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β‐ and γ‐Disubstituted Olefins: Substrates for Copper‐Catalyzed Asymmetric Allylic Substitution
Author(s) -
Falciola Caroline A.,
TissotCroset Karine,
Reyneri Hugo,
Alexakis Alexandre
Publication year - 2008
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200800086
Subject(s) - chemistry , allylic rearrangement , stereocenter , electrophile , reagent , tsuji–trost reaction , copper , catalysis , ligand (biochemistry) , substitution reaction , combinatorial chemistry , enantioselective synthesis , medicinal chemistry , organic chemistry , receptor , biochemistry
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.