Theoretical Study on the Activity of a-COOH and b-COOH of N-Phosphoryl Aspartic Acids |
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Authors: | Zhong Zhou CHEN Bo TAN Yan Mei LI Yu Fen ZHAO Key Laboratory for Bioorganic Phosphorus Chemistry of Education Ministry |
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Institution: | Zhong Zhou CHEN,Bo TAN,Yan Mei LI*,Yu Fen ZHAO Key Laboratory for Bioorganic Phosphorus Chemistry of Education Ministry,Department of Chemistry,School of Life Science and Engineering,Tsinghua University,Beijing 100084 |
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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 a-COOH and b-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 a-COOH or b-COOH group had energy barriers of DE = 58.67 kJmol-1 and 103.94 kJmol-1, respectively. These results were in agreement with the experimental data. So the a-COOH group was involved in form of the intramolecular penta-coordinate phosphoric-carboxylic mixed anhydride intermediates, but not b-COOH group. |
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Keywords: | a-Carboxylic group b- carboxylic group theoretical study N-phosphorylation |
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