引用本文:
Zhong Zhou CHEN, Bo TAN, Yan Mei LI, Yu Fen ZHAO. Theoretical Study on the Activity of α-COOH and β-COOH of N-Phosphoryl Aspartic Acids[J]. Chinese Chemical Letters,
2001, 12(12): 1093-1096.
Citation: Zhong Zhou CHEN, Bo TAN, Yan Mei LI, Yu Fen ZHAO. Theoretical Study on the Activity of α-COOH and β-COOH of N-Phosphoryl Aspartic Acids[J]. Chinese Chemical Letters, 2001, 12(12): 1093-1096.
Citation: Zhong Zhou CHEN, Bo TAN, Yan Mei LI, Yu Fen ZHAO. Theoretical Study on the Activity of α-COOH and β-COOH of N-Phosphoryl Aspartic Acids[J]. Chinese Chemical Letters, 2001, 12(12): 1093-1096.
Theoretical Study on the Activity of α-COOH and β-COOH of N-Phosphoryl Aspartic Acids
摘要:
The bio-mimic reactions of N-phosphoryl amino acids are very important in the study of many biochemical processes. The difference of reactivity between α-COOH and β-COOH in phosphoryl aspartic acid was studied by theoretical study (Hartree-Fock and Density Functional methods) in this paper. The intermediates II containing five-membered ring were more stable than III with six-membered ring. While for intermediates III, the isomers with six-membered ring in apical-equatorial spanning arrangement were more stable than those with di-equatorial spanning arrangement. At B3LYP/6-31G** level, it was shown that transition states IV and V involving α-COOH or β-COOH group had energy barriers of ΔE=58.67 kJ·mol-1 and 103.94 kJ·mol-1, respectively. These results were in agreement with the experimental data. So the α-COOH group was involved in form of the intramolecular penta-coordinate phosphoric-carboxylic mixed anhydride intermediates, but not β-COOH group.
English
Theoretical Study on the Activity of α-COOH and β-COOH of N-Phosphoryl Aspartic Acids
Abstract:
The bio-mimic reactions of N-phosphoryl amino acids are very important in the study of many biochemical processes. The difference of reactivity between α-COOH and β-COOH in phosphoryl aspartic acid was studied by theoretical study (Hartree-Fock and Density Functional methods) in this paper. The intermediates II containing five-membered ring were more stable than III with six-membered ring. While for intermediates III, the isomers with six-membered ring in apical-equatorial spanning arrangement were more stable than those with di-equatorial spanning arrangement. At B3LYP/6-31G** level, it was shown that transition states IV and V involving α-COOH or β-COOH group had energy barriers of ΔE=58.67 kJ·mol-1 and 103.94 kJ·mol-1, respectively. These results were in agreement with the experimental data. So the α-COOH group was involved in form of the intramolecular penta-coordinate phosphoric-carboxylic mixed anhydride intermediates, but not β-COOH group.
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Key words:
- α-Carboxylic group
- / β-carboxylic group
- / theoretical study
- / N-phosphorylation
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