β-Silyl β-amino acids and derivatives have proven utility as building blocks for molecules with applications in pharmaceutical and material science. Silicon-containing β-amino acids are virtually unknown, but are expected to exhibit different properties than the carbon analogues, such as lipophilicity. Reverse aza-Brook rearrangement reaction was efficiently applied in the synthesis of β-silyl β-amino acids. β-Silyl dipeptide has been made from the corresponding β-silyl β-amino acid.