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Synfacts 2008(5): 0485-0485  
DOI: 10.1055/s-2008-1072664
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Rhodium-Catalyzed Enantioselective Hydroacylation of Ketones

Contributor(s):Mark Lautens, Praew Thansandote
Z. Shen, H. A. Khan, V. M. Dong*
University of Toronto, Canada
Rh-Catalyzed Carbonyl Hydroacylation: An Enantioselective Approach to Lactones
J. Am. Chem. Soc.  2008,  130:  2916-2917  
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Publication History

Publication Date:
23 April 2008 (online)

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Key words

rhodium - ketone hydroacylation - enantioselective lactonization

Significance

A conceptually novel approach to enantioselective lactonization is presented based on a previously unknown Rh-catalyzed C-H bond activation and intramolecular hydroacylation of ketones. The phosphine ligand is crucial since increased phosphine basicities improved the selectivity of the product over the competing decarbonylation of starting material. Excellent yields and enantioselectivities are seen for a variety of aromatic and aliphatic ketones.

Comment

The intramolecular hydroacylation occurs with complete regiocontrol to form Tishchenko-type products instead of benzoin-type products. The present methodology is atom-economic and provides a great alternative to popular lactonization strategies such as the Yamaguchi macrolactonization.

Review

For a review on macrolactonizations, see: A. Parenty, X. Moreau, J.-M. Campagne Chem. Rev. 2006 , 106, 911.

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