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In a review of this work written about the same time, Shoppee5) changes his wording slightly to imply a half boat structure 2 as the transition state for interconversion.
Shoppee, C. W.: Ann. Rep. 43, 200 (1946).
Beckett, C. W., Pitzer, K. S., Spitzer, R.: J. Am. Chem. Soc. 69, 2488 (1947).
They were also implicitly aware of an entropy term favouring the transition state and thus implied a free energy of activation for inversion a few hundred calories less than 14 kcal/mol.
Jensen, F. R., Noyce, D. S., Sederholm, C. H., Berlin, A. J.: J. Am. Chem. Soc. 82 1256 (1960).
For early references see 10).
Hendrickson, J. B.: J. Am. Chem. Soc. 83, 4537 (1961).
Davis, M., Hassel, O.: Acta. Chem. Scand. 17, 1181 (1963).
Altona, C., Sundaralingam, M.: Tetrahedron 26, 925 (1970) and earlier references therein.
For a recent discussion of this technique see Ref. 14) where references to earlier reviews are given.
Sutherland, I. O.: Ann. Rep. N. M. R. Spectr. 4, 71 (1971).
Eccleston, G., Wyn-Jones, E.: J. Chem. Soc. B 1971, 2469; and references therein.
Allinger and his coworkers 17a also concluded that there is a very small contribution (see Table 1) from bond-deformation. Others 20a) have presumed that this contribution is negligible.
Allinger, N. L., Miller, M. A., Van Catledge, F. A.: Hirsch, J. A.: J. Am. Chem. Soc. 89, 4345 (1967)
Allinger, N. L., Hirsch, J. A., Miller, M. A., Tyminski, I. J., Van-Catledge, F. A.: J. Am. Chem. Soc. 90, 1199 (1968)
Allinger, N. L.: Personal communication, March 1971.
Schmid, H. G.: Thesis, Albert-Ludwigs-Universität, Freiburg 1967
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Williams, J. E., Stang, P. J., Schleyer, P. V. R.: Ann. Rev. Phys. Chem. 19, 531 (1968).
See for example several reviews 14, 23, 24), and individual papers cited therein.
Anderson, J. E.: Quart. Rev. 19, 426 (1965).
Anet, F. A. L., Bourn, A. J. R.: J. Am. Chem. Soc. 89, 760 (1967).
Schmid, and his collaborators 18b) have made the point that there are several conformations similar to the half chair and half boat of comparable energies.
This point has been elegantly demonstrated by Wolfe and Campbell. 27)
Wolfe, S., Campbell, J. R.: Chem. Commun. 1967, 874.
The term “twist conformation” will be used in this review to represent the pseudorotation among boat and twist-boat conformations.
Pickett, H. M., Strauss, H. L.: J. Am. Chem. Soc. 92, 7281 (1970).
Pickett, H. M., Strauss, H. L.: J. Chem. Phys. 53, 376 (1970).
Footnote 20 in the Ref. 29), supra.
Unpublished results of Scholler, W. W. quoted by Dewar, M. J. S.: Topics in Curr. Chem./Fortschr. Chem. Forsch. 23, 1 (1971).
Literature results have been reduced to the chair → twist barrier value where necessary, though often it is not clear whether results are for chair → chair or for chair → twist interconversion. Where there is any explicit or implicit evidence that a change should be made to give the chair → twist barrier, this has been done. Values calculated at the coalescence temperature are given. In some cases where coalescence of an AB-quartet has been treated as coalescence of a doublet, results have been re-calculated on the basis of an AB quartet. Many results quoted in this review differ from these in the original literature for one or several of these reasons. In some cases barriers reported are for partially deuterated compounds but this may not be pointed out in this text.
Harris, R. K., Sheppard, N.: J. Mol. Spectr. 23, 231 (1967).
Bovey, F. A., Anderson, E. W., Hood, F. P., Kornegay, R. L.: J. Chem. Phys. 40, 3099 (1964).
Bushweller, C. H.: Thesis, University of California 1966.
Reisse, J., Stein, M. L., Gilles, J. M., Oth, J. F. M: Tetrahedron Letters 1969, 1917.
Sources of these values are given by Lowe, J. P.: Prog. Phys. Org. Chem. 6, 1 (1968).
Anderson, J. E., Pearson, H.: Tetrahedron Letters 1972, 2779.
Campbell, J. R.: Ph. D. Thesis, Queen's University. Kingston, Ontario, Canada 1969.
Brownstein, S.: Can. J. Chem. 40, 870 (1962).
Harris, R. K., Sheppard, N.: Mol. Phys. 7, 595 (1964).
The claim44 that the barrier to inversion of 1,1-dimethyl-4,4-dibenzyl-cyclohexane is greater than 20 kcal/mol is unconvincing.
Kwart, H., Rank, M. E., Sanchez-Obregon, R., Walls, F.: J. Am. Chem. Soc. 94, 1759 (1972).
Werner, H., Mann, G., Muhlstadt, M., Kohler, H. J.: Tetrahedron Letters 1970, 3563.
Harris, R. K., Spragg, R. A.: J. Chem. Soc. B 1968, 684.
This assumes that at all times van der Waals' forces are repulsive. They may in certain. circumstances be attractive but this qualification is relegated to a footnote since any attractive forces involved are expected to be small from the nature of the Lennard-Jones potential. Further, in the case of bulky substituents such as we are considering here, there are inevitably large van der Waals' repulsive interactions which swamp any small attractive interactions present.
Friebolin, H., Schmid, H., Kabuss, S., Faisst, W.: Org. Mag. Res. 1, 147 (1969).
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St. Jacques, M., Bernard, M., Vaziri, C.: Can. J. Chem. 48, 2386 (1970).
Jefford, C. W., Hill, D. T., Ramey, K. C.: Helv. Chim. Acta 53, 1184 (1970).
Murray, R. W., Kaplan, M. L.: Tetrahedron 27, 1575 (1967).
We have chosen these substitution patterns since they must have axial substituents in any chair conformation, and 1,3 diaxial substituent-hydrogen interactions are expected to be the strongest van der Waals' interaction in cyclohexane, We have excluded 1,1,2,2-tetrasubstituted cyclohexanes, since 1,2 interactions are presumably the principal factors in these molecules.
This is a manifestation of the reflex effect, see Sandris, C., Ourissson, G.: Bull. Soc. Chim. France 1958, 1529; and subsequent references.
Roberts, J. D.: Chem. Brit. 1966, 529.
The Thorpe-Ingold effect.
This is discussed on pp. 200 ff of Ref.58)
Eliel, E. L., Allinger, N. L., Angyal, S. J., Morrison, G. A.: Conformational Analysis. New York: Interscience 1965.
Upper limit for cycloheptane deduced from results for 1,1-difluoro-4,4-dimethyl-cycloheptane given by Glazer, E. S., Ph. D. Thesis, California Institute of Technology, Pasadena 1965.
Anet, F. A. L., St. Jacques, M.: J. Am. Chem. Soc. 88, 2585 (1966).
Anet, F. A. L., Wagner, J.: J. Am. Chem. Soc. 93, 5266 (1971).
This result was obtained for 1,1-difluorocyclodecane, Noe, E. A., Roberts, J. D.: J. Am. Chem. Soc. 94, 2020 (1972).
Riddell, F. G.: Quart. Rev. (London) 21, 364 (1967).
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Values taken from Ref.68) which are refinements of those given in Ref.66).
Friebolin, H., Schmid, H. G., Kabuss, S., Faisst, W.: Org. Mag. Res. 1, 67 (1969).
This is a consequence principally of carbon-oxygen bonds being shorter than carbon-carbon bonds in cyclohexane.
Since the ultimate effect of a large number of 1,3-diaxial interactions in a six-membered ring is to cause a molecule to adopt a twist conformation, see the section on the twist conformation below, it is reasonable to assume such interactions are considerably relieved in the twist conformation and somewhat relieved in the intermediate half-chair conformation.
Lambert, J. B., Keske, R. G., Weary, D. K.: J. Am. Chem. Soc. 89, 5921 (1967).
Lambert, J. B., Keske, R. G., Carhart, R. E., Jovanovich, A. P.: J. Am. Chem. Soc. 89, 3761 (1967).
Calculated from the value for 20d., using a factor derived from tetramethyl analogues 74).
Cleason, G., Androes, G. M., Calvin, M.: J. Am. Chem. Soc. 82, 4428 (1960); 83 4357 (1961).
Anderson, J. E.: J. Am. Chem. Soc. 91, 6374 (1969).
Lüttringhaus, A., Kabuss, S., Maier, W., Friebolin, H.: Z. Naturforsch. 166, 761 (1961).
Riddell, F. G.: J. Chem. Sec. B 1967, 560.
Anet, F. A. L., Sandstrom, J.: Chem. Commun. 1971, 1558.
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Anderson, J. E.: J. Chem. Soc. B 1971, 2030.
Bushweller, C. H., O'Neill, J. W., Bilofsky, H. S.: Tetrahedron 27, 3065 (1971).
The barriers to methyl group rotation in tetramethyl silane and dimethylselenane are 1.4 and 1.5 kcal/mol respectively38). Bond lengths are carbon-silicon, 1.94, carbon-selenium 1.94, carbon-tellurium 2.14; based on the sum of covalent radii85).
Pauling, L.: The nature of the chemical bond, 3rd edit., p. 225. Ithaca, N.Y.: Cornell University Press 1960.
Hutchins, R. O., Kopp, L., Eliel, E. L.: J. Am. Chem. Soc. 90, 7174 (1968).
Murray, R. W., Story, P. R., Kaplan, M. L.: J. Am. Chem. Soc. 88, 526 (1966).
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Feher, F., Degan, B., Söhngen, B.: Angew. Chem. Intern. Ed. Engl. 7, 301 (1968). Lower limit for barrier on basis of data given.
A recent listing of these can be found in Ref.14).
Anderson, J. E.: Chem. Commun. 1969, 669.
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Lambert, J. B., Gosnell, Jr., J. L., Bailey, D. S., Greifenstein, L. G.: Chem. Commun. 1004 (1970). It is not clear here whether results are for chair-boat or chair-chair interconversion.
The results in Tables 8 and 9 are slightly different from those in references 91) and 93) due to a correction in temperature measurement.
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Reusch, W., Anderson, D. F.: Tetrahedron 22, 583 (1966)
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Anderson, J.E. (1974). Chair-chair interconversion of six-membered rings. In: Dynamic Chemistry. Topics in Current Chemistry Fortschritte der Chemischen Forschung, vol 45. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-06471-0_16
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