β- and γ-Disubstituted Olefins: Substrates for Copper-Catalyzed Asymmetric Allylic Substitution

The copper‐catalyzed asymmetric allylic alkylation has shown through many examples that it is a powerful means to generate stereogenic centers with mono β‐ and γ‐substituted olefinic substrates. However, little has been reported about more substituted olefinic patterns, such as β‐disubstituted allyl...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2008-05, Vol.350 (7-8), p.1090-1100
Main Authors: Falciola, Caroline A., Tissot-Croset, Karine, Reyneri, Hugo, Alexakis, Alexandre
Format: Article
Language:English
Subjects:
allylic alkylation
allylic compounds
asymmetric catalysis
copper
nucleophilic substitution
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Summary:The copper‐catalyzed asymmetric allylic alkylation has shown through many examples that it is a powerful means to generate stereogenic centers with mono β‐ and γ‐substituted olefinic substrates. However, little has been reported about more substituted olefinic patterns, such as β‐disubstituted allylic electrophiles. In this paper, we show that a simple procedure using easily accessible Grignard reagents and as low as 3 mol% of copper/ligand can promote high to nearly perfect enantioselectivities (up to >99% ee) with very good γ‐selectivities on a wide panel of aliphatic or aromatic β‐disubstituted substrates.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.200800086