Issue

Vol. 33 No. 2 (2021): Vol 33 Issue 2

Copyright (c) 2021 AJC

Creative Commons License

This work is licensed under a Creative Commons Attribution 4.0 International License.

Can Aromaticity of Fused Aromatic Ring in 1,3-Pentadiene Modulate its Reactivity towards [1,5]-Halo Shift? - A DFT Study

https://doi.org/10.14233/ajchem.2021.23092
Padmanaban Kalpana
Department of Chemistry, Sri Sarada College for Women (Autonomous), Salem-636016, India
Lakshminarayanan Akilandeshwari
Department of Chemistry, Sri Sarada College for Women (Autonomous), Salem-636016, India

Corresponding Author(s) : Lakshminarayanan Akilandeshwari

akilchem@gmail.com

Asian Journal of Chemistry, Vol. 33 No. 2 (2021): Vol 33 Issue 2

Abstract

In (Z)-1,3-pentadienes, [1,5]-H migration is suprafacially allowed while fluorine shift in this system takes place by a Contra Hoffmann antarafacial pathway for which aromaticity is the driving force. If aromaticity of the transition structure (TS) can drive a reaction towards a disallowed pathway as found in the case of fluorine, the role of aromatic ring annealed to (Z)-1,3-pentadienes in determining the reaction pathway and barrier is worth noting. Hence, the combined role of aromaticity of transition state and the loss in aromaticity of the annealed ring has been explored during the [1,5]-X (X = H, F, Cl, Br) shifts in aromatic (benzene/naphthalene) annealed 1,3-pentadiene system. Notable correlations between various aromaticity index NICS(0,1) with activation barriers show that aromaticity of transition structure in pericyclic reaction can drive the stereochemical course of a reaction. The distinct effect of fluorine to other halogens is the antara migration while the other halogens (Cl & Br) prefer supramode.

Keywords

Aromaticity DFT study Nucleus independent chemical shift Supra/antarafacial mode [1,5]-Halogen shift
Kalpana, P., & Akilandeshwari, L. (2021). Can Aromaticity of Fused Aromatic Ring in 1,3-Pentadiene Modulate its Reactivity towards [1,5]-Halo Shift? - A DFT Study. Asian Journal of Chemistry, 33(2), 447–452. https://doi.org/10.14233/ajchem.2021.23092
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. R.B. Woodward and R. Hoffmann, J. Am. Chem. Soc., 87, 2511 (1965);https://doi.org/10.1021/ja01089a050
  2. T.H. Lowry and K.S. Richardson, Mechanism of Theory in Organic Chemistry, Harper and Row Publishers: New York (1987).
  3. K.N. Houk, eds.: A. Scott, Pericyclic Reactions and Orbital Symmetry, In: Survey of Progress in Chemistry, Academic Press, vol. 6, p. 113 (1973).
  4. D.S. Glass, R.S. Boikess and S. Winstein, Tetrahedron Lett., 7, 999 (1966);https://doi.org/10.1016/S0040-4039(00)70230-9
  5. J.E. Baldwin, P.A. Leber and T.W. Lee, J. Org. Chem., 66, 5269 (2001);https://doi.org/10.1021/jo010389o
  6. J.J. Looker, J. Org. Chem., 37, 1059 (1972);https://doi.org/10.1021/jo00972a035
  7. J. Zhao, R.Y. Zhang and S.W. North, Chem. Phys. Lett., 369, 204 (2003); https://doi.org/10.1016/S0009-2614(02)02006-7
  8. Y.-L. Lin and E. Turos, J. Org. Chem., 66, 8751 (2001); https://doi.org/10.1021/jo0103221
  9. H.P. Wu, R. Aumann, R. Frohlich, B. Wibbeling and O. Kataeva, Chem. Eur. J., 7, 5084 (2001); https://doi.org/10.1002/1521-3765(20011203)7:23<5084::AID-CHEM5084>3.0.CO;2-H
  10. I.V. Alabugin, M. Manoharan, B. Breiner and F.D. Lewis, J. Am. Chem. Soc., 125, 9329 (2003); https://doi.org/10.1021/ja035729x
  11. J. Wolinsky, B. Chollar and M. Baird, J. Am. Chem. Soc., 84, 2775 (1962); https://doi.org/10.1021/ja00873a027
  12. N.G. Rondan and K.N. Houk, Tetrahedron Lett., 25, 2519 (1984); https://doi.org/10.1016/S0040-4039(01)81220-X
  13. N.J. Saettel and O. Wiest, J. Org. Chem., 65, 2331 (2000); https://doi.org/10.1021/jo991488t
  14. B.A. Hess and J.E. Baldwin, J. Org. Chem., 67, 6025 (2002); https://doi.org/10.1021/jo025917q
  15. T. Okajima and K. Imafuku, J. Org. Chem., 67, 625 (2002); https://doi.org/10.1021/jo010084+
  16. K.N. Houk, Y. Li and J.D. Evanseck, Angew. Chem. Int. Ed. Engl., 31, 682 (1992); https://doi.org/10.1002/anie.199206821
  17. L. Akilandeswari, Ph.D. Thesis, Modelling Tandem Reactions, Bharathidasan University, Tiruchirappalli, India, p. 110 (2007).
  18. L. Akilandeswari and C. Prathipa, J. Chem. Sci., 127, 1505 (2015); https://doi.org/10.1007/s12039-015-0936-5
  19. K.N. Houk, J. Gonzalez and Y. Li, Acc. Chem. Res., 28, 81 (1995); https://doi.org/10.1021/ar00050a004
  20. J.E. Baldwin and B.M. Broline, J. Org. Chem., 47, 1385 (1982); https://doi.org/10.1021/jo00347a001
  21. H. Jiao and P.R. Schleyer, J. Phys. Org. Chem., 11, 655 (1998); https://doi.org/10.1002/(SICI)1099-1395(199808/09)11:8/9<655::AID-POC66>3.0.CO;2-U
  22. P.B. Karadakov, J.G. Hill and D.L. Cooper, Faraday Discuss., 135, 285 (2007); https://doi.org/10.1039/B605100F
  23. W.R. Roth and J. Konig, Liebigs Ann. Chem., 699, 24 (1966); https://doi.org/10.1002/jlac.19666990103
  24. M. Manoharan, F. De Proft and P. Geerlings, J. Chem. Soc. Perkin Trans. II, 8, 1767 (2000); https://doi.org/10.1039/b002344m
  25. M. Manoharan, F. De Proft and P. Geerlings, J. Org. Chem., 65, 7971 (2000); https://doi.org/10.1021/jo001156k
  26. M. Manoharan, F. De Proft and P. Geerlings, J. Org. Chem., 65, 6132 (2000); https://doi.org/10.1021/jo000588s
  27. M. Manoharan and P. Venuvanalingam, J. Phys. Org. Chem., 10, 768 (1997); https://doi.org/10.1002/(SICI)1099-1395(199710)10:10<768::AID-POC938>3.0.CO;2-6
  28. R.B. Woodward and R. Hoffmann, The Conservation of Orbital Symmetry, Academic Press: New York, edn 1 (1971).
  29. H. Nohira and T. Nohira, J. Theor. Comput. Chem., 16, 1750055 (2017); https://doi.org/10.1142/S0219633617500559
  30. L. Akilandeswari, M. Jaccob and P. Venuvanalingam, J. Chem. Sci., 121, 859 (2009); https://doi.org/10.1007/s12039-009-0101-0
  31. S. Yamabe, N. Tsuchida and S. Yamazaki, J. Chem. Theory Comput., 1, 944 (2005); https://doi.org/10.1021/ct0500646
  32. B.S. Jursic, J. Mol. Struct., 427, 165 (1998); https://doi.org/10.1016/S0166-1280(97)00209-1
  33. J. Clarke, P.W. Fowler, S. Gronert and J.R. Keeffe, J. Org. Chem., 81, 8777 (2016); https://doi.org/10.1021/acs.joc.6b01261
  34. Y. Itou, S. Mori, T. Udagawa, M. Tachikawa, T. Ishimoto and U. Nagashima, J. Phys. Chem. A, 111, 261 (2007); https://doi.org/10.1021/jp065759x
  35. L.S. Kobrina and V.N. Kovtonyuk, Russ. Chem. Rev., 57, 62 (1988); https://doi.org/10.1070/RC1988v057n01ABEH003335
  36. F.D. Lewis, X. Zuo, V. Gevorgyan and M. Rubin, J. Am. Chem. Soc., 124, 13664 (2002); https://doi.org/10.1021/ja028251q
  37. P. Kalpana and L. Akilandeswari, J. Phys. Org. Chem., 32, e3991 (2019); https://doi.org/10.1002/poc.3991
  38. A.D. Becke, Phys. Rev. A, 38, 3098 (1988); https://doi.org/10.1103/PhysRevA.38.3098
  39. C. Lee, W. Yang and R.G. Parr, Phys. Rev. B Condens. Matter Mater. Phys., 37, 785 (1988); https://doi.org/10.1103/PhysRevB.37.785
  40. A.D. Becke, J. Chem. Phys., 98, 5648 (1993); https://doi.org/10.1063/1.464913
  41. M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, V.G. Zakrzewski, J.A. Montgomery Jr., R.E. Stratmann, J.C. Burant, S. Dapprich, J.M. Millam, A.D. Daniels, K.N. Kudin, M.C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G.A. Petersson, P.Y. Ayala, Q. Cui, K. Morokuma, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J. Cioslowski, J.V. Ortiz, A.G. Baboul, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, J.L. Andres, C. Gonzalez, M. Head-Gordon, E.S. Replogle and J.A. Pople, Gaussian 98, Review A.9. Gaussian, Inc., Pittsburgh PA (1998).
  42. P.R. Schleyer, C. Maerker, A. Dransfeld, H. Jiao and N.J.R. van Eikema Hommes, J. Am. Chem. Soc., 118, 6317 (1996); https://doi.org/10.1021/ja960582d
  43. K. Wolinski, J.F. Hinton and P. Pulay, J. Am. Chem. Soc., 112, 8251 (1990); https://doi.org/10.1021/ja00179a005
  44. L. Akilandeswari and P. Venuvanalingam, J. Theor. Comput. Chem., 6, 233 (2007); https://doi.org/10.1142/S0219633607003040
Read More
Author biographies is not available.
Download
PDF
Statistic
Read Counter : 1 Download : 0