β-Isocupreidine (β-ICD)-catalyzed asymmetric Baylis−Hillman reactions of aromatic imines with 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA)
give (S)-enriched N-protected-α-methylene-β-amino acid esters. In contrast to the corresponding aldehydes, imines show the opposite
enantioselectivity. A mechanistic proposal governed by hydrogen bonding is presented.