Skip to main content
SpringerLink
Log in

Strain release in conformational and geometric adaptation of moderately and highly congested systems: Interplay of small structural effects

  • Published:
Structural Chemistry Aims and scope Submit manuscript

Abstract

Local and global steric strains are studied by spectroscopy and crystallography and by theoretical models. Double-bond and heteroatom pair contributions are investigated with regard to cyclic and acyclic hydrocarbons. Theoretical investigation of steric strain release (SSR) through conformational dodging and geometric deformation from molecular standard values reveals details about congested structures which are not accessible through experimentation. Qualitative rules concerning access to blocked sites—distorted gem-6 structures, bi-sected double bonds—and the control of anomeric structures are understood through studying SSR processes based on the interplay of the Pitzer or related strain and of the hyperconjugative effect, the ring or backbone strain and various through-space interactions (TSI). The empirical and semi-empirical computational modelization of strain release processes leading to the control of complex rotations disclose surprising flexibility in hyper-crowded molecules.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Greenberg, A., Liebman, J. F.Strained Organic Molecules; Academic Press, New York, 1978;

    Google Scholar 

  2. Rüchardt, C.; Beckhaus, H. D.Angewandte Chem.,1985,24, 529;

    Google Scholar 

  3. Rüchardt, C.; Beckhaus, H. D.Top. Curr. Chem.,1986,130, 1.

    Google Scholar 

  4. Engler, E. M.; Andose, J. D.; von R. Schleyer, P.J. Am. Chem. Soc.,1973,95, 8005;

    Google Scholar 

  5. De Tar, D. F.; Binzet, S.; Darba, P.J. Org. Chem.,1985,50, 2826;

    Google Scholar 

  6. Rüchardt, C.; Beckhaus, H. D.Angewandte Chem. Int. Ed.,1980,19, 429;

    Google Scholar 

  7. Wertz, D. H.; Allinger, N. L.Tetrahedron,1974,31, 1579;

    Google Scholar 

  8. Allinger, N. L.J. Am. Chem. Soc.,1977,99, 8127.

    Google Scholar 

  9. Allinger, N. L.; Geise, H. J.; Pyckhout, W.; Paquette, L. A.; Galluci, J. C.J. Am. Chem. Soc.,1989,111, 1106;

    Google Scholar 

  10. Pettersson, I.; Liljefors, T.J. Comp. Chem.,1987,8, 1139;

    Google Scholar 

  11. Allinger, N. L.; Lü, J. H.J. Comp. Chem.,1987,8, 1146;

    Google Scholar 

  12. Vedani, A.; Dobler, M.; Dunitz, J. D.J. Comp. Chem.,1986,6, 701;

    Google Scholar 

  13. Liljefors, T.; Tai, J. C.; Li, S.; Allinger, N. L.,J. Comp. Chem.,1987,8, 1051;

    Google Scholar 

  14. Allinger, N. L.; Pathiaseril, A.J. Comp. Chem.,1987,8, 1225.

    Google Scholar 

  15. Various authors [6] have proposed original approaches to the equilibrium between the repulsive and attractive parts of energy.

  16. Bürgi, H. B.; Dunitz, J. D.J. Am. Chem. Soc.,1987,109, 2924;

    Google Scholar 

  17. Sutter, U. W.;J. Am. Chem. Soc.,1979,101, 6481;

    Google Scholar 

  18. Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Steward, J. J. P.J. Am. Chem. Soc.,1985,107, 3902;

    Google Scholar 

  19. Burshtein, K. Ya; Shorygin, P. P.; Anikin, N. A.Optika Spektrosk,1978,44, 913 (Optics Spectrosc.,1978,44, 538);

    Google Scholar 

  20. Cossé-Barbi, A.Mol. Phys.,1981,42, 655.

    Google Scholar 

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

    Google Scholar 

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

    Google Scholar 

  23. Hansch, C.; Leo, A.Substituent Constants for Correlation Analysis in Chemistry and Biology; Wiley Interscience, New York, 1979;

    Google Scholar 

  24. Dubois, J.-E.; Laurent, D.; Viellard, H.C. R. Acad. Sci.,1976,264C, 1019;

    Google Scholar 

  25. Dubois, J.-E.; Laurent, D.; Aranda, A.J. Chim. Phys. 1973,11–12, 1608, 1616;

    Google Scholar 

  26. Dubois, J.-E.Pure Appl. Chem.,1981,53, 1313.Bull. Soc. Chim.,1956, 1058.

    Google Scholar 

  27. Gallo, R.;Prog. Phys. Org. Chem.,1983,14, 115;

    Google Scholar 

  28. Seeman, J. I.; Viers, J. W.; Schug, J. C.; Stovall, M. D.J. Am. Chem. Soc.,1984,106, 143.

    Google Scholar 

  29. Seeman, J. I.; Schug, J. C.; Viers, J. W.J. Org. Chem.,1983,48, 2399;

    Google Scholar 

  30. Charton, M.J. Org. Chem.,1980,43, 3995;

    Google Scholar 

  31. De Tar, D. F.J. Org. Chem.,1980,45, 5166.

    Google Scholar 

  32. De Tar, D. F.J. Org. Chem.,1980,45, 5174;

    Google Scholar 

  33. Mac Phee, J. A.; Panaye, A.; Dubois, J.-E.Tetrahedron,1978,34, 3553;

    Google Scholar 

  34. Panaye, A.; Mac Phee, J. A.; Dubois, J.-E.Tetrahedron,1980,36, 759;

    Google Scholar 

  35. Dubois, J.-E.; Viellard, H.Bull. Soc. Chim. Fr.,1968, 900;

  36. Dubois, J.-E.; Lion, C.; Panaye, A.Nouv. J. Chim.,1981,5, 381.

    Google Scholar 

  37. Seeman, J. I.;Pure App. Chem.,1987,59 (12) 1661;

    Google Scholar 

  38. Wipke, W. T.; Gund, P.J. Am. Chem. Soc.,1976,98, 8170;

    Google Scholar 

  39. Dubois, J.-E.; Mac Phee, J. A.; Panaye; A.Tetrahedron,1980,36, 919.

    Google Scholar 

  40. Roussel, C.; Chanon, M.; Metzger, J.Tetrahedron Lett.,1971, 1861;

  41. Berg, U.; Liljefors, T.; Roussel, C.; Sandström, J.Acc. Chem. Res.,1985,18, 80;

    Google Scholar 

  42. Hounshell, W. D.; Iroff, L. D.; Iverson, D. J.; Wroczynski, R. J.; Mislow, K.Isr. J. Chem.,1980,20, 65;

    Google Scholar 

  43. Iwamura, H.; Mislow, K.Acc. Chem. Res.,1988,21, 175.

    Google Scholar 

  44. Cossé-Barbi, A.; Dubois, J.-E.;Tetrahedron Lett.,1987,28, 1169;

    Google Scholar 

  45. Cossé-Barbi, A.; Massat, A.; Dubois, J.-E.Bull. Soc. Chim. Beige,1985,94, 919;

    Google Scholar 

  46. Cossé-Barbi, A.; Dubois, J.-E.J. Am. Chem. Soc.,1987,109, 1503;

    Google Scholar 

  47. Mac Phee, J. A.; Panaye, A.; Dubois, J.-E.; Leroy, F.; Hospital, M.Tetrahedron Letters,1979,7, 653;

    Google Scholar 

  48. Dubois, J.-E.Pure Appl. Chem.,1978,49, 1029.

    Google Scholar 

  49. Dubois, J.-E.; Cossé-Barbi, A.J. Am. Chem. Soc.,1988,110, 1270;

    Google Scholar 

  50. Dubois, J.-E.; Cossé-Barbi, A.Phys. Org. Chem., Kobayashi, M., Ed.,1986,31, 415.

    Google Scholar 

  51. March, J.Advanced Organic Chemistry: Reactions, Mechanisms and Structure; Wiley, New York, 1985, 3rd ed.

    Google Scholar 

  52. Kemp, J. D.; Pitzer, K. S.J. Chem. Phys.,1936,4, 749; or]J. Am. Chem. Soc.,1937,59, 276;

    Google Scholar 

  53. Pitzer, K. S.Discussions Faraday Soc.,1951,10, 66;

    Google Scholar 

  54. Pitzer, R. M.Acc. Chem. Res.,1983,16, 207.

    Google Scholar 

  55. Hehre, W. J.; Pople, J. A.; Devaquet, A. J. P.J. Am. Chem. Soc.,1976,98, 664;

    Google Scholar 

  56. Pross, A.; Radom, L.; Riggs, N. V.J. Am. Chem. Soc.,1980,102, 2253;

    Google Scholar 

  57. Dorigo, A.; Pratt, D. W.; Houk, K. N.J. Am. Chem. Soc.,1987,109, 6571.

    Google Scholar 

  58. Kirby, A. J.The Anomeric Effect and Related Stereoelectronic Effects at Oxygen; Springer Verlag: Berlin, 1983.

    Google Scholar 

  59. Deslongchamps, P.Stereoelectronic Effects in Organic Chemistry, Wiley: New York, 1983.

    Google Scholar 

  60. Lambert, J. B.; Clikeman, R. R.; Kalulu, M. T.; Marko, D. E.; Bosch, R. J.; Xue, L.Acc. Chem. Res.,1987,20, 454.

    Google Scholar 

  61. Flood, E.; Pulay, P.; Boggs, J. E.J. Am. Chem. Soc.,1977,99, 5570.

    Google Scholar 

  62. Allen, F. H.; Bellard, S.; Brice, M. D.; Cartwright, B. A.; Doubleday, A.; Higgs, H.; Hummerlink, T.; Hummerlink-Peters, B.; Kennard, O.; Motherwell, W. D. S.; Rodgers, J. R.; Watson, D. G.Acta Crystallogr., Sect. B,1979,35, 2331.

    Google Scholar 

  63. Allen, F. H.; Kennard, O.; Taylor, R.Acc. Chem. Res. 1983,16, 146.

    Google Scholar 

  64. Maroni, P.; Dubois, J.-E.J. Chim, Phys.,1954;402, 51;

    Google Scholar 

  65. Massat; A.; Dubois, J.-E.J. Mol. Struct.,1969,4, 385; Dubois, J.-E.; Massat, A.; Guillaume, P.J. Mol. Struct.,1969;4, 402;

    Google Scholar 

  66. Cossé-Barbi, A.C. R. Acad. Sci.,1971,273, 380;

    Google Scholar 

  67. Jackman, L. M.; Kelly, D. P.;J. Chem. Soc., Sect. B,1970, 102;

  68. Dubois, J.-E.; Doucet, J. P.; Tiffon, B.J. Chim. Phys.,1973, 805; Dubois, J.-E.; Carabedian, M.Org. Magn. Reson.,1980,14, 264;

    Google Scholar 

  69. Delseth, C.; Kintzinger, J. P.Helv. Chim. Acta,1976,59, 466;1976,58, 1410;

    Google Scholar 

  70. Dubois, J.-E.; Herzog, H.J. Chem. Soc. Chem. Commun.,1972, 932;

  71. Panaye, A.; Doucet, J. P.; Dubois, J.-E.Tetrahedron Lett.,1981,22, 1235; Doucet, J. P.; Panaye, A.; Dubois, J.-E.;J. Org. Chem.,1983,48, 3174;

    Google Scholar 

  72. Andrieu, C. G.; Debruyne, D.; Paquer, D.Org. Magn. Reson.,1978,11, 528;

    Google Scholar 

  73. Delseth, C.; Kintzinger, J. P.Helv. Chim. Acta,1978,61, 1327;

    Google Scholar 

  74. Dyer, J. C.; Harris, D. L.; Evans, S. A.;J. Org. Chem.,1982,47, 3660.

    Google Scholar 

  75. Nachbar, R. B.; Johnson, C. A.; Mislow, K.J. Org. Chem.,1982,47, 4829.

    Google Scholar 

  76. Allinger, N. L.;J. Am. Chem. Soc.,1977,99, 8127.

    Google Scholar 

  77. Radom, L.; Hehre, W. J.; Pople, J. A.J. Am. Chem. Soc.,1972,94, 2371.

    Google Scholar 

  78. Wiberg, K. B.; Martin, E.J. Am. Chem. Soc.,1985,107, 5035.

    Google Scholar 

  79. Hehre, W. J.; Pople, J. A.; Devaquet, A. J. P.J. Am. Chem. Soc.,1976,98, 664;

    Google Scholar 

  80. Dorigo, A. E.; Pratt, D. W.; Houk, K. N.J. Am. Chem. Soc.,1987,109, 6591;

    Google Scholar 

  81. Pross, A.; Radom, L.; Riggs, N.J. Am. Chem. Soc.,1980,102, 2853.

    Google Scholar 

  82. Cossé-Barbi, A.; Bhattacharjee, A.; Doucet, J. P.; Dubois, J.-E.J. Mol. Struct. Theochem.,1990,204, 67.

    Google Scholar 

  83. Cossé-Barbi, A.J. Chim. Phys.,1979,76, 489;

    Google Scholar 

  84. Cossé-Barbi, A.; Dubois, J.-E.Spectrochim. Acta, Part A,1972,28, 561;

    Google Scholar 

  85. Cohen Addad, C.; Cohen Addad, J. P.J. Chem. Soc. Perkin Trans. II,1978,2, 168;

    Google Scholar 

  86. Cohen Addad, C.; D'Assenza, G.Acta Crystallogr., Sect. B,1976,32, 239;

    Google Scholar 

  87. Cohen Addad, C.Spectrochim. Acta, Sect. A.,1980,36, 587;

    Google Scholar 

  88. Lepicard, G.; Berthou, J.; Delettre, J.; Laurent, A.; Mornon, J. P.C. R. Acad. Sci., Ser. C,1973,276, 575;

    Google Scholar 

  89. Cossé-Barbi, A.; Massat, A.J. Mol. Struct.,1980,6331.

  90. Guillaume, P.; Massat, A.; Cossé-Barbi, A.; Dubois, J.-E.;Tetrahedron Lett.,1980,21, 1937.

    Google Scholar 

  91. Cossé-Barbi, A.J. Mol. Struct.,1978,49, 181.

    Google Scholar 

  92. Cossé-Barbi, A.; Dubois, J.-E.Spectrochim. Acta, Sect. A,1972,28, 539.

    Google Scholar 

  93. Pettersson, I.; Rang, K.; Sandström, J.Acta Chem. Scand., Sect. B,1986,40, 751.

    Google Scholar 

  94. Romers, C.; Altona, C.; Buys, H. R.; Havinga, E.Top. Stereochem.,1969,4, 39;

    Google Scholar 

  95. David, S.; Eisenstein, O.; Hehre, W. J.; Salem, L.J. Am. Chem. Soc.,1973,95, 3806.

    Google Scholar 

  96. Sweigart, D. W.; Turner, D. W.J. Am. Chem. Soc.,1972,94, 5599.

    Google Scholar 

  97. Cossé-Barbi, A.; Watson, D. G.; Dubois, J.-E.Tetrahedron Lett.,1989,30, 163.

    Google Scholar 

  98. Dubois, J.-E.; Cossé-Barbi, A.; Watson, D. G.Tetrahedron Lett.,1989,30, 167.

    Google Scholar 

  99. Jeffrey, G. A.; Pople, J. A.; Binkley, J. S.; Vishveshwara, S.J. Am. Chem. Soc.,1978;100, 373;

    Google Scholar 

  100. Briggs, A. J.; Glenn, R.; Jones, P. G.; Kirby, A. J.; Ramaswamy, P.J. Am. Chem. Soc.,1984,106, 6200;

    Google Scholar 

  101. Kirby, A. J.;Pure Appl. Chem.,1987,59, 1605.

    Google Scholar 

  102. Ferguson, D. M.; Raber, D. J.J. Am. Chem. Soc.,1989,111, 4371;

    Google Scholar 

  103. Chang, G.; Guida, W. C.; Clark Still, W.J. Am. Chem. Soc.,1989,111, 4379;

    Google Scholar 

  104. Taylor, R.J. Mol. Graphics,1986,4, 123.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. ITODYS(Institut de Topologie et de Dynamique des Systèmes), de l'Université Paris 7, associé au CNRS, 75005, Paris, France

    Jacques-Emile Dubois & Aliette Cossé-Barbi

Authors
  1. Jacques-Emile Dubois
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Aliette Cossé-Barbi
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Dubois, JE., Cossé-Barbi, A. Strain release in conformational and geometric adaptation of moderately and highly congested systems: Interplay of small structural effects. Struct Chem 2, 89–105 (1991). https://doi.org/10.1007/BF00676620

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00676620

Keywords

Search

Navigation