Abstract By using a methyl tetramate derivative (R)-or (S)-9 as a novel chiral building block, a direct, flexible, and highly enantioselective approach to methyl (R)-or (S)-5-alkyltetramates (2) is disclosed. Among the synthesized methyl 5-alkyltetramates 2, methyl 5- methyltetramate (2 a) is found in cytotoxic mirabimide E (4) and dysideapyrrolidone (5), and methyl 5-benzyltetramate (2 g) is a substructure in the potent antineoplastic dolastatin 15 ( ...