Mechanism of intramolecular mixed anhydride formation as intermediates in the reactions of N-phosphorylamino-acids —An MNDO research
N-phosphoryl-α-amino acids can react to form esters, peptides, phosphoryl ester-exchanged products and phosphoryl group migration products under mild conditions, which are very important in researches on arohebiont. It has been proposed that intramolecular mixed carboxylic-phosphoric anhydrides (IMCPAs) might be the common intermediates of the reactions, which are difficult to be experimentally observed because of their high activity. In this note, it has been revealed, by means of MNDO, that the IMCPAs arc situated at the relatively minimal points of the potential surface and can form in a non-synchronous concerted reaction pathway that passes through a transition state with a hydrogen-bond-bridge structure. The results give a successful explanation to the structure and formation of IMCPAs and their ability to promote the various reactions mentioned above.
KeywordsN-phosphorylamino-acid intramolecular mixed anhydride mechanism MNDO
Unable to display preview. Download preview PDF.
- 1.Li, Y. M., Yin, Y. W., Zhao, Y. F., Phosphoryl group participation leads to peptide formation from N-phmphorylemino acids,Int. J. Peptide Pmtein Res., 1992, 39: 375.Google Scholar
- 2.Cohen, P.,Recently Discorrend Systems of Enzyme Regulation by Reversible Phosporylation, New York: Elsevier/North Holland, 1980.Google Scholar
- 3.Zhm, Y. F., Li, Y. M., Yin, Y. W.et al., The interaction between phoephyl group and the side cham of amino acids,Science in China, Ser. B. 1993. 23(6): 561.Google Scholar
- 4.Wang, Q., Zhao, Y. F., An, F. L.et al., Observation of penta-coordinate phosphorus through the reaction of 1,2-phenylene phosphorochloridate and trimethylsilyl derivatives of α-amino acids,Science in China, Ser. B, 1995, 25(7): 683.Google Scholar
- 5.Zhao, Y. F., Ju, Y. Li, Y. M.et al., Self-activation of N-phosphmim acids and N-phoaph~dipe~tides in oligopeptide formation,J. Peptide Protein Res., 1995, 10: 1.Google Scholar