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Conformational flexibility of 4,4-dimethyl-3,4-dihydro-2H-1,4-thiasiline and its monoheterocyclic analogs

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Abstract

Conformational behavior of the first cyclic organosilicon vinylsulfide, 4,4-dimethyl-3,4-dihydro-2H-1,4-thiasiline as well as its monoheterocyclic analogs, 3,4-dihydro-2H-pyran, 3,4-dihydro-2H-thiopyran, and 1,1-dimethyl-1,2,3,4-tetrahydrosiline is studied in comparison with the carbocyclic analog, cyclohexene, using the methods of low-temperature NMR spectroscopy and theoretical calculations at the DFT and MP2 levels of theory. The barrier to the ring inversion with respect to that in cycloxene is increased in 3,4-dihydro-2H-pyran and 1,1-dimethyl-1,2,3,4-tetrahydrosiline, but, in contrast to the suggestions made in the literature, is decreased in 3,4-dihydro-2H-thiopyran. In 4,4-dimethyl-3,4-dihydro-2H-1,4-thiasiline the barrier is intermediate between those in the corresponding monoheterocycles, 1,1-dimethyl-1,2,3,4-tetrahydrosiline and 3,4-dihydro-2H-thiopyran. The observed variations are rationalized from the viewpoint of the interaction of the π-electrons of the C=C double bond with the orbitals of heteroatoms in the ring. The structure of the transition state for the ring inversion is discussed.

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References

  1. Suslova, E.N. and Shainyan, B.A., Mendeleev Comm., 2013, vol. 23, no. 5, p. 2917.

    Article  Google Scholar 

  2. Kirpichenko, S.V., Kleinpeter, E., and Shainyan, B.A., J. Phys. Org. Chem., 2010, vol. 23, p. 859.

    CAS  Google Scholar 

  3. Kirpichenko, S.V., Kleinpeter, E., Ushakov, I.A., and Shainyan, B.A., J. Phys. Org. Chem., 2011, vol. 24, p. 320.

    CAS  Google Scholar 

  4. Shainyan, B.A., Suslova, E.N., and Kleinpeter, E., J. Phys. Org. Chem., 2011, vol. 24, p. 1188.

    CAS  Google Scholar 

  5. Shainyan, B.A. and Kleinpeter, E., Tetrahedron, 2012, vol. 68, p. 114.

    Article  CAS  Google Scholar 

  6. Jensen, F.R. and Bushweller, C.H., J. Am. Chem. Soc., 1969, vol. 91, p. 5774.

    Article  CAS  Google Scholar 

  7. Anet, F.A.L. and Bourn, A.J.R., J. Am. Chem. Soc., 1967, vol. 89, p. 760.

    Article  CAS  Google Scholar 

  8. Bushweller, C.H. and O’Neil, J.W., Tetrahedron Lett., p. 4713.

  9. Larkin, R.H. and Lord, R.C., J. Am. Chem. Soc., 1973, vol. 95, p. 5129.

    Article  CAS  Google Scholar 

  10. Brunskill, J.S.A., De, A., and Ewing, D.F., Org. Magn. Reson., 1979, vol. 12, p. 257.

    Article  CAS  Google Scholar 

  11. Arnason, I., Kvaran, A., Jonsdottir, S., Gudnason, P.I., and Oberhammer, H., J. Org. Chem., 2002, vol. 67, p. 3827.

    Article  CAS  Google Scholar 

  12. Favero, L.B., Velino, B., Caminati, W., Árnason, I., and Kvaran, Á., Organometallics, 2006, vol. 25, p. 3813.

    Article  CAS  Google Scholar 

  13. Weldon, A.J. and Tschumper, G.S., Int. J. Quant. Chem., 2007, vol. 107, p. 2261.

    Article  CAS  Google Scholar 

  14. Bjornsson, R. and Arnason, I., Phys. Chem. Chem. Phys., 2009, vol. 11, p. 8689.

    Article  CAS  Google Scholar 

  15. Bodi, A., Bjornsson, R., and Arnason, I., J. Mol. Struct., 2010, vol. 978, p. 14.

    Article  CAS  Google Scholar 

  16. Wallevik, S.Ó., Bjornsson, R., Kvaran, Á., Jonsdottir, S., Girichev, G.V., Giricheva, N.L., Hassler, K., and Arnason, I., J. Mol. Struct., 2010, vol. 978, p. 209-–19.

    Article  CAS  Google Scholar 

  17. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G.A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H.P., Izmaylov, A.F., Bloino, J., Zheng, G., Sonnenberg, J.L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J.A., Peralta, J.E., Ogliaro, F., Bearpark, M., Heyd, J.J., Brothers, E., Kudin, K.N., Staroverov, V.N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Rega, N., Millam, J.M., Klene, M., Knox, J.E., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Martin, R.L., Morokuma, K., Zakrzewski, V.G., Voth, G.A., Salvador, P., Dannenberg, J.J., Dapprich, S., Daniels, A.D., Farkas, O., Foresman, J.B., Ortiz, J.V., Cioslowski, J., and Fox, D.J., Gaussian 09, Revision A.01, Gaussian, Inc., Wallingford, CT, 2009.

    Google Scholar 

  18. Anet, F.A.L., Freedberg, D.I., Storer, J.W., and Houk, K.N., J. Am. Chem. Soc., 1992, vol. 114, p. 10969.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, ul. Favorskogo 1, Irkutsk, 664033, Russia

    B. A. Shainyan

  2. Institut für Chemie der Universität Potsdam, Karl-Liebknecht-Str. 24-25, D-14476, Potsdam, Germany

    E. Kleinpeter

Authors
  1. B. A. Shainyan
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  2. E. Kleinpeter
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Correspondence to B. A. Shainyan.

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Original Russian Text © B.A. Shainyan, E. Kleinpeter, 2014, published in Zhurnal Obshchei Khimii, 2014, Vol. 84, No. 7, pp. 1129–1133.

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Shainyan, B.A., Kleinpeter, E. Conformational flexibility of 4,4-dimethyl-3,4-dihydro-2H-1,4-thiasiline and its monoheterocyclic analogs. Russ J Gen Chem 84, 1325–1329 (2014). https://doi.org/10.1134/S1070363214070135

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  • DOI: https://doi.org/10.1134/S1070363214070135

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