Communication

Decoupling Deprotonation from Metalation: Thia-Fries Rearrangement†

  1. Alan M. Dyke Dr.1,
  2. Duncan M. Gill Dr.2,
  3. Jeremy N. Harvey Prof. Dr.1,
  4. Alison J. Hester Dr.1,
  5. Guy C. Lloyd-Jones Prof. Dr.1,
  6. M. Paz Muñoz Dr.1,
  7. Ian R. Shepperson Dr.1

Article first published online: 27 MAY 2008

DOI: 10.1002/anie.200800750

Issue

Angewandte Chemie International Edition

Angewandte Chemie International Edition

Volume 47, Issue 27, pages 5067–5070, June 23, 2008

Additional Information

How to Cite

Dyke, Alan M., Gill, Duncan M., Harvey, Jeremy N., Hester, Alison J., Lloyd-Jones, Guy C., Muñoz, M. Paz. and Shepperson, Ian R. (2008), Decoupling Deprotonation from Metalation: Thia-Fries Rearrangement. Angew. Chem. Int. Ed., 47: 5067–5070. doi: 10.1002/anie.200800750

Author Information

  1. 1

    School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS (UK), Fax: (+44) 117-929-8611

  2. 2

    Process R&D, AstraZeneca R&D Charnwood, Bakewell Road, Loughborough, LE11 5RH (UK)

  1. †

    We thank AstraZeneca and the MEC (Spain) for generous funding.

Publication History

  1. Issue published online: 16 JUN 2008
  2. Article first published online: 27 MAY 2008
  3. Manuscript Received: 14 FEB 2008

Funded by

  • AstraZeneca
  • MEC

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Keywords:

  • basicity;
  • metalation;
  • migration;
  • rearrangements;
  • superbases
Thumbnail image of graphical abstract

Label-enabled: Studies with 2H-, 18O-, and 34S-labeled aryl triflates show that lithium diisopropylamide-mediated thia-Fries rearrangement proceeds through an irreversible ortho deprotonation (see scheme; DIPA=diisopropylamine, LDA=lithium diisopropylamide). In contrast, ortho metalation results exclusively in the generation of a benzyne.

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