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Activity Difference between α-COOH and β-COOH in N-Phosphorylaspartic Acids

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Key Laboratory for Bioorganic Phosphorus Chemistry of Education Ministry, Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China
Center for Molecular Biology, National Laboratory of Biomacromolecules, Institute of Biophysics, Academia Sinica, 15 Datun Road, Beijing 100101, P. R. China
Cite this: J. Org. Chem. 2003, 68, 10, 4052–4058
Publication Date (Web):April 23, 2003
https://doi.org/10.1021/jo0300082
Copyright © 2003 American Chemical Society
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    Abstract

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    N-phosphorylamino acids are chemically active species that have many biomimic activities. α-COOH in amino acids and peptides behaviors rather differently than β-COOH in many biochemical processes and takes a more important role in the origin of life. Activity differences between α-COOH and β-COOH in the peptide formation of phosphoryl amino acids are studied by 1D, 2D NMR techniques and by ab initio and density functional theory (DFT) calculations in this paper. Phosphoryl dipeptide is formed directly from phosphoryl aspartic acids without any coupling reagents. Only the α-dipeptide ester is observed by 1D 1H, 13C, and 31P NMR and 2D NMR. In the ab initio and DFT calculations, the pentacoordinate phosphorane intermediates containing five-membered rings are predicted to be more favored than those with six-membered rings. Both the experimental results and the theoretical calculations suggest that only the α-COOH group is activated by N-phosphorylation in N-phosphorylaspartic acid under mild conditions.

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