The synthesis of four types of optically active β-carbon-substituted analogs of threo-β- hydroxy aspartate (THA) and a β-carbon-substituted analog of threo-β-benzyloxy aspartate (TBOA), which are potent blockers of excitatory amino acid transporters in the mammalian central nervous system, via the chirality-transferring ester–enolate Claisen rearrangement of α-acyloxytrialkylsilane is described.