A series of alpha-silyl amino acids and their polypeptide derivatives have been studied to determine their stability and potential for applications in unnatural polypeptides and pharmaceuticals. These amino acids were prepared from furfurylamine, via reverse aza-Brook rearrangement followed by ozonolysis. The C-Si bond stability toward hydrolysis and methanolysis was evaluated as a function of the substituents on silicon, nitrogen and the carbonyl group, revealing an interesting interplay of steric and electronic effects.