Synfacts 2011(3): 0277-0277  
DOI: 10.1055/s-0030-1259478
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart ˙ New York

1,4-Rhodium-Silicon Shift in an Enantioselective Synthesis of Indanols

Contributor(s):Mark Lautens, Jane Panteleev
T. Seiser, N. Cramer*
ETH Zürich, Switzerland
Rhodium(I)-Catalyzed 1,4-Silicon Shift of Unactivated Silanes from Aryl to Alkyl: Enantioselective Synthesis of Indanol Derivatives
Angew. Chem. Int. Ed.  2010,  49:  10163-10167  
Further Information

Publication History

Publication Date:
16 February 2011 (online)


The tendency of rhodium and palladium catalysts to undergo 1,4-shifts from alkyl or vinyl to aryl positions is a well-documented phenomenon (see Review). In contrast to their earlier work (Angew. Chem. Int. Ed. 2009, 48, 6320), the authors describe a 1,4-rhodium-silicon shift. This strategy is superior to the rhodium-hydrogen shift in the sense that functionality is introduced at the alkyl position, which can be easily further modified.

Review: F. Shi, R. C. Larock Top. Curr. Chem. 2010, 292, 123-164.


Several selectivity issues were addressed by this work. High enantioselectivity in β-carbon cleavage could be achieved for the trans products using Difluorphos or Dolefin ligands. The trans/cis selectivity of the ketone addition could be modulated by the solvent and the ligand used. Olefin ligands were selective for silicon versus ­hydrogen migrations, with phosphine ligands ­favoring hydrogen shifts. Tricyclic products could also be formed, possibly from a rhodium-catalyzed Si-alkyl insertion. The silicon group could easily be converted into an alcohol, and vinyl or allyl silyl groups could also participate in the migration.