Abstract
One-carbon unit transfer reaction of folate cofactor model compound, 1-acetyl-2-methyl-imidazolinium, with 1,2-diaminobenzene has been studied theoretically with ONIOM method. The result shows that there are two pathways to complete this reaction because the imidazolinium ring has two breaking patterns. Both the two pathways have six steps. They are combination of two reactants, proton migration, break of five-membered ring, formation of benzimidazole derivate, another proton migration, and formation of final products. In each of the above pathways, the two proton migration steps have higher energy, which illuminate that the reaction is catalyzed by general acid-base. This fact agrees with the experimental results of enzymatic one-carbon unit transfer at oxidation level of formate.
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Huang, T., Wang, C., Maras, B. et al., Thermodynamic analysis of the binding of the polyglutamate chain of 5-formyltetrahydropteroylpolyglutamates to serine hydroxymethyltransferase, Biochemistry, 1998, 37: 13536–13542.
Blakley, R. L., The Biochemistry of Folic Acid and Related Pteridines, Amsterdam: North-Holland Publishing Co., 1969, 15–28.
Kim, Y.-I., Folate and carcinogenesis: Evidence, mechanisms, and implications, J. Nutr. Biochem., 1999, 10: 66–88.
Leary, R. P., Beaudette, N., Kisliuk, R. L., Interaction of deoxyuridylate with thymidylate synthetase, J. Biol. Chem., 1975, 250: 4864–4868.
Warren, L., Buchanan, J. M., 2-Amino-N-ribosylacetamide 5′-phosphate (glycinamide ribotide) transformylase, J. Biol. Chem., 1957, 229: 613–626.
Warren, L., Flaks, J. G., Buchanan, J. M., Integration of enzymatic transformylations, J. Biol. Chem., 1957, 229: 627–640.
Reinald, H., Pandit, U. K., A route to optically active octahydroindolo [2,3-a] quinolizines, Tetrahedron, 1992, 48: 6521–6528.
Stoit, A. R., Pandit, U. K., An approach to deethyleburnamonine, Tetrahedron, 1989, 45: 849–853.
Bieraugel, H., Plemp, R., Hiemstra, H. C. et al., Synthesis and carbon transfer reactions of N5, N10-methenyl and N5, N10-methylentetrahydrofolate models, Tetrahedron, 1983, 39: 3971–3979.
Huizenga, R. H., van Wiltenburg, J., Bieraugel, H. et al., A synthetic strategy to the aspidosperma skeleton, Synthesis of the 21-epimer of 20-deethyl-3,17-dioxo-16-echoxycarbonyl-1-methylaspidospermidine, Tetrahedron, 1991, 47: 4165–4174.
Chen Jianxin, Pan Jigang, Xia Chizhong, Mimicking of structure and propertied of tetrahydrofolic coenzyme and study on their substituted one-carbon unit transfer reactions, Acta Chim. Sinica, 1998, 56: 819–826.
Xia Chizhong, Zhao Bingjun, Zhou Peiwen, Synthesis of tetrahydrofolate coenzyme models, 1,2-dimethyl-3-m(p)-nitro-phenylsulfonyl imidazolinium iodide and their methyl-substituted one carbon unit transfer reactions, Chin. Sci. Bull., 1996, 41(2): 172–173.
Daniel, A. D., Scuseria, G. E., What is the best alternative to diagonalization of the Hamiltonian in large scale semiempirical calculations? J. Chem. Phys., 1999, 110: 1321–1329.
Millam, J. M., Scuseria, G. E., Linear scaling conjugate gradient density matrix search as an alternative to diagonalization for first principles electronic structure calculations, J. Chem. Phys., 1997, 106: 5569–5574.
Titmuss, S. J., Cummins, P. L., Bliznyuk, A. A., Comparison of linear-scaling semiempirical methods and combined quantum mechanical/molecular mechanical methods applied to enzyme reactions, Chem. Phys. Lett., 2000, 320: 169–176.
York, D. M., Lee, T. -S., Yang, W., Parameterization and efficient implementation of a solvent model for linear-scaling semiempirical quantum mechanical calculations of biological macromolecules, Chem. Phys. Lett., 1996, 263: 297–304.
Lee, T. -S., York, D. M., Yang, W., Linear-scaling semiempirical quantum calculations for macromolecules, J. Chem. Phys., 1996, 105: 2744–2747.
Lewis, J. P., Carter, W. Jr., Hermans, J. et al., Active species for the ground-state complex of cytidine deaminase: A linear-scaling quantum mechanical investigation, J. Am. Chem. Soc., 1998, 120: 540–5410.
Malsubara, T., Sieber, S., Morokuma, K., A test of the new “integrated MO + MM” (IMOMM) method for the conformational energy of ethane and n-butane, Inter. J. Quantum Chem., 1996, 60: 1101–1109.
Svensson, M., Humbel, S., Froese, R. D., ONIOM: A multilayered integrated MO+MM method for geometry optimizations and single point energy predictions, A test for Diels-Alder reactions and Pt(P(t-Bu)3)2 + H2 oxidative addition, J. Phys. Chem.,1996, 100: 19357–19363.
Stewart, J. J. P., Optimization of parameters for semiempirical methods, II. Applications, J. Comput. Chem., 1989, 10: 221–264.
Benkovics, J., On the Mechanism of action of folate-and biopterin-requiring enzymes, Ann. Rev. Biochem., 1980, 49: 227–251.
Burdick, B. A., Benkovic, P. A., Benkovic, S. J., Studies on models for tetrahydrofolic acid, hydrolysis and melhoxyaminolysis of amidines, J. Am. Chem. Soc., 1977, 99: 5716–5725.
Bullard, W. P., Farina, L. J., Farina, P. R. et al., Studies on models for tetrahydrofolic acid, kinetically significant transport process in general base catalyzed aminolysis of a formamidine, J. Am. Chem. Soc., 1974, 96: 7295–7302.
Fife, T. H., Pellino, A. M., General-acid catalysis of imidazolidine ring opening, The hydrolysis of ethyl N, N-[1-(p-(dimethylamino) phenyl) propenediyl]-p-[((2-tetrahydroquinolinyl) methylene) amino] benzoate, J. Am. Chem. Soc., 1981, 103: 1201–1207.
Fife, T. H., Pellino, A. M., General-acid-catalyzed imidazolidine ring opening, hydrolysis of symmetrical and unsymmetrical 1, 3-imidazolindine of p-dimethylaminocinnamaldehyde, J. Am. Chem. Soc., 1980, 102: 3062–3071.
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Kang, C., Qi, C., Feng, D. et al. Quantum chemical study on the one-carbon unit transfer of imidazolinium. Sc. China Ser. B-Chem. 45, 257–266 (2002). https://doi.org/10.1360/02yb9034
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DOI: https://doi.org/10.1360/02yb9034