Abstract The aza-Michael addition of secondary amines to α, β-or β, β-disubstituted α, β- unsaturated esters was efficiently achieved under high pressure (10–16 kbar) in protic solvents in the absence of any catalyst. The expected cumbersome β-aminoesters bearing a tertiary amine directly connected to a quaternary carbon atom could be isolated in fair to good yields. By using α, β, δ, γ-unsaturated esters (alkyl sorbate), the addition took place ...