Several new N-Boc-protected α-aminoacylsilanes from l-phenylalanine and l-isoleucine are synthesized via silylcupration of the corresponding imidazolides. The addition reaction of nucleophiles to the carbonyl moiety gives satisfactory yields of highly functionalized β-amino alcohols and statine analogues. The diastereoselectivity ranges from 30 to 98% and depends upon the nature of the C-nucleophile, on the structure of the starting amino acid as well as on the chelating properties of the Lewis acid employed.