Zusammenfassung
Beim Cyclohexan und seinen Abkömmlingen kann man die nicht an der Ringbildung beteiligten Valenzen der Kohlenstoffatome in «äquatoriale» und «polare» einteilen. Jedes Ringkohlenstoffatom hat eine polare und eine äquatoriale Bindung.
An einem gegebenen Kohlenstoffatom ist ein äquatorial gebundener Ligand thermodynamisch stabiler als ein polar gebundener. Zwei benachbarte Substituenten werden, wenn es sich um Ionenreaktion handelt, leichter abgespalten, wenn sie beide «polar» gebunden sind, als wenn einer von ihnen oder beide «äquatoriale» Bindungen besetzen. Ein Ligand in der polaren Stellung an einem gegebenen Kohlenstoffatom unterliegt stärkerer sterischer Hinderung als in der äquatorialen Anordnung.
Die Anwendung dieser allgemeinen. Regeln auf die Steroidchemie wird kurz beschrieben. Dabei wird die Abhängigkeit dieser Anwendung von der für den Sterinkern angenommenen Konfiguration betont.
Die Ausdehnung dieser Ideen auf das Gebiet der Di-und Triterpenoide wird angedeutet.
References
C. W. Beckett, K. S. Pitzer, andR. Spitzer, J. Amer. Chem. Soc.69, 2488 (1947).
O. Hassel's nomenclature5 is different, but the distinction remains the same.
O. Hassel andH. Viervoll, Acta Chem. Scand.1, 149 (1947).
SeeO. Hassel andB. Ottar, Acta chem. Scand.1, 929 (1947) for a summarizing paper and references to earlier work.
C. W. Beckett, K. S. Pitzer, andR. Spitzer, J. Amer. Chem. Soc.69, 2488 (1947).
G. Vavon, Bull. Soc. Chim. [4],49, 937 (1931).
W. Hückel, Ann. Chem.533, 1 (1937).
A. Skita andW. Faust, Ber. Dtsch. Chem. Ges.64, 2878 (1931).
G. Vavon andP. Anziani, Bull. Soc. Chim. [5],4, 1080 (1937). In connection with the conformations of poly-substituted cyclohexanes it should be mentioned thatO. Bastiansen, O. Ellersen, andO. Hassel, (Acta chem. Scand.3, 918 [1949]) have recently shown that the five stereoisomeric benzene hexachlorides assume, in agreement with our general argument, those conformations which have the maximum possible number of equatorial carbon-chlorine bonds.
Conformations (XIII) and (XIV) are unambiguous representations of the steroid nucleus provided that rings A, B, and C are chairs. This is almost certainly true for a trans-A/B ring fusion (compare the X-ray evidence ofC. H. Carlisle andD. Crowfoot (Proc. Roy. Soc. A184, 64 [1945]) on the conformation of cholesteryl iodide) and a similar situation, at least in solution, probably holds for a cis-A/B fusion. The justification for the latter has been more extensively presented elsewhere4,5. See also the discussion bySobotka 6.
L. F. Fieser,The Chemistry of Natural Products Related to Phenanthrene (1st Ed. 1936, Reinhold Publishing Corporation).
See footnotes 2 and 3 on p. 316, 2nd column.
E. D. Hughes andC. K. Ingold et al., J. Chem. Soc. 2117 (1948).
D. H. R. Barton andE. Miller, J. Amer. Chem. Soc.72, 1066 (1950).
O. Bastiansen andO. Hassell, Nature157, 765 (1946).
O. Hassel andH. Viervoll, Acta chem. Scand.1, 149 (1947) and papers there cited.
D. H. R. Barton, J. Chem. Soc. 340 (1948).
H. Sobotka,The Chemistry of the Steroids, 1938, p. 48et seq. (The Williams and Wilkins Co.).
G. Vavon, Bull. Soc. Chim. [4],49, 937 (1931).
For summary seeJ. L. Simonsen andL. N. Owen,The Terpenes, Vol. I (Cambridge University Press, 1947).
Of course for pyrolytic elimination of substituents by “unimolecular” mechanisms (seeD. H. R. Barton, J. Chem. Soc. 2174 [1949]) cis-elimination is the rule and the discussion given here is no longer relevant.
W. Hückel, Ann. Chem.533, 1 (1937).
Compare the preceding paper in whichL. F. Fieser has discussed steric effects under the headings intraradial and extraradial.
G. Vavon, Bull. Soc. Chim. [4],49, 937 (1931).
W. Hückel et al., Ann. Chem.533, 128 (1937).
For summary see:J. L. Simonsen andL. N. Owen,The Terpenes, Vol. I (Cambridge University Press, 1947).
G. Vavon, Bull. Soc. Chim. [4],49, 937 (1931).
L. F. Fieser, Exper.6, 312 (1950).
W. Hückel, Ann. Chem.533, 1 (1937).
W. Hückel et al., Ann. Chem.533, 128 (1937).
D. H. R. Barton, Quart. Rev.3, 36 (1949).
D. H. R. Barton, Quart. Rev.3, 36 (1949).
T. R. Ames andE. R. H. Jones, Nature164, 1090 (1949).
L. Ruzicka andH. Gubser, Helv. chim. acta28, 1054 (1945); these authors assigned the opposite configuration at C2.
R. Nowak, O. Jeger, andL. Ruzicka, Helv. chim. acta,32, 323 (1949). The equatorial conformation for the hydroxyl group in these compounds is also indicated by the fact thatβ-amyrin is more stable thermodynamically than epi-β-amyrin (L. Ruzicka andW. Wirz,ib., 24, 248 (1941).
L. Ruzicka, M. Montavon, andO. Jeger, Helv. chim. acta31, 819 (1948); and earlier papers from the same laboratory.
L. Ruzicka, O. Jeger, A. Grob, andH. Hösli, Helv. chim. acta,26, 2283 (1943).
Author information
Authors and Affiliations
Additional information
The word conformation is used to denote differing strainless arrangements in space of a set of bonded atoms. In accordance with the tenets of classical stereochemistry, these arrangements represent only one molecular species.
Rights and permissions
About this article
Cite this article
Barton, D.H.R. The conformation of the steroid nucleus. Experientia 6, 316–320 (1950). https://doi.org/10.1007/BF02170915
Published:
Issue Date:
DOI: https://doi.org/10.1007/BF02170915