Activity difference between alpha-COOH and beta-COOH in N-phosphorylaspartic acids.
N-phosphorylamino acids are chemically active species that have many biomimic activities. alpha-COOH in amino acids and peptides behaviors rather differently than beta-COOH in many biochemical processes and takes a more important role in the origin of life. Activity differences between alpha-COOH and beta-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 alpha-dipeptide ester is observed by 1D (1)H, (13)C, and (31)P 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 alpha-COOH group is activated by N-phosphorylation in N-phosphorylaspartic acid under mild conditions.
Key Laboratory for Bioorganic Phosphorus Chemistry of Education Ministry, Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China.
Zhong-Zhou
ZZ
Chen
Bo
B
Tan
Yan-Mei
YM
Li
Yu-Fen
YF
Zhao
Yu-Feng
YF
Tong
Jin-Feng
JF
Wang
D001224:Aspartic Acid / Q000031:analogs & derivatives* / Q000737:chemistry*; D007700:Kinetics; D008962:Models, Theoretical; D008968:Molecular Conformation; D018716:Molecular Mimicry; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D009943:Organophosphorus Compounds / Q000737:chemistry*; D010455:Peptides / Q000737:chemistry*; D013237:Stereoisomerism; D013329:Structure-Activity Relationship
D009943:Organophosphorus Compounds; D010455:Peptides; D001224:Aspartic Acid