Chemodivergence in Enantioselective Desymmetrization of Diazabicycles: Ring-Opening versus Reductive Arylation†
Frederic Menard
Davenport Chemistry Laboratories, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6, Canada, Fax: (+1) 416-946-8185
Search for more papers by this authorMark Lautens Prof.
Davenport Chemistry Laboratories, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6, Canada, Fax: (+1) 416-946-8185
Search for more papers by this authorFrederic Menard
Davenport Chemistry Laboratories, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6, Canada, Fax: (+1) 416-946-8185
Search for more papers by this authorMark Lautens Prof.
Davenport Chemistry Laboratories, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6, Canada, Fax: (+1) 416-946-8185
Search for more papers by this authorThis 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.
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 CH insertion/1,4-metal migration occurs to give reductive arylation products (left).
Supporting Information
Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z704708_s.pdf or from the author.
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
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