Subscribe to RSS
DOI: 10.1055/s-0033-1340687
Transfer of Chirality for Synthesis of Bicyclo[5.3.0]decatrienes
Transfer of Chirality in the Rhodium-Catalyzed Intramolecular [5+2] Cycloaddition of 3-Acyloxy-1,4-enynes (ACEs) and Alkynes: Synthesis of Enantioenriched Bicyclo[5.3.0]decatrienes.
Angew. Chem. Int. Ed. 2013;
52: 13601-13605
Publication History
Publication Date:
17 February 2014 (online)
Significance
The authors describe a novel synthesis of bicycle[5.3.0]decatrienes utilizing transfer of chirality in the rhodium-catalyzed [5+2] cycloaddition of 3-acyloxy-1,4-enynes (ACEs) with tethered alkynes. The bicyclo[5.3.0]decatrienes are obtained in moderate to good yields (up to 88%) and enantioselectivities (up to 95%).
#
Comment
Toste and co-workers (J. Am. Chem. Soc. 2005, 127, 5802) previously reported the synthesis of cyclopentanones via gold(I)-catalyzed transfer of chirality from ACEs (Δee = 2–9%). A center-to-helix-to-center chirality-transfer mechanism was proposed in this Rautenstrauch rearrangement (O. Nieto Faza , C. Silva López , R. Álvarez, A. R. de Lera J. Am. Chem. Soc. 2006, 128, 2434). The mechanistic rational in the present work suggests that the same mechanism is not operative in the rhodium(I)-catalyzed [5+2] cycloaddition. A possible reason for the erosion of enantiomeric excess is also discussed.
#
#