Phosphono and Phosphino Analogues and Derivatives of the Natural Aminocarboxylic Acids and Peptides 1. Synthesis and Enzyme-Substrate Interactions of N-Phosphono-, and N-Phosphinomethylated Cyclic Amides

Ivan A. Natchev

doi:10.1055/s-1987-28175

Synthesis 1987; 1987(12): 1079-1084
DOI: 10.1055/s-1987-28175

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Phosphono and Phosphino Analogues and Derivatives of the Natural Aminocarboxylic Acids and Peptides 1. Synthesis and Enzyme-Substrate Interactions of N-Phosphono-, and N-Phosphinomethylated Cyclic Amides

Ivan A. Natchev^*

^*Research Centre "Konstrukcionni Polymeri", 5-003 Gara lskar, BG-1528 Sofia, Bulgaria

Abstract

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In analogy to the Arbuzov reaction, phosphorylation has been carried out on the N-hydroxymethylated cyclic amides, dioxopiperazine 1, hydantoine 4, and the L-pyrrolidinones 10, 11 and 12, with triethylphosphite and diethyl methylphosphonite, to give the organophosphorous derivatives 2, 3, 5-8, 13-18, respectively. For the first time, strict selectivity has been observed in the enzyme-substrate interaction of esters of organophosphorous acids with the phosphoesterase enzymes phosphodiesterase I and alkaline phosphatase. The enzyme phosphodiesterase I enhances the hydrolysis of esters of phosphonic and phosphinic acids to the corresponding free acids 19-26, whereas alkaline phosphatase catalyzes the hydrolysis of only one of the two diethoxyphosphono groups to monoethoxyphosphono derivatives 27-29. A general synthesis pathway has been developed for enzyme-catalyzed hydrolysis of the above esters.

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