Stereospecific and Stereoselective Reactions. V. Alkylation of Active Methylene Compounds by the Use of Alcohols, Diethyl Azodicarboxylate, and Triphenylphosphine

Article abstract of DOI:10.1246/bcsj.54.2107

The reagent formed by the reaction of diethyl azodicarboxylate (1) and triphenylphosphine (2) reacted with alcohols and ethyl cyanoacetate (6) to give alkylated products in 30 - 80percent yields.When ethyl acetoacetate, 1,3-1,3-coclopentanedione, or 1,3-cyclohexanedione was used in place of 6, the corresponding O-alkylated products were obtained.The reaction of either (S)-(-)-ethyl lactate or (S)-(-)-ethyl 2-hydroxy-3-phenylpropionate with 1, 2, and 6, followed by hydrolysis resulted in the formation of (S)-(-)-methylsuccinic acid or (S)-(-)-benzylsuccinic acid.The results indicate that nearly complete inversion of the configuration takes place in the alkylation step.