Reaction of N-Acyl-alpha-triphenylphosphonio-alpha-amino Acid Esters with Organic Bases: Mechanism of the Base-Catalyzed Nucleophilic Substitution of the Triphenylphosphonium Group

摘要

Reactions of N-acyl-alpha-triphenylphosphonio-alpha-amino acid methyl esters with organic bases (triethylamine or DBU) were investigated as the crucial step of the base-catalyzed displacement of the triphenylphosphonium group by nucleophiles. It was proved that N-acyl-alpha-triphenylphosphoniogly-cinates are transformed to an equilibrium mixture of the corresponding N-acyliminoacetates were detected to be the only primary reaction product which, however, can undergo further tautomerization to the corresponding alpha,beta-dehydeo-alpha-amino acid derivatives. In both these cases the reaction of N-acyl-alpha-triphenylphosphonio-alpha-amino acid esters with nucleophiles proceeds via the addition of a nucleophile to the activated C=N double bond of the N-acylimino intermediate.