Rearrangement

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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