Communication

Chemodivergence in Enantioselective Desymmetrization of Diazabicycles: Ring-Opening versus Reductive Arylation†

  1. Frederic Menard,
  2. Mark Lautens Prof.

Article first published online: 7 FEB 2008

DOI: 10.1002/anie.200704708

Issue

Angewandte Chemie International Edition

Angewandte Chemie International Edition

Volume 47, Issue 11, pages 2085–2088, February 28, 2008

Additional Information

How to Cite

Menard, F. and Lautens, M. (2008), Chemodivergence in Enantioselective Desymmetrization of Diazabicycles: Ring-Opening versus Reductive Arylation. Angew. Chem. Int. Ed., 47: 2085–2088. doi: 10.1002/anie.200704708

Author Information

  1. Davenport Chemistry Laboratories, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6, Canada, Fax: (+1) 416-946-8185

  1. †

    This work was supported by NSERC, Merck-Frosst, and the University of Toronto. F.M. thanks the Government of Ontario for a postgraduate scholarship. Solvias Inc, Takasago, and Digital Specialty Chemicals are thanked for generous gifts of chiral ligands. We acknowledge A. Martins for the preparation of some substrates, a referee for useful comments, as well as Y. Bolshan for checking our experimental procedure.

Publication History

  1. Issue published online: 22 FEB 2008
  2. Article first published online: 7 FEB 2008
  3. Manuscript Revised: 14 DEC 2007
  4. Manuscript Received: 11 OCT 2007

Funded by

  • NSERC
  • Merck-Frosst
  • University of Toronto

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Keywords:

  • asymmetric catalysis;
  • C–H activation;
  • desymmetrization;
  • rhodium;
  • ring-opening reactions
Thumbnail image of graphical abstract

Divergent bicycle paths: A chemodivergent desymmetrization occurs after an initial enantioselective carbometalation step. The reaction brings a solution to the challenging problem of the enantioselective ring-opening of diazabicyclo[2.2.1]heptanes to obtain arylated cyclopentenamines (see scheme, right). An alternative reaction pathway was discovered in which C[BOND]H insertion/1,4-metal migration occurs to give reductive arylation products (left).

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