A facile, general route to adamantanophanes. Synthesis and conformational behavior of [4.4](1,3)adamantanophan-trans,trans-1,8-diene

Tetrahedron Letters

Volumn 37, Issue 28, 1996, Pages 4829-4832

  Mlinarić Majerski, Kata ^a   Pavlović, Dražen ^a   Marinić, Željko ^a  

^a RUDER BO KOVI INSTITUTE   (Croatia)

Author keywords

[No Author keywords available]

Indexed keywords

ADAMANTANE DERIVATIVE;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL BOND; CHEMICAL MODIFICATION; CONFORMATION; CRYSTAL STRUCTURE; CYCLIZATION; OXIDATION; PROTON NUCLEAR MAGNETIC RESONANCE; SYNTHESIS; THERMODYNAMICS; X RAY CRYSTALLOGRAPHY;

EID: 0030575403     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00523-0     Document Type: Article

References (24)

1. 1. For overview see: (a) Vögtle, F. Cyclophane Chemistry, Wiley, Chichester, 1993.
2. (b) Diedench, F. Cyclophanes; in Monographs in Supramolecular Chemistry; Ed. J. F. Stoddart; Royal Society of Chemistry, 1991.
3. 2. Mitchell, R. H.; Boekelheide, V. J. Am. Chem. Soc. 1974, 96, 1547.
4. 3. Mitchell, R. H.; Otsubo, T.; Boekelheide, V. Tetrahedron Lett. 1975, 219.
5. 4. Boekelheide, V.; Andersen, P. H. Tetrahedron Lett. 1970, 1207.
6. 5. Otsubo, T.; Boekelheide, V. J. Org. Chem. 1977, 42, 1085.
7. 6. For a systematic set of rules on cyclophane nomenclature see: (a) Vögtle, F.; Neumann, P. Tetrahedron 1970, 26, 5847
8. (b) Vögtle, F.; Dohm, J.; Rissanen, K. Angew. Chem. Int. Ed. Engl. 1990, 29, 909.
9. (c) Dohm, J.; Nieger, M.; Rissanen, K.; Vögtle, F. Chem. Ber. 1991, 124, 915.
10. 7. Lemmerz, R.; Nieger, M.; Vögtle, F. Chem. Ber. 1994, 174, 1147.
11. 8. (a)Boekelheide, V. Acc. Chem. Res. 1980, 13, 65.
12. (b) Rossa, L.; Vögtle, F. Top. Curr. Chem. 1983, 113, 1.
13. 9. Meyers, C. Y.; Malte, A. M.; Matthews, W. S. J. Am. Chem. Soc. 1969, 91, 7510.
14. 10. Mlinarić-Majerski, K.; Pavlović, D.; Luić, M.; Kojić-Prodić, B. Chem. Ber. 1994, 127, 1327.
15. 4 (508.76): C, 66.09; H, 8.72 % ; Found: C, 66.16; H, 8.75 %.
16. 13
17. 40 (376 60): C, 89.29; H, 10.71 %, Found: C, 89.09, H, 10.88 %.
18. 3) δ 128.72 (d), 58.12 (d), 47.43 (t), 46.79 (t), 46.23 (t), 44.63 (t), 44.54 (t), 40,61 (t), 40.51 (t), 36.79 (t), 33.52 (s), 32.61 (s), 29.59(s), 29.28 (d), 28.74 (d).
19. 15. Crystals of diene 3a are monoclinic and belong to the space group C2/c: a = 14.119 (3) Å, b = 12.022 (1) Å, c = 12.826 (1) Å, β = 97.72 (1) °, z = 4. The details of the X-ray structure of 3a will be published separately : Mlinarić-Majerski, K., Pavlović, D.; Milinković, V.; Kojić-Prodić, B., in preparation.
20. 16. Molecular mechanics calculations (MM2) gave a strain energy of 23.90 kcal/mol for 3a and 27.24 kcal/mol for 3b The program used was written and parametrized by N. L. Allinger and Y. H. Yuh (University of Georgia, Athens, GA, (1980). For strain energies of other cyclophanes see Bickelhaupt, F. Pur. Appl. Chem. 1990, 62, 373.
21. 17. Carefull examination of spectra reveals the presence of two very broad peaks (C-5/6), which are hardly discernible from the base line.
22. 19
23. 19. Sandström, J. Dynamic NMR Spectroscopy; Academic, New York, 1982.
24. 1H Relay COSY) and by considering analogous data for related adamantanophanes: Pavlović, D., Synthesis and Chemistry of Macrocyclic Molecules with Adamantane as a Building Block, Ph. D. Thesis, Ruder Bošković Institute, University of Zagreb, 1994.