Iminodicarboxylic acid

The reductive alkylation of methyl pyruvate with and the t-butyl esters of amino acids using Pd/C catalyst leads to the formation of iminodicarboxylic acids such as 67 in selectivities of 29-75% d.e. depending on the amino acid and solvent used (hexane gave the best results). Hydrolysis of the t-butyl ester to the acid 68 followed by hypochlorite-promoted decarboxylation and imine hydrolysis leads to the formation of ( -alanine 69 in correspondingly high e.e.s278,281. The likely decarboxylation mechanism as far as the imine stage is shown in Scheme 65. 

Studies on the transamination reaction between f-butyl esters of optically active amino acids and methyl pyruvate were carried out, as shown in Scheme 7. The resulting iminodicarboxylic acid (16) was partially hydrolyzed and then oxidized with f-butyl hypochlorite to form alanine. The oxidation is a generally applicable one, and the optical purity of alanine is high (50-70%). Similar asymmetric transamination between an (S)-amino acid and ketones was carried out. Catalytic hydrogenation of the Schiff s bases prepared from a-keto acid esters and amino acid esters was carried out, and a substituent and temperature effect observed (de 40-70%). ... 

Depending on the reaction conditions, a-iminodicarboxylic acid derivatives or 2,6-di-piperazinediones [120] are formed from a-amino acids, oxocompounds and isocyanides. The isomeric 2,4-piperazinediones can thus also be formed by some of the U-4CR of vicinal diamines, isocyanides, oxocompounds and glyoxylic monoesters [121,122],The libraries of highly substituted 2-piperazones were produced by the chemists of Merck Inc. from N-monosubstituted ethylenediamines, carboxylic acids, isocyanides and chloroacetalde-hyde. 

Iminodicarboxylic acid derivatives such as 99 or 100 react with DBN to afford tricyclic uracil derivatives 101 which are found55 to be useful as plant protective agents Eq. (28). DBN has also been reported56 to react... 

Iminodicarboxylic acid diamides from cyanocarboxylic acid amides s. 15, 47 2 GN-vGHaNHGHg ... 

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