Synfacts 2008(3): 0272-0272  
DOI: 10.1055/s-2008-1042701
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

1,2,3-Trisubstituted Indanes via Tandem Conjugate Additions

Contributor(s):Mark Lautens, Frédéric Ménard
C. Navarro, A. G. Csákӱ*
Universidad Complutense, Madrid, Spain
Stereoselective Rh(I)-Catalyzed Tandem Conjugate Addition of Boronic Acids-Michael Cyclization
Org. Lett.  2008,  10:  217-219  
Further Information

Publication History

Publication Date:
21 February 2008 (online)


Significance

The method provides a simple way to prepare highly substituted indane molecules. In one domino sequence, a boronic acid added to the unsaturated system and the resulting enolate cyclizes on the pendant second Michael acceptor. The diastereoselectivity observed was good and favored the thermodynamically more stable all-trans product. Though esters were not suitable substrates for the reaction, the authors showed that they could still be accessed via a Baeyer-Villiger oxidation of the phenyl ketones.

Review

L. F. Tietze, G. Brasche, K. Gericke In Domino Reactions in Organic Synthesis; Wiley-VCH: Weinheim, 2006, 631.

Comment

In cases where the Michael acceptors were different (R1 ∂ R2), the initial addition occurred on the system with the lowest LUMO, i.e. phenyl over methyl ketone. Since the relative stereo­chemistry is controlled by an irreversible initial addition of the organorhodium nucleophile, it should be possible to obtain the cyclized product enantio­selectively with the same level of diastereo­selectivity - especially in view of the success of Hayashi’s work with similar systems (T. Hayashi, K. Yamasaki Chem. Rev. 2003, 103, 2829).