Exploring the scope of the copper-catalyzed cascade addition of vinyl Grignard reagents to carboxylic esters, a set of substituted homoallylic ketones (γ, δ-unsaturated ketones) have been synthesized in 11%-94% yields from treatment of methyl 4-methoxybenzoate and methyl N-Boc-β-alaninate with different methyl-, dimethyl-, and phenyl-substituted vinyl Grignard reagents in the presence of catalytic amounts of CuCN in THF. The respective 2, ...