A third-generation bicyclopropylidene: Straightforward preparation of 15,15'-bis(hexaspiro[2.0.2.0.0.0.2.0.2.0.1.0]pentadecyclidene) and a C(2v)-symmmetric branched [15]triangulane

Angewandte Chemie - International Edition

Volumn 39, Issue 14, 2000, Pages 2495-2498

  Von Seebach, Malte ^a   Kozhushkov, Sergei I ^a   Boese, Roland ^b   Benet Buchholz, Jordi ^b   Yufit, Dmitrii S ^c   Howard, Judith A K ^c   De Meijere, Armin ^a  

^a UNIVERSITY OF GÖTTINGEN   (Germany)

^b UNIVERSITY OF DUISBURG ESSEN   (Germany)

^c DURHAM UNIVERSITY   (United Kingdom)

Author keywords

Carbenoids; Cyclopropanations; Small ring systems; Spiro compounds; Strained molecules

Indexed keywords

BICYCLO COMPOUND; CYCLOPROPANE DERIVATIVE; HYDROCARBON;

ARTICLE; CHEMICAL MODIFICATION; CHEMICAL REACTION; CRYSTAL STRUCTURE; DIMERIZATION; REACTION ANALYSIS; SYNTHESIS;

EID: 0034679487     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3773(20000717)39:14<2495::AID-ANIE2495>3.0.CO;2-U     Document Type: Article

References (49)

1. P. Le Perchec, J.-M. Conia, Tetrahedron Lett. 1970, 1587-1588.
2. a) A. de Meijere, S. I. Kozhushkov, T. Spaeth, N. S. Zefirov, J. Org. Chem. 1993, 58, 502-505;
3. b) A. de Meijere, S. I. Kozhushkov, T. Späth, Org. Synth. 2000, 79, in press.
4. Reviews: a) A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Zh. Org. Khim. 1996, 32, 1607-1626; A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Russ. J. Org. Chem. (Engl. Transl.) 1996, 32, 1555- 1575; b) A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Top. Curr. Chem. 2000, 207, 89-147; c) latest application in combinatorial chemistry: A. de Meijere, H. Nüske, M. Es-Sayed, T. Labahn, M. Schroen, S. Bräse, Angew. Chem. 1999, 111, 3881-3884; Angew. Chem. Int. Ed. 1999, 38, 3669-3672.
5. Reviews: a) A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Zh. Org. Khim. 1996, 32, 1607-1626; A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Russ. J. Org. Chem. (Engl. Transl.) 1996, 32, 1555-1575; b) A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Top. Curr. Chem. 2000, 207, 89-147; c) latest application in combinatorial chemistry: A. de Meijere, H. Nüske, M. Es-Sayed, T. Labahn, M. Schroen, S. Bräse, Angew. Chem. 1999, 111, 3881-3884; Angew. Chem. Int. Ed. 1999, 38, 3669-3672.
6. Reviews: a) A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Zh. Org. Khim. 1996, 32, 1607-1626; A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Russ. J. Org. Chem. (Engl. Transl.) 1996, 32, 1555- 1575; b) A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Top. Curr. Chem. 2000, 207, 89-147; c) latest application in combinatorial chemistry: A. de Meijere, H. Nüske, M. Es-Sayed, T. Labahn, M. Schroen, S. Bräse, Angew. Chem. 1999, 111, 3881-3884; Angew. Chem. Int. Ed. 1999, 38, 3669-3672.
7. Reviews: a) A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Zh. Org. Khim. 1996, 32, 1607-1626; A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Russ. J. Org. Chem. (Engl. Transl.) 1996, 32, 1555- 1575; b) A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Top. Curr. Chem. 2000, 207, 89-147; c) latest application in combinatorial chemistry: A. de Meijere, H. Nüske, M. Es-Sayed, T. Labahn, M. Schroen, S. Bräse, Angew. Chem. 1999, 111, 3881-3884; Angew. Chem. Int. Ed. 1999, 38, 3669-3672.
8. Reviews: a) A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Zh. Org. Khim. 1996, 32, 1607-1626; A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Russ. J. Org. Chem. (Engl. Transl.) 1996, 32, 1555- 1575; b) A. de Meijere, S. I. Kozhushkov, A. F. Khlebnikov, Top. Curr. Chem. 2000, 207, 89-147; c) latest application in combinatorial chemistry: A. de Meijere, H. Nüske, M. Es-Sayed, T. Labahn, M. Schroen, S. Bräse, Angew. Chem. 1999, 111, 3881-3884; Angew. Chem. Int. Ed. 1999, 38, 3669-3672.
9. Reviews: a) A. de Meijere, S. I. Kozhushkov, Chem. Rev. 2000, 100, 93-142; b) A. de Meijere, S. I. Kozhushkov in Advances in Strain in Organic Chemistry, Vol. 4 (Ed.: B. Halton), JAI Press, London, 1995, pp. 225-282; c) N. S. Zefirov, T. S. Kuznetsova, A. N. Zefirov, Izv. Akad. Nauk 1995, 1613-1621; N. S. Zefirov, T. S. Kuznetsova, A. N. Zefirov, Russ. Chem. Bull. (Engl. Trans.) 1995, 1613-1621.
10. Reviews: a) A. de Meijere, S. I. Kozhushkov, Chem. Rev. 2000, 100, 93-142; b) A. de Meijere, S. I. Kozhushkov in Advances in Strain in Organic Chemistry, Vol. 4 (Ed.: B. Halton), JAI Press, London, 1995, pp. 225-282; c) N. S. Zefirov, T. S. Kuznetsova, A. N. Zefirov, Izv. Akad. Nauk 1995, 1613-1621; N. S. Zefirov, T. S. Kuznetsova, A. N. Zefirov, Russ. Chem. Bull. (Engl. Trans.) 1995, 1613-1621.
11. Reviews: a) A. de Meijere, S. I. Kozhushkov, Chem. Rev. 2000, 100, 93-142; b) A. de Meijere, S. I. Kozhushkov in Advances in Strain in Organic Chemistry, Vol. 4 (Ed.: B. Halton), JAI Press, London, 1995, pp. 225-282; c) N. S. Zefirov, T. S. Kuznetsova, A. N. Zefirov, Izv. Akad. Nauk 1995, 1613-1621; N. S. Zefirov, T. S. Kuznetsova, A. N. Zefirov, Russ. Chem. Bull. (Engl. Trans.) 1995, 1613-1621.
12. Reviews: a) A. de Meijere, S. I. Kozhushkov, Chem. Rev. 2000, 100, 93-142; b) A. de Meijere, S. I. Kozhushkov in Advances in Strain in Organic Chemistry, Vol. 4 (Ed.: B. Halton), JAI Press, London, 1995, pp. 225-282; c) N. S. Zefirov, T. S. Kuznetsova, A. N. Zefirov, Izv. Akad. Nauk 1995, 1613-1621; N. S. Zefirov, T. S. Kuznetsova, A. N. Zefirov, Russ. Chem. Bull. (Engl. Trans.) 1995, 1613-1621.
13. a) S. Zöllner, H. Buchholz, R. Boese, R. Gleiter, A. de Meijere, Angew. Chem. 1991, 103, 1544-1546; Angew. Chem. Int. Ed. Engl. 1991, 30, 1518-1520;
14. a) S. Zöllner, H. Buchholz, R. Boese, R. Gleiter, A. de Meijere, Angew. Chem. 1991, 103, 1544-1546; Angew. Chem. Int. Ed. Engl. 1991, 30, 1518-1520;
15. b) S. Zöllner, Dissertation, Universität Hamburg, 1991.
16. S. I. Kozhushkov, T. Haumann, R. Boese, A. de Meijere, Angew. Chem. 1993, 105, 426-424; Angew. Chem. Int. Ed. Engl. 1993, 32, 401-403.
17. S. I. Kozhushkov, T. Haumann, R. Boese, A. de Meijere, Angew. Chem. 1993, 105, 426-424; Angew. Chem. Int. Ed. Engl. 1993, 32, 401-403.
18. W. R. Moore, H. R. Ward, J. Org. Chem. 1960, 25, 2073; W. R. Moore, M. R. Ward, J. Org. Chem. 1962, 27, 4179-4181. For a recent review on the dimerization of halometallocyclopropylidenoids from 1.1-dibromocyclopropanes see ref. [3b].
19. W. R. Moore, H. R. Ward, J. Org. Chem. 1960, 25, 2073; W. R. Moore, M. R. Ward, J. Org. Chem. 1962, 27, 4179-4181. For a recent review on the dimerization of halometallocyclopropylidenoids from 1.1-dibromocyclopropanes see ref. [3b].
20. a) M. Borer, T. Loosli, M. Neuenschwander, Chimia 1991, 45, 382-386;
21. b) T. Loosli, M. Borer, I. Kulakowska, A. Minder, M. Neuenschwander, P. Engel, Helv. Chim. Acta 1995, 78, 1144-1165;
22. c) M. Borer, T. Loosli, A. Minder, M. Neuenschwander, P. Engel, Helv. Chim. Acta 1995, 78, 1311-1324;
23. d) M. Borer, M. Neuenschwander, Helv. Chim. Acta 1997, 80, 2486-2501;
24. e) R. Huwyler, X. Li, P. Bönzli, M. Neuenschwander, Helv. Chim. Acta 1999, 82, 1242-1249.
25. a) L. Fitjer, J.-M. Conia, Angew. Chem. 1973, 85, 832-833; Angew. Chem. Int. Ed. Engl. 1973, 12, 761-762;
26. a) L. Fitjer, J.-M. Conia, Angew. Chem. 1973, 85, 832-833; Angew. Chem. Int. Ed. Engl. 1973, 12, 761-762;
27. b) K. A. Lukin, N. S. Zefirov, D. S. Yufit, Yu. T. Struchkov, Tetrahedron 1992, 48, 9977-9984.
28. Systematic name: 15,15′-bis(hexaspiro[2.0.2.0.0.0.2.0.2.0.1.0]pentadecylidene).
29. [3b] See for example H.-D. Beckhaus, C. Rüchardt, S. I. Kozhushkov, V. N. Belov, S. P. Verevkin, A. de Meijere, J. Am. Chem. Soc. 1995, 117, 11854-11860.
30. Several examples of attempted, but unsuccessful dibromocarbene addition to sterically congested bicyclopropylidenes have been reported: a) Y. Fukuda, Y. Yamamoto, K. Kimura, Y. Odaira, Tetrahedron Lett. 1979, 877-878; b) A. Tubul, M. Bertrand, Tetrahedron Lett. 1984, 25, 2219-2222. In addition, permethylbicyclopropylidene also did not react with dibromocarbene under different conditions; c) M. von Seebach, Dissertation, Universität Göttingen, 2000.
31. Several examples of attempted, but unsuccessful dibromocarbene addition to sterically congested bicyclopropylidenes have been reported: a) Y. Fukuda, Y. Yamamoto, K. Kimura, Y. Odaira, Tetrahedron Lett. 1979, 877-878; b) A. Tubul, M. Bertrand, Tetrahedron Lett. 1984, 25, 2219-2222. In addition, permethylbicyclopropylidene also did not react with dibromocarbene under different conditions; c) M. von Seebach, Dissertation, Universität Göttingen, 2000.
32. Several examples of attempted, but unsuccessful dibromocarbene addition to sterically congested bicyclopropylidenes have been reported: a) Y. Fukuda, Y. Yamamoto, K. Kimura, Y. Odaira, Tetrahedron Lett. 1979, 877-878; b) A. Tubul, M. Bertrand, Tetrahedron Lett. 1984, 25, 2219-2222. In addition, permethylbicyclopropylidene also did not react with dibromocarbene under different conditions; c) M. von Seebach, Dissertation, Universität Göttingen, 2000.
33. a) W. von E. Doering; A. K. Hoffman, J. Am. Chem. Soc. 1954, 76, 6162-6165;
34. b) W. von E. Doering, W. A. Henderson, J. Am. Chem. Soc. 1958, 80, 5274-5277.
35. D. Seyferth, V. A. Mai, J. Y.-P. Mui, K. V. Darragh, J. Org. Chem. 1966, 31, 4079-4081. For a review on dihalocyclopropanations see: E. V. Dehmlow, Methoden Org. Chem. (Houben-Weyl), 4th ed., 1952-, Vol. E 19b, 1989, pp. 1461-1627.
36. D. Seyferth, V. A. Mai, J. Y.-P. Mui, K. V. Darragh, J. Org. Chem. 1966, 31, 4079-4081. For a review on dihalocyclopropanations see: E. V. Dehmlow, Methoden Org. Chem. (Houben-Weyl), 4th ed., 1952-, Vol. E 19b, 1989, pp. 1461-1627.
37. W. Kirmse, U. Jansen, Chem. Ber. 1985, 118, 2607-2625, and references therein.
38. a) R. Paulissen, A. J. Hubert, P. Teyssie, P. Tetrahedron Lett. 1972, 1465-1466;
39. b) J. Kottwitz, H. Vorbrüggen, Synthesis 1975, 636-637;
40. c) A. J. Anciaux, A. J. Hubert, A. F. Noels, P. Teyssie, J. Org. Chem. 1980, 45, 695-702. For a review see also: Yu. V. Tomilov, V. A. Dokichev, U. M. Dzhemilev, O. M. Nefedov, Usp. Khim. 1993, 62, 847-886; Yu. V. Tomilov, V. A. Dokichev, U. M. Dzhemilev, O. M. Nefedov, Russ. Chem. Rev. 1993, 62, 799-838.
41. c) A. J. Anciaux, A. J. Hubert, A. F. Noels, P. Teyssie, J. Org. Chem. 1980, 45, 695-702. For a review see also: Yu. V. Tomilov, V. A. Dokichev, U. M. Dzhemilev, O. M. Nefedov, Usp. Khim. 1993, 62, 847-886; Yu. V. Tomilov, V. A. Dokichev, U. M. Dzhemilev, O. M. Nefedov, Russ. Chem. Rev. 1993, 62, 799-838.
42. c) A. J. Anciaux, A. J. Hubert, A. F. Noels, P. Teyssie, J. Org. Chem. 1980, 45, 695-702. For a review see also: Yu. V. Tomilov, V. A. Dokichev, U. M. Dzhemilev, O. M. Nefedov, Usp. Khim. 1993, 62, 847-886; Yu. V. Tomilov, V. A. Dokichev, U. M. Dzhemilev, O. M. Nefedov, Russ. Chem. Rev. 1993, 62, 799-838.
43. 34 (406.6): C 91.57, H 8.43; found: C 91.81, H 8.56.
44. Systematic names: 24-dichloro- (7), 24-bromo-24-fluoro- (8), (tetradecaspiro[2.0.2.0.0.0.0.0.2.0.2.0.0.0.2.0.2.0.0.1.0.0.2.0.2.0.0.0.] untriacontane (9).
45. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nos. CCDC-142835 (6), -142836 (7), -142041 (8), and -142837 (9). Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
46. R. Boese, T. Miebach, A. de Meijere, J. Am. Chem. Soc. 1991, 113, 1743-1748.
47. For comparison, in spiropentane itself the angles Ψ and Φ are 90.2 and 179.6, respectively, while in ethano-bridged spiropentane Ψ and Φ are 80.0 and 154.0, respectively. See for example R. Boese, D. Bläser, K. Gomann, U. H. Brinker, J. Am. Chem. Soc. 1989, 111, 1501-1503.
48. Thus, the previously published additivity Scheme for bonding parameters in [n]triangulanes also hold for [15]triangulane 9. See for example R. Boese, T. Haumann, E. D. Jemmis, B. Kiran, S. Kozhushkov, A. de Meijere, Liebigs Ann. 1996, 913-919.
49. A. Bondi, J. Phys. Chem. 1964, 68, 441-451.