2,3,6,7-tetrasubstituted perhydroanthracenes: Stereoselective synthesis and biconformationality studies

European Journal of Organic Chemistry

Volumn , Issue 4, 1999, Pages 875-884

  Berninger, Jörn ^a   Krauss, Rolf ^a   Weinig, Hans Georg ^a   Koert, Ulrich ^a   Ziemer, Burkhard ^a   Harms, Klaus ^b  

^a HUMBOLDT UNIVERSITY   (Germany)

^b PHILIPPS UNIVERSITY MARBURG   (Germany)

Author keywords

Biconformational triple ring flip; Conformational analysis; Perhydroanthracene; Synthesis design

Indexed keywords

ANTHRACENE DERIVATIVE;

ARTICLE; CONFORMATION; NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

EID: 0032877168     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/(sici)1099-0690(199904)1999:4<875::aid-ejoc875>3.0.co;2-%23     Document Type: Article

References (13)

1. R. W. Hoffmann, M. Stahl, U. Schopfer, G. Frenking, Chem. Eur. J. 1998, 4, 559-566. The term biconformational refers to molecules with two low-energy conformers. If these conformers are populated to > 80%, the compound is called biconformational. In the case of the unsubstituted perhydroanthracene the two conformers have the same energy and are equally populated. In the case of the tetrasubstituted perhydroanthracene with different substituents A, B, the two conformers do not necessarily have the same energy and are differently populated. As long as the substituted perhydroanthracene systems display two distinct chair-chair-chair low-energy conformations, we consider it as reasonable to call them biconformational. One has to keep in mind that it is often the environment (e.g. solvent, membrane) that has a major influence on conformational preferences.
2. E. L. Eliel, S. H. Wilen, L. N. Mander, Stereochemistry of Organic Compounds Wiley, New York. 1994, p. 686 ff.
3. P. Vanhee, B. van de Graaf, D. Tavernier, J. M.A. Baas, J. Org. Chem. 1983, 48, 648-652; P. Vanhee, B. van de Graaf, J. M. A. Baas, D. Tavernier, Tetrahedron Lett. 1982, 23, 3837-3838: D. Tavernier, M. J. O. Anteunis, Org. Magn. Res. 1982, 18, 109-111.
4. P. Vanhee, B. van de Graaf, D. Tavernier, J. M.A. Baas, J. Org. Chem. 1983, 48, 648-652; P. Vanhee, B. van de Graaf, J. M. A. Baas, D. Tavernier, Tetrahedron Lett. 1982, 23, 3837-3838: D. Tavernier, M. J. O. Anteunis, Org. Magn. Res. 1982, 18, 109-111.
5. P. Vanhee, B. van de Graaf, D. Tavernier, J. M.A. Baas, J. Org. Chem. 1983, 48, 648-652; P. Vanhee, B. van de Graaf, J. M. A. Baas, D. Tavernier, Tetrahedron Lett. 1982, 23, 3837-3838: D. Tavernier, M. J. O. Anteunis, Org. Magn. Res. 1982, 18, 109-111.
6. The cycloadduct is produced in the racemic form. The synthesis of the tetrasubstituted perhydroanthracene is described for the racemic series here. For the use of chiral fumarates as an potential approach to enantiomerically enriched cyclohexenones see: J. Jurczak, T. Bauer, C. Chapuis in Methods Org. Chem. - E 21 Stereoselective Synthesis, (Eds. G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann), vol. 5, p. 2735, Thieme, Stuttgart, 1996.
7. F. Frinquelli, L. Minuti, F. Pizzo, A. Taticchi, Acta Chem. Scand. 1993, 47, 255-263.
8. D. H. R. Barton, S. W. McCombie, J. Chem. Soc., Perkin Trans. 1, 1975, 1574-1585.
9. A. Fürst, P. A. Plattner, Helv. Chim. Acta 1949, 32, 275-283.
10. A quantitative analysis on the different populations of the all-chair conformers is not yet possible with the existing data.
11. S. V. Ley, H. W. M. Priepke, S. L. Warriner, Angew. Chem. 1994, 106, 2410-2412; Angew. Chem. Int. Ed. Engl. 1994, 33, 2290-2292; J.-L. Montchamp, F. Tian, M. E. Hart, J. W. Frost, J. Org. Chem. 1996, 61, 3897-3899.
12. S. V. Ley, H. W. M. Priepke, S. L. Warriner, Angew. Chem. 1994, 106, 2410-2412; Angew. Chem. Int. Ed. Engl. 1994, 33, 2290-2292; J.-L. Montchamp, F. Tian, M. E. Hart, J. W. Frost, J. Org. Chem. 1996, 61, 3897-3899.
13. S. V. Ley, H. W. M. Priepke, S. L. Warriner, Angew. Chem. 1994, 106, 2410-2412; Angew. Chem. Int. Ed. Engl. 1994, 33, 2290-2292; J.-L. Montchamp, F. Tian, M. E. Hart, J. W. Frost, J. Org. Chem. 1996, 61, 3897-3899.