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Synthesis 2009(12): 2101-2112  
DOI: 10.1055/s-0029-1216838
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart ˙ New York

Copper-Catalyzed Asymmetric Ring-Opening Reaction of Oxabenzonorbornadienes with Grignard and Aluminum Reagents

Renaud Millet, Ludovic Gremaud, Tania Bernardez, Laëtitia Palais, Alexandre Alexakis*
Department of Organic Chemistry, University of Geneva, 30 Quai Ernest Ansermet, 1211 Geneva 4, Switzerland
Fax: +41(22)3793215; e-Mail: alexandre.alexakis@chiorg.unige.ch;
Further Information

Publication History

Received 7 April 2009
Publication Date:
19 May 2009 (online)

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Abstract

A highly enantioselective method for the copper-catalyzed desymmetrization of oxabenzonorbornadienes with aluminum reagents and SimplePhos as chiral ligand has been developed. The same reaction with Grignard reagents is also reported. A wide range of alkyl chains have been used with moderate to high enantio­selectivity and high trans selectivity. The transfer of a methyl group is also reported with high enantiomeric and diastereomeric excess and yields for different substrates. We finally have been able to perform the first trans enantioselective desymmetrization of oxabenzonorbornadienes with an aromatic group.

Key words

copper catalysis - asymmetric transformation - Grignard reagents - aluminum reagents - SimplePhos

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