Highly enantioselective allylic amination and alkylation of racemic sterically hindered aryl-substituted Morita-Baylis-Hillman (MBH) adducts have been achieved by using an in situ formed Pd-catalyst from an axially chiral phenanthroline ligand. This dynamic kinetic asymmetric transformation (DYKAT) is compatible with cyclic and acyclic secondary amines, dialkyl malonates, β-keto esters, acetylacetone, and malononitrile, affording the corresponding chiral products, such as β-amino acid esters, in up to 95% yield and with up to a 99:1 enantiomeric ratio.