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GIAO Calculations of Chemical Shifts in Heterocyclic Compounds

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Abstract

In this review, the GIAO calculations of absolute shieldings and their relationship with experimental chemical shifts for aromatic heterocycles will be summarized. Automatic assignment, conformational analysis, E/Z isomerism, and, in particular, tautomerism, will be discussed in detail. Solid-state and solvent effects will be examined, as well as the problem of heteroaromaticity. The review ends with the discussion of some methodological problems with special emphasis on the calculation of references, such as TMS and nitromethane.

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References

  1. Schleyer, P. v. R.; Maerker, C.; Dransfeld, A.; Jiao, H. H.; van Eikema Hommes, N. J. R.; J. Amer. Chem. Soc. 1996, 118, 6317.

    Google Scholar 

  2. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Inc.: Pittsburgh, PA, 1998.

  3. Seminario, J. M.; Politzer, P., Eds. Modern Density Functional Theory, A Tool for Chemistry; Elsevier: Amsterdam, 1995.

    Google Scholar 

  4. Bartolotti, J.; Flurcuck, K. Rev. Comp. Chem., 1996, 7, Chapter 4, p. 187.

    Google Scholar 

  5. Kohn, W.; Becke, A. D.; Parr, R. G. J. Phys. Chem. 1996, 100, 12974.

    Google Scholar 

  6. Becke, A. D. J. Chem. Phys. 1993, 98, 5648.

    Google Scholar 

  7. Becke, A. D. Phys. Rev. A 1988, 38, 3098.

    Google Scholar 

  8. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.

    Google Scholar 

  9. Miehlich, B.; Savin, A.; Stoll H.; Preuss, H. Chem. Phys. Lett. 1989, 157, 200.

    Google Scholar 

  10. London, F. J. Phys. Radium 1937, 8, 397.

    Google Scholar 

  11. Ditchfield, R. Mol. Phys. 1974, 27, 789.

    Google Scholar 

  12. Alkorta, I.; Elguero, J. Struct. Chem. 1998, 9, 187.

    Google Scholar 

  13. He, Y.; Wu, D.; Shen, L.; Li, B.; Webb, G. A. Magnetic Resonance Chem. 1995, 33, 701.

    Google Scholar 

  14. Hathaway, B. A.; Day, G.; Lewis, M.; Glaser, R. J. Chem. Soc. Perkin Trans. 2 1998, p. 2713.

  15. Martínez-Merino, V.; Gil, M. J. J. Chem. Soc. Perkin Trans. 2 1999, p. 33.

  16. Cmoch, P.; Wiench, J. W.; Stefaniak, L.; Sitkowski, J. J. Mol. Struct. 1999, 477, 119.

    Google Scholar 

  17. Dokalik, A.; Kalchhauser, H.; Mikenda, W.; Schweng, G. Magnetic Resonance Chem. 1999, 37, 895.

    Google Scholar 

  18. Jaroszewska-Manaj, J.; Maciejewska, D.; Wawer, I. Magnetic Resonance Chem. 2000, 38, 482.

    Google Scholar 

  19. Wiench, J. W.; Stefaniak, L.; Barszczewicz, A.; Webb, G. A. J. Mol. Struct. 1994, 327, 321.

    Google Scholar 

  20. Claramunt, R. M.; Lopez, C.; Schmidpeter, A.; Willhalm, A.; Elguero, J.; Alkorta, I. Spectroscopy 2001, 15, 27.

    Google Scholar 

  21. Bocian, W.; Stefaniak, L.; Wiench, J. W.; Webb, G. A. Pol. J. Chem. 1996, 70, 65.

    Google Scholar 

  22. Ortíz, P. J.; Evleth, E. M.; Montero, L. A. Theochem 1998, 432, 121.

    Google Scholar 

  23. Begtrup, M.; Balle, T.; Claramunt, R. M.; Sanz, D.; Jiménez, J. A.; Mó, O.; Yáñez, M.; Elguero, J., Theochem 1998, 453, 255.

    Google Scholar 

  24. Kleinpeter, E.; Hilfert, L.; Koch, A. J. Phys. Org. Chem. 2000, 13, 473.

    Google Scholar 

  25. Ferraro, M. B. Theochem 2000, 528, 199.

    Google Scholar 

  26. Bocian, W.; Jazwinski, J.; Staszewska, O.; Wiench, J. W.; Stefaniak, L.; Webb, G. A. Khim. Geterotsikl. Soedin. 1996, p. 1581.

  27. Koch, R.; Wiedel, B.; Wentrup, C. J. Chem. Soc. Perkin Trans. 2 1997, p. 1851.

  28. Koch, A.; Kleinpeter, E. J. Mol. Model. 1997, 3, 375.

    Google Scholar 

  29. Mazurek, A. P.; Dobrowolski, J. Cz.; Sadlej, J. J. Mol. Struct. 1997, 436–437, 435.

    Google Scholar 

  30. Rak, J.; Skurski, P.; Gutowski, M.; Jozwiak, L.; Blazejowski, J. J. Phys. Chem. A 1997, 101, 283.

    Google Scholar 

  31. Wiench, J. W.; Stefaniak, L.; Grech, E.; Webb, G. A. Bull. Polon. Acad. Sci. Chem. 1999, 47, 67.

    Google Scholar 

  32. Claramunt, R. M.; Alkorta, I.; Elguero, J. Heterocycles 1999, 51, 355.

    Google Scholar 

  33. Eckert, F.; Rauhut, G.; Katritzky, A. R.; Steel, P. J. J. Amer Chem. Soc. 1999, 121, 6700.

    Google Scholar 

  34. Cmoch, P.; Wiench, J. W.; Stefaniak, L.; Webb, G. A. J. Mol. Struct. 1999, 510, 165.

    Google Scholar 

  35. Kozlowski, P. M.; Wolinski, K.; Pulay, P.; Ye, B.-H.; Li, X.-Y. J. Phys. Chem. A 1999, 103, 420.

    Google Scholar 

  36. Cmoch, P.; Korczak, H.; Stefaniak, L.; Webb, G. A. J. Phys. Org. Chem. 1999, 12, 470.

    Google Scholar 

  37. Cmoch, P.; Stefaniak, L.; Melzer, E.; Batoniak, S.; Webb, G. A. Magnetic Resonance Chem. 1999, 37, 493.

    Google Scholar 

  38. Alkorta, I.; Elguero, J.; Donnadieu, B.; Etienne, M.; Jaffart, J.; Schagen, D.; Limbach, H.-H. New J. Chem. 1999, 23, 1231.

    Google Scholar 

  39. Alderete, J. B.; Belmar, J.; Parra, M.; Zuniga, C. Boll. Soc. Chil. Quim. 2000, 45, 85.

    Google Scholar 

  40. Dobado, J. A.; Grigoleit, S.; Molina-Molina, J. J. Chem. Soc. Perkin 2 2000, p. 1675.

  41. Plug, C.; Wallfisch, B.; Gade Andersen, H; Bernhardt, P. V.; Baker, L.-J.; Clark, G. R.; Wah Wong, M.; Wentrup, C. J. Chem. Soc. Perkin Trans. 2 2000, p. 2096.

  42. Kleinpeter, E.; Hilfert, L.; Koch, A. J. Phys. Org. Chem. 2000, 13, 473.

    Google Scholar 

  43. López, C.; Claramunt, R. M.; Alkorta, I.; Elguero, J., Spectroscopy 2000, 14, 121.

    Google Scholar 

  44. Claramunt, R. M.; López, C.; Sanz, D.; Alkorta, I.; Elguero, J. Heterocycles 2001, 55, 2109.

    Google Scholar 

  45. Garnuszek, P.; Dobrowolski, J. C.; Sitkowski, J.; Bednarek, E.; Witowska, J.; Mazurek, A. P. J. Mol. Struct. 2001, 565–566, 361.

    Google Scholar 

  46. Kleinpeter, E.; Koch, A. J. Phys. Org. Chem. 2001, 14, 566.

    Google Scholar 

  47. Osmialowski, B.; Kolehmainen, E.; Gawinecki, R. Magnetic Resonance Chem. 2001, 39, 334.

    Google Scholar 

  48. Claramunt, R. M.; López, C.; García, M. A.; Otero, M. D.; Torres, M. R.; Pinilla, E.; Alarcón, S. H.; Alkorta, I.; Elguero, J., New J. Chem. 2001, 25, 1061.

    Google Scholar 

  49. Elguero, J.; Marzin, C.; Katritzky, A. R.; Linda, P. The Tautomerism of Heterocycles; Academic Press: New York, 1976.

    Google Scholar 

  50. Claramunt, R. M.; Elguero, J.: Katritzky, A. R. Advan. Heterocycl. Chem. 2000, 77, 1.

    Google Scholar 

  51. Minkin, V. I.; Garnovskii, A. D.; Elguero, J.; Katritzky, A. R.; Denisko, O. V. Advan. Heterocycl. Chem. 2000, 76, 157.

    Google Scholar 

  52. Llamas-Saiz, A. L.; Foces-Foces, C.; Sobrados, I.; Elguero, J.; Meutermans, W. Acta Crystallogr., C 1993, 49, 724.

    Google Scholar 

  53. Szelejewska-Wozniakowska, A.; Chilmonczyk, Z.; Les, A.; Wawer, I. Solid State Nucl. Magnetic Resonance, 1998, 13, 63.

    Google Scholar 

  54. Maciejewska, D.; Herold, F.; Wolska, I. J. Mol. Struct. 2000, 553, 73.

    Google Scholar 

  55. Jaszunski, M.; Mikkelsen, K. V.; Rizzo, A.; Witanowski, M. J. Phys. Chem. A 2000, 104, 1466.

    Google Scholar 

  56. Koppel, I. A.; Palm, V. A. In Advances in Linear Free Energy Relationships; Chapman, N. B.; Shorter, J., Eds.; Plenum Press: London, 1972; p. 215.

    Google Scholar 

  57. Mauret, P.; Fayet, J.-P.; Fabre, M. Bull. Soc. Chim. Fr. 1975, p. 1675.

  58. Manalo, M. N.; de Dios, A. C.; Cammi, R. J. Phys. Chem. A 2000, 104, 9600.

    Google Scholar 

  59. Catalán, J. J. Chem. Soc. Perkin Trans. 2 2001, p. 1117.

  60. Bednarek, E.; Dobrowolski, J. C.; Dobrosz-Teperek, K.; Kozerski, L.; Lewandowski, W.; Mazurek, A. P. J. Mol. Struct. 2000, 554, 233.

    Google Scholar 

  61. Facelli, J. C. Chem. Phys. Lett. 2000, 322, 91.

    Google Scholar 

  62. Llamas-Saiz, A. L.; Foces-Foces, C.; Mó, O.; Yáñez, M.; Elguero, J. Acta Crystallogr. Sect. B 1992, 48, 700.

    Google Scholar 

  63. Potrzebowski, M. J.; Cypryk, M.; Michalska, M.; Koziol, A. E.; Kazmierski, S.; Ciesielski, W.; Klinowski, J. J. Phys. Chem. B 1998, 102, 4488.

    Google Scholar 

  64. Megiel, E.; Kasprzycka-Guttman, T.; Jagielska, A.; Wroblewska, L. J. Mol. Struct. 2001, 569, 111.

    Google Scholar 

  65. Foces-Foces, C.; Fontenas, C.; Elguero, J.; Sobrados, I. An. Quim. Intern. Ed. 1997, 93, 219.

    Google Scholar 

  66. Schurko, R. W.; Wasylishen, R. E. J. Phys. Chem. A 2000, 104, 3410.

    Google Scholar 

  67. Chesnut, D. B.; Quin, L. D. J. Amer. Chem. Soc. 1994, 116, 9638.

    Google Scholar 

  68. Alagona, G.; Ghio, C.; Monti, S. Theochem 1998, 433, 203.

    Google Scholar 

  69. Subramanian, G.; Schleyer, P. v. R.; Jiao, H. Angew. Chem. Intern. Ed. Engl. 1996, 35, 2638.

    Google Scholar 

  70. Bettinger, H. F.; Sulzbach, H. M.; Schleyer, P. v. R.; Schaefer, H. F. J. Org. Chem. 1999, 64, 3278.

    Google Scholar 

  71. Fabian, J.; Herzog, K. Vib. Spectrosc. 1998, 16, 77.

    Google Scholar 

  72. Fabian, J.; Gloe, K.; Wust, M.; Kruger-Rambusch, T.; Rademacher, O.; Graubaum, H. Phosphorus Sulfur Silicon Related Elements 1998, 140, 35.

    Google Scholar 

  73. Delaere, D.; Nguyen, M. T.; Vanquickenborne, L. G. Chem. Phys. Lett. 2001, 333, 103.

    Google Scholar 

  74. Cyranski, M. K.; Wawer, I.; Zielinska, A.; Mrozek, A.; Koleva, V.; Lozanova, C. J. Phys. Org. Chem. 2001, 14, 323.

    Google Scholar 

  75. Karney, W. L.; Kastrup, C. J.; Oldfield, S. P.; Rzepa, H. S. J. Chem. Soc. Perkin Trans. 2 2002, p. 388.

  76. Cyranski, M. K.; Krygowski, T. M.; Katritzky, A. R.; Schleyer, P. v. R. J. Org. Chem. 2002, 67, 1333.

    Google Scholar 

  77. Katritzky, A. R.; Barczynski, P.; Musumarra, G.; Pisano, D.; Szafran, M. J. Amer. Chem. Soc. 1989, 111, 7.

    Google Scholar 

  78. Schleyer, P. v. R.; Freeman, P. K.; Jiao, H.; Goldfuss, B. Angew. Chem. Intern. Ed. Engl. 1995, 34, 337.

    Google Scholar 

  79. Schleyer, P. v. R.; Puchta, R.; Boggavarapu, K.; Mauksch, M.; Eikema Hommes, N. v.; Alkorta, I.; Elguero, J. manuscript in preparation.

  80. Alkorta, I.; Elguero, J. New J. Chem. 1999, 23, 951.

    Google Scholar 

  81. Bühl, M.; Thiel, W.; Fleischer, U.; Kutzelnigg, W. J. Phys. Chem. 1995, 99, 4000.

    Google Scholar 

  82. Bocian, W.; Wiench, J. W.; Stefaniak, L.; Webb, G. A. Magnetic Resonance Chem. 1996, 34, 453.

    Google Scholar 

  83. Wiench, J. W.; Stefaniak, L.; Tabaszewska, A.; Webb, G. A. Electron. J. Theoret. Chem. 1997, 2, 71.

    Google Scholar 

  84. Jazwinski, J.; Staszewska, O.; Staszewski, P.; Stefaniak, L.; Wiench, J. W.; Webb, G. A. J. Mol. Struct. 1999, 475, 181.

    Google Scholar 

  85. Jazwinski, J.; Staszewska, O.; Wiench, J. W.; Stefaniak, L.; Araki, S.; Webb, G. A. Magnetic Resonance Chem. 2000, 38, 617.

    Google Scholar 

  86. Witanowski, M.; Biedrzycka, Z.; Grabowski, Z. Magnetic Resonance Chem. 2000, 38, 580.

    Google Scholar 

  87. Witanowski, M.; Biedrzycka, Z.; Sicinska, W.; Grabowski, Z.; Webb, G. A. J. Magnetic Resonance 1997, 124, 127.

    Google Scholar 

  88. Wrackmeyer, B.; Schwarze, B.; Milius, W.; Boese, R.; Parchment, O. G.; Webb, G. A. J. Organomet. Chem. 1998, 552, 247.

    Google Scholar 

  89. Bednarek, E.; Dobrowolski, J. Cz.; Dobrosz-Teperek, K.; Sitkowski, J.; Kozerski, L.; Lewandowski, W.; Mazurek, A. P. J. Mol. Struct. 1999, 482–483, 333.

    Google Scholar 

  90. Kaczmarek, L.; Zagrodzki, B.; Kamienski, B.; Pietrzak, M.; Schilf, W.; Les, A. J. Mol. Struct. 2000, 553, 61.

    Google Scholar 

  91. Kupka, T.; Pasterna, G.; Jaworska, M.; Karali, A.; Dais, P. Magnetic Resonance Chem. 2000, 38, 149.

    Google Scholar 

  92. Corbally, R. P.; Mehta, L. K.; Parrick, J.; Short, E. L. Magnetic Resonance Chem. 2000, 38, 1034.

    Google Scholar 

  93. Olah, G. A.; Prakash, G. K. Surya; Rasul, G. J. Amer. Chem. Soc. 2001, 123, 3308.

    Google Scholar 

  94. Mattmann, E.; Mathey, F.; Sevin, A.; Frison, G. J. Org. Chem. 2002, 67, 1208.

    Google Scholar 

  95. Juselius, J.; Sundholm, D. Phys. Chem. Chem. Phys. 2000, 2, 2145.

    Google Scholar 

  96. Witanowski, M.; Biedrzycka, Z.; Sicinska, W.; Grabowski, Z. J. Magnetic Resonance 1998, 131, 54.

    Google Scholar 

  97. Mroz, P.; Pietrusiewicz, K. M.; Wolinski, K. Mol. Phys. Rept. 2000, 29, 205.

    Google Scholar 

  98. Witanowski, M.; Stefaniak, L.; Szymanski, S.; Januszewski, J. Magnetic Resonance 1977, 28, 217.

    Google Scholar 

  99. Srinivasan, P. R.; Lichter, R. L. J. Magnetic Resonance 1977, 28, 227.

    Google Scholar 

  100. Barfield, M.; Fagerness, P. J. Amer. Chem. Soc. 1997, 119, 8699.

    Google Scholar 

  101. Witanowski, M.; Stefaniak, L.; Webb, G. A. Annu. Rept. NMR Spetrosc. 1993, 25, 88.

    Google Scholar 

  102. Jameson, C. J.; Jameson, A. K.; Oppusungu, D.; Wille, S.; Burrell, P. M.; Mason, J. J. Chem. Phys. 1981, 74, 81.

    Google Scholar 

  103. Zhan, C.-G.; Chipman, D. M. J. Chem. Phys. 1999, 110, 1611.

    Google Scholar 

  104. Witanowski, M.; Biedrzycka, Z.; Sicinska, W.; Webb, G. A. J. Mol. Struct. 2000, 516, 107.

    Google Scholar 

  105. Rablen, P. R.; Pearlman, S. A.; Finkbiner, J. J. Phys. Chem. A 1999, 103, 7357.

    Google Scholar 

  106. Chapmann, N. B.; Shorter, J. Eds., Advances in Linear Free Energy Relationships; Plenum Press: London, 1972.

    Google Scholar 

  107. Faure, R.; Llinares, J.; Elguero, J.; Goya, P. Bull. Soc. Chim. Belg. 1987, 96, 603.

    Google Scholar 

  108. Chapmann, N. B., Shorter, J. Eds.; Correlation Analysis in Chemistry; Plenum Press: New York, 1978.

    Google Scholar 

  109. Abboud, J.-L. M.; Boyer, Elguero, J. G.; Cabildo, P.; Claramunt, R. M. Spectrochim. Acta 1991, 47A, 785.

    Google Scholar 

  110. Christe, K. O.; Wilson, W. W.; Sheehy, J. A.; Boatz, J. A. Angew, Chem. Int. Ed. Engl. 1999, 38, 2004.

    Google Scholar 

  111. Gauss, J. J. Chem. Phys. 1993, 99, 3629.

    Google Scholar 

  112. Gauss, J.; Stanton, J. F. J. Chem. Phys. 1995, 103, 3561.

    Google Scholar 

  113. Gauss, J.; Stanton, J. F. J. Chem. Phys. 1996, 105, 2574.

    Google Scholar 

  114. Gauss, J.; Stanton, J. F. Phys. Chem. Chem. Phys. 2000, 2, 2047.

    Google Scholar 

  115. Gauss, J.; Werner, H.-J. Phys. Chem. Chem. Phys. 2000, 2, 2083.

    Google Scholar 

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  1. Instituto de Química Médica (C.S.I.C.), Juan de la Cierva, 3, E-28006, Madrid, Spain

    Ibon Alkorta & José Elguero

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  1. Ibon Alkorta
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Alkorta, I., Elguero, J. GIAO Calculations of Chemical Shifts in Heterocyclic Compounds. Structural Chemistry 14, 377–389 (2003). https://doi.org/10.1023/A:1024402027760

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