Reactivity of a propiolate dimer with nucleophiles and an efficient synthesis of dimethyl α-aminoadipate

An enyne dimer (1) of methyl propiolate was reacted with amines to form dimethyl (E,E)-2-amino-2,4-hexadiene dioates with remarkable chemospecificity, regiospecificity, and stereospecificity. This enyne was also reduced by Ph3P stereospecifically to form dimethyl (E,E)-muconic ester. Hydrogenation of the conjugated amino-diene led to an efficient production of dimethyl α-aminoadipate. A lactam of dimethyl α-aminoadipate was obtained in high yield by simply varying the hydrogenation conditions.