Abstract
In the last decade, pyridoxine derivatives were widely used for the synthesis of molecules with important biological and physical properties. However, rational synthesis of the compounds with desirable biochemical or physical properties often requires information about their spatial structure and conformational mobility. NMR spectroscopy is a powerful tool for conformational analysis of biologically important samples, such as pyridoxine derivatives, in solution. This paper is devoted to a review of the results obtained by our group over the last 5 years on the NMR study of nine newly synthesized pyridoxine derivatives in acetone solution. It was shown that studied compounds are involved into several conformational exchange processes. The activation energies of all observed conformational exchange processes were calculated.
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References
Shtyrlin, N. V., Lodochnikova, O. A., & Shtyrlin, Y. G. (2012). Regioisomeric oximes and thiosemicarbazones derived from 6-substituted pyridoxines. Mend Commun, 22(3), 169–170. https://doi.org/10.1016/j.mencom.2012.05.021.
Pugachev, M. V., Shtyrlin, N. V., Sysoeva, L. P., Nikitina, E. V., Abdullin, T. I., Iksanova, A. G., Ilaeva, A. A., Musin, R. Z., Berdnikov, E. A., & Shtyrlin, Y. G. (2013). Synthesis and antibacterial activity of novel phosphonium salts on the basis of pyridoxine. Bioorganic & Medicinal Chemistry, 21, 4388–4395. https://doi.org/10.1016/j.bmc.2013.04.051.
Ziganshin, A. U., Kalinina, O. S., Strelnik, A. D., Garipov, M. R., Koshkin, S. A., Ziganshina, L. E., & Shtyrlin, Y. G. (2015). Antagonistic properties of new non-phosphorylated derivatives of nitrogen-containing heterocycles towards P2 receptors. International Journal of Pharmacology, 11, 400–404. https://doi.org/10.3923/iup.2015.400-404.
Kayumov, A. R., Nureeva, A. A., Trizna, E. Y., Gazizova, G. R., Bogachev, M. I., Shtyrlin, N. V., Pugachev, M. V., Sapozhnikov, S. V., & Shtyrlin, Y. G. (2015). New derivatives of pyridoxine exhibit high antibacterial activity against biofilm-embedded staphylococcus cells. Biomed Research International, 890968. https://doi.org/10.1155/2015/890968.
Strelnik, A. D., Petukhov, A. S., Zueva, I. V., Zobov, V. V., Petrov, K. A., Nikolsky, E. E., Balakin, K. V., Bachurin, S. O., & Shtyrlin, Y. G. (2016). Novel potent pyridoxine-based inhibitors of AChE and BChE, structural analogs of pyridostigmine, with improved in vivo safety profile. Bioorganic & Medicinal Chemistry Letters, 26, 4092–4094. https://doi.org/10.1016/j.bmcl.2016.06.070.
Litvinov IA, Morozov OA, Shtyrlin YG, Petukhov AS, Garipov MR, Shtyrlin NV, Lodochnikova OA, Lovchev AV, Strel’nik AD (2003) Pyridoxine derivatives with nonlinear optical properties. Pat. RU2501801, Kazan Federal University, MPC C07D491/056, 20.12.2003.
Strel'nik, A. D., Garipov, M. R., Petukhov, A. S., Shtyrlin, N. V., Lodochnikova, O. A., Litvinov, I. A., Naumov, A. K., Morozov, O. A., Klimovitskii, A. E., & Shtyrlin, Y. G. (2014). Structural and spectral characterization of novel non-centrosymmetric 2,4-dintrobenzene derivative. Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy, 117, 793–797. https://doi.org/10.1016/j.saa.2013.09.092.
Arbuzov, B. A., Klochkov, V. V., Aganov, A. V., Klimovitskii, E. N., & Samitov, U. U. (1980). Anizoenergy of inversion of six-membered cycles and pseudotransformations of seven-membered cycles in cyclohexanone spiroketals. Doklady Chemistry (Doklady Akademii Nauk SSSR), 250, 378–381 [in russian].
Arbuzov, B. A., Klimovitskii, E. N., Remizov, A. B., Klochkov, V. V., Aganov, A. V., & Timirbaev, M. B. (1980). Stereochemistry of seven-membered heterocycles. 3. Conformation of 5,6-dichloro-1,3-dioxacyclopent-5-enes and the planar-fragment effect. Bulletin of the Academy of Sciences of the USSR, Division of chemical science, 29, 1276–1281. https://doi.org/10.1007/BF00950572.
Arbuzov, B. A., Klimovitskii, E. N., Remizov, A. B., & Timirbaev, M. B. (1981). Stereochemistry of seven-membered heterocycles. VI. Quantitative estimation of conformational energies of planar fragments and substitutes of at C2 in the series of 1,3-dioxacyclogept-5-enes and some of their derivatives. Russian Journal of General Chemistry, 51, 2705–2710 [in russian].
Klochkov, V. V., Latypov, S. K., & Aganov, A. V. (1993). The influence of the medium on thermodynamic parameters of conformational transformations in cycles. Russian Journal of General Chemistry, 63, 721–739 [in russian].
Shtyrlin, Y. G., Shaikhutdinova, G. R., & Klimovitskii, E. N. (2001). Kinetics of the conformer reactions: II. Significance of media in the electrophilic addition reactions. Russian Journal of General Chemistry, 71, 464–468. https://doi.org/10.1023/A:1012385808022.
Shtyrlin, Y. G., Fedorenko, V. Y., & Klimovitskii, E. N. (2001). Anomalous steric effect of a remote substituent in a high-pressure reaction. Russian Journal of General Chemistry, 71, 819–820. https://doi.org/10.1023/A:1012346410690.
Petukhov, A. S., Strel'nik, A. D., Fedorenko, V. Y., Litvinov, I. A., Lodochnikova, O. A., Shtyrlin, Y. G., & Klimovitskii, E. N. (2007). Stereochemical transformations of some seven-membered pyridoxine dimethyl ketals. Russian Journal of General Chemistry, 77, 1416–1421. https://doi.org/10.1134/S1070363207080208.
Casarini, D., Lunazzi, L., & Mazzanti, A. (2010). Recent advances in stereodynamics and conformational analysis by dynamic NMR and theoretical calculations. European Journal of Organic Chemistry, (11), 2035–2056. https://doi.org/10.1002/ejoc.200901340.
Jackman, L., & Cotton, F. (1975). Dynamic nuclear magnetic resonance spectroscopy. New York: Academic Press.
Rakhmatullin, I. Z., Galiullina, L. F., Garipov, M. R., Strel'nik, A. D., Shtyrlin, Y. G., & Klochkov, V. V. (2014). Dynamic NMR study of cyclic derivatives of pyridoxine. Magnetic Resonance in Chemistry, 52, 769–778. https://doi.org/10.1002/mrc.4123.
Rakhmatullin, I. Z., Galiullina, L. F., Garipov, M. R., Strel'nik, A. D., Shtyrlin, Y. G., & Klochkov, V. V. (2015). Dynamic NMR study of dinitrophenyl derivatives of seven-membered cyclic ketals of pyridoxine. Magnetic Resonance in Chemistry, 53, 805–812. https://doi.org/10.1002/mrc.4251.
Rakhmatullin, I. Z., Galiullina, L. F., Garipov, M. R., Strel'nik, A. D., Shtyrlin, Y. G., & Klochkov, V. V. (2016). 1H NMR characterization of two new pyridoxine derivatives. BioNanoSci, 6, 243–245. https://doi.org/10.1007/s12668-016-0214-0.
Rakhmatullin, I. Z., Galiullina, L. F., Balandina, A. A., Garipov, M. R., Strel'nik, A. D., Galiullina, A. S., Shtyrlin, Y. G., & Klochkov, V. V. (2017). Stereodynamics of some pyridoxine derivatives. Magnetic Resonance in Chemistry, 55, 304–311. https://doi.org/10.1002/mrc.4528.
Hans J (2002) Simulating NMR Spectra with WINDNMR-Pro. https://www.chem.wisc.edu/areas/reich/plt/windnmr.htm. Accessed 2 November 2002.
Sidney, W., & Benson, S. (1960). The foundations of chemical kinetics. New York: McGraw-Hill.
Klimovitskii, E. N., Shtyrlin, Y. G., Kashaeva, E. A., Kiselev, V. D., Vafina, R. M., & Khotinen, A. V. (1996). Kinetics of conformer reactions. I. a new approach. Russian Journal of General Chemistry, 3, 477–483.
Casarini, D., Foresti, E., Gasparrini, F., Lunazzi, L., Macciantelli, D., Misiti, D., & Villani, C. (1993). Atropisomerism in hindered naphthyl sulfoxides: Structure, stereodynamics, and chiral resolution. The Journal of Organic Chemistry, 58, 5674–5682. https://doi.org/10.1021/jo00073a028.
Casarini, D., Lunazzi, L., Gasparrini, F., Villani, C., Cirilli, M., & Gavuzzo, E. (1995). Conformational assignment, absolute configuration, and chiral separation of all the stereoisomers created by the combined presence of stereogenic centers and stereogenic conformational axes in a highly hindered 1,5-naphthyl sulfoxide. The Journal of Organic Chemistry, 60, 97–102. https://doi.org/10.1021/jo00106a020.
Casarini, D., Lunazzi, L., & Mazzanti, A. (1997). Conformational studies by dynamic nuclear magnetic resonance. Stereodynamics of conformational enantiomers in the atropisomers of hindered naphthylcarbinols. Journal of Organic Chemistry, 62, 3315–3323. https://doi.org/10.1021/jo970113+.
Casarini, D., Lunazzi, L., & Mazzanti, A. (1997). Conformational studies by dynamic NMR. Stereomutations of rotamers and of conformational enantiomers in 1,2-diacylbenzenes. The Journal of Organic Chemistry, 62, 7592–7596. https://doi.org/10.1021/jo970669x.
Wade, E. O., Valiulin, R. A., Ruybal, L. A., & Kutateladze, A. G. (2006). Conformational analysis of spiro-bis-dithiepins: A peculiar case of axial chirality. Organic Letters, 8, 5121–5124. https://doi.org/10.1021/ol062172s.
Acknowledgments
The work has been performed according to the Russian Government Program of Competitive Growth of Kazan Federal University.
Funding
This work was partially financially supported by the subsidy allocated to Kazan Federal University for the state assignment in the sphere of scientific activities (VK - 3.5283.2017/6.7).
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Rakhmatullin, I.Z., Galiullina, L.F., Balandina, A.A. et al. Spatial Structure and Conformational Mobility of Seven-Membered Cyclic Acetals and Ketals Containing Pyridoxine Moiety in Solution by NMR Methods. BioNanoSci. 8, 963–970 (2018). https://doi.org/10.1007/s12668-018-0562-z
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DOI: https://doi.org/10.1007/s12668-018-0562-z