Synthesis of c(αα)-unsymmetrically disubstituted nitroesters by electron transfer C-alkylation of ethyl 2-nitropropionate anion

Article abstract of DOI:10.1016/S0040-4020(98)00194-X

The ethyl 2-nitropropionate anion was shown to react with six reductive alkylating agents to give new C(αα)-unsymmetrically disubstituted nitroesters and in some cases new ethyl monosubstituted methacrylates. The C- alkylation was shown to proceed by the S(RN)1 mechanism which was confirmed by the classical criteria for S(RN)1 reaction: the electron-withdrawing group effect and classical inhibition experiments by dioxygen, p-dinitrobenzene, cupric chloride or TEMPO. For example, ethyl 2-methyl-2-nitro-3-p- nitrophenylpropionate was transformed in the corresponding amino acid.