Preparation of N-protected allylic amines and α-methylene-β-amino acids from vinylalumination/Baylis–Hillman products via tandem SN2′ substitution–Overman rearrangement

SN2′ 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.