Abstract
The mechanism of acylation of oxaloacetic acid (OA) with acetyl-CoA was studied at the DFT level using the basis functions 6-311G(d,p) and different numbers of diffuse functions. Four mechanisms are considered in this study. It is found that the most probable mechanism, in the approximation of isolated molecules, starts with the enol forms of oxaloacetic acid and acetylcystamine (final fragment from acetyl-CoA). The mechanisms are commented from the viewpoint of their thermodynamics. The calculations and UV/VIS spectroscopic analysis of OA showed that the enol form of the compound is available in ethanol, water and diethyl ether. The higher stability of the OA enol form (compared to the stability of the ketoform) was also reconfirmed by its experimental IR spectrum. The energy barrier of the enolization reaction of OA was calculated to be very high.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
A. Lehninger, Principles of Biochemistry, Freeman, New York (2004), p. 608.
M. Karpusas, B. Branchaud, and S. J. Remington, Biochemistry, 29, 2213–2219 (1990).
A. J. Mulholland and W. G. Richards, J. Mol. Struct. (Theochem), 429, 13–21 (1998).
S. F. Tayyari, S. Salemi, M. Z. Tabrizi, and M. Behforouz, J. Mol. Struct., 694, 91–104 (2004).
A. J. Mulholland and W. G. Richards, J. Mol. Struct. (Theochem), 427, 175–184 (1998).
A. D. Becke, J. Chem. Phys., 98, 5648–5652 (1993).
M. Mons, I. Dimicoli, and F. Piuzzi, Int. Rev. Phys. Chem., 21, 101–135 (2002).
M. D. Sevilla, D. Becker, M. Yan, and S. R. Summerfield, J. Phys. Chem., 95, 3409–3415 (1991).
J. H. Hendricks, S. A. Lyapustina, H. L. de Clercq, and K. H. Bowen, ibid., 108, 8–11 (1998).
V. M. Orlov, A. N. Smirnov, and Yu. M. Varshavskii, Tetrahedron Lett., 17, 4377/4378 (1976).
X. Li, Z. Cai, and M. D. Sevilla, J. Phys. Chem. B, 105, 10115–10123 (2001).
J. R. Carney and T. S. Zwier, J. Phys. Chem. A, 104, 8677–8688 (2000).
J. R. Carney and T. S. Zwier, Chem. Phys. Lett., 341, 77–85 (2001).
R. J. Graham, R. T. Kroemer, M. Mons, et al., J. Phys. Chem. A, 103, 9706–9711 (1999).
L. C. Snoek, E. G. Robertson, R. T. Kroemer, and J. P. Simons, Chem. Phys. Lett., 321, 49–56 (2000).
P. Butz, R. T. Kroemer, N. A. MacLeod, E. G. Robertson, and J. P. Simons, J. Phys. Chem. A, 105, 1050–1056 (2001).
P. Butz, R. T. Kroemer, N. A. MacLeod, and J. P. Simons, ibid., 105, 544–551 (2001).
T. van Mourik and L. E. Emson, Phys. Chem. Chem. Phys., 4, 5863–5871 (2002).
M. J. Frisch, G. W. Trucks, H. B. Schlegel, et al., Gaussian-98., A.3, Revision, Gaussian Inc., Pittsburgh, PA (1998).
SDBSWeb: http://www.aist.go.jp/RIODB/SDBS/ (National Institute of Advanced Industrial Science and Technology).
L. Gorb and J. Leszczynski, J. Am. Chem. Soc., 120, 5024–5032 (1998).
Y. Podolyan, L. Gorb, and J. Leszczynski, Int. J. Mol. Sci., 4, 410–421 (2003).
A. K. Chandra, M. T. Nguyen, T. Uchimaru, and T. Zeegers-Huyskens, J. Phys. Chem. A, 103, 8853–8860 (1999).
J. Gu and J. Leszczynski, ibid., 103, 2744–2750 (1999).
Author information
Authors and Affiliations
Corresponding author
Additional information
The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 48, No. 4, pp. 666–673, July–August, 2007.
Original Russian Text Copyright © 2007 by V. B. Delchev and G. T. Delcheva
Rights and permissions
About this article
Cite this article
Delchev, V.B., Delcheva, G.T. DFT study of oxaloacetic acid condensation — The first step of the citric acid cycle. J Struct Chem 48, 615–622 (2007). https://doi.org/10.1007/s10947-007-0094-9
Received:
Issue Date:
DOI: https://doi.org/10.1007/s10947-007-0094-9