Asymmetric Heck reactions establish quaternary or tertiary stereocenters. If migratory insertion generates a quaternary center adjacent to the palladium-carbon bond (as in reactions of trisubstituted or 1,1-disubstituted alkenes), β-hydride elimination toward that center is not possible and it is retained in the product. Similarly, β-hydride elimination is not possible if a hydrogen syn to the palladium-carbon bond is not available. Thus, tertiary stereocenters can be established in conformationally restricted systems.