Preparation of N-Protected Allylic Amines and α-Methylene-β-amino Acids from Vinylalumination/Baylis—Hillman Products via Tandem SN2′ Substitution—Overman Rearrangement

S N 2′ reaction on the acetates obtained from vinylalumination or Baylis–Hillman products, followed by in situ reduction afforded allylic alcohols. Upon conversion to trichloroacetimidates and [3,3]-sigmatropic rearrangement, the corresponding N -protected β-substituted allylic amines were obtained in good yields. Utilization of hydroxy group as the nucleophile furnished allylic hydroxy esters, which were converted to protected α-methylene-β-amino acids via Overman rearrangement.