Description:
<jats:title>Abstract</jats:title><jats:p>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% <jats:italic>ee</jats:italic>) with very good γ‐selectivities on a wide panel of aliphatic or aromatic β‐disubstituted substrates.</jats:p>