Full Paper

Isothiourea-Mediated Asymmetric O- to C-Carboxyl Transfer of Oxazolyl Carbonates: Structure–Selectivity Profiles and Mechanistic Studies

  1. Caroline Joannesse1,
  2. Craig P. Johnston1,
  3. Louis C. Morrill1,
  4. Philip A. Woods1,
  5. Madeleine Kieffer1,
  6. Dipl.-Chem. Tobias A. Nigst2,
  7. Prof. Herbert Mayr2,
  8. Dr. Tomas Lebl1,
  9. Prof. Douglas Philp1,
  10. Dr. Ryan A. Bragg3,
  11. Dr. Andrew D. Smith1,*

Article first published online: 19 JAN 2012

DOI: 10.1002/chem.201102847

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 18, Issue 8, pages 2398–2408, February 20, 2012

Additional Information

How to Cite

Joannesse, C., Johnston, C. P., Morrill, L. C., Woods, P. A., Kieffer, M., Nigst, T. A., Mayr, H., Lebl, T., Philp, D., Bragg, R. A. and Smith, A. D. (2012), Isothiourea-Mediated Asymmetric O- to C-Carboxyl Transfer of Oxazolyl Carbonates: Structure–Selectivity Profiles and Mechanistic Studies. Chem. Eur. J., 18: 2398–2408. doi: 10.1002/chem.201102847

Author Information

  1. 1

    EaStCHEM, School of Chemistry, University of St Andrews, North Haugh, St Andrews, KY16 9ST (United Kingdom)

  2. 2

    Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5–13 (Haus F), 81377 München (Germany)

  3. 3

    AstraZeneca UK Ltd, Mereside, Alderley Park, Macclesfield, Cheshire, SK10 4TG (United Kingdom)

*EaStCHEM, School of Chemistry, University of St Andrews, North Haugh, St Andrews, KY16 9ST (United Kingdom)

Publication History

  1. Issue published online: 10 FEB 2012
  2. Article first published online: 19 JAN 2012
  3. Manuscript Received: 12 SEP 2011

Funded by

  • Royal Society for a University Research Fellowship
  • EPSRC
  • Fonds der Chemischen Industrie

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Keywords:

  • asymmetric catalysis;
  • isothioureas;
  • Lewis bases;
  • NMR spectroscopy;
  • reaction mechanisms

Abstract

The structural motif within a series of tetrahydropyrimidine-based isothioureas necessary for generating high asymmetric induction in the asymmetric Steglich rearrangement of oxazolyl carbonates is fully explored, with crossover and dynamic 19F NMR experiments used to develop a mechanistic understanding of this transformation.

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