The first enantiomerically pure triangulane (M)- trispiro[2.0.0.2.1.1]nonane Is a σ-[4]helicene

Angewandte Chemie - International Edition

Volumn 38, Issue 23, 1999, Pages 3474-3477

  De Meijere, Armin ^a   Khlebnikov, Alexander F ^b   Kostikov, Rafael R ^b   Kozhushkov, Sergei I ^a   Schreiner, Peter R ^a   Wittkopp, Alexander ^a   Yufit, Dmitrii S ^c  

^a UNIVERSITY OF GÖTTINGEN   (Germany)

^b ST PETERSBURG STATE UNIVERSITY   (Russian Federation)

^c DURHAM UNIVERSITY   (United Kingdom)

Author keywords

Ab initio calculations; Chirality; Cyclopropanations; Density functional calculations; Small ring systems

Indexed keywords

ALKENE DERIVATIVE;

ARTICLE; CALCULATION; CHEMICAL BOND; CHIRALITY; CHROMATOPHORE; ENANTIOMER; OPTICAL ROTATION;

EID: 0033521187     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19991203)38:23<3474::AID-ANIE3474>3.0.CO;2-6     Document Type: Article

References (50)

1. K. Mislow, P. Bickart, Isr. J. Chem. 1976/1977, 15, 1. In considering what the term "cryptochiral" is meant to describe, one has to point out a serious deficiency, as any racemate might also be called cryptochiral. "Crypto-optically active" appears to be a more appropriate term.
2. H. Wynberg, G. L. Hekkert, J. P. M. Houbiers, H. W. Bosch, J. Am. Chem. Soc. 1965, 87, 2635.
3. Reviews: a) A. de Meijere, S. I. Kozhushkov in Advances in Strain in Organic Chemistry, Vol. 4 (Ed.: B. Halton), JAI, London, 1995. pp. 225-282; b) N. S. Zefirov, T. S. Kuznetsova, A. N. Zefirov, Izv. Akad. Nauk 1995, 1613-1621; Russian Chem. Bull. (Engl. Trans.) 1995, 1613-1621: c) A. de Meijere, S. I. Kozhushkov, Chem. Rev. 2000, 100, in press.
4. Reviews: a) A. de Meijere, S. I. Kozhushkov in Advances in Strain in Organic Chemistry, Vol. 4 (Ed.: B. Halton), JAI, London, 1995. pp. 225-282; b) N. S. Zefirov, T. S. Kuznetsova, A. N. Zefirov, Izv. Akad. Nauk 1995, 1613-1621; Russian Chem. Bull. (Engl. Trans.) 1995, 1613-1621: c) A. de Meijere, S. I. Kozhushkov, Chem. Rev. 2000, 100, in press.
5. Reviews: a) A. de Meijere, S. I. Kozhushkov in Advances in Strain in Organic Chemistry, Vol. 4 (Ed.: B. Halton), JAI, London, 1995. pp. 225-282; b) N. S. Zefirov, T. S. Kuznetsova, A. N. Zefirov, Izv. Akad. Nauk 1995, 1613-1621; Russian Chem. Bull. (Engl. Trans.) 1995, 1613-1621: c) A. de Meijere, S. I. Kozhushkov, Chem. Rev. 2000, 100, in press.
6. Reviews: a) A. de Meijere, S. I. Kozhushkov in Advances in Strain in Organic Chemistry, Vol. 4 (Ed.: B. Halton), JAI, London, 1995. pp. 225-282; b) N. S. Zefirov, T. S. Kuznetsova, A. N. Zefirov, Izv. Akad. Nauk 1995, 1613-1621; Russian Chem. Bull. (Engl. Trans.) 1995, 1613-1621: c) A. de Meijere, S. I. Kozhushkov, Chem. Rev. 2000, 100, in press.
7. The stereochemical features of unbranched triangulanes 1 have been thoroughly analyzed: N. S. Zefirov, S. I. Kozhushkov, T. S. Kuznetsova, O. V. Kokoreva, K. A. Lukin, B. I. Ugrak, S. S. Tratch, J. Am. Chem. Soc. 1990, 112, 7702-7707.
8. L. Fitjer, J.-M. Conia, Angew. Chem. 1973, 85, 832-833; Angew. Chem. Int. Ed. Engl. 1973, 12, 761-762.
9. L. Fitjer, J.-M. Conia, Angew. Chem. 1973, 85, 832-833; Angew. Chem. Int. Ed. Engl. 1973, 12, 761-762.
10. N. S. Zefirov, K. A. Lukin, S. I. Kozhushkov, T. S. Kuznetsova, A. M. Domarev, I. M. Sosonkin, Zh. Org. Khim. 1989, 25, 312-319; J. Org. Chem. USSR Engl. Transl. 1989, 25, 278-284.
11. N. S. Zefirov, K. A. Lukin, S. I. Kozhushkov, T. S. Kuznetsova, A. M. Domarev, I. M. Sosonkin, Zh. Org. Khim. 1989, 25, 312-319; J. Org. Chem. USSR Engl. Transl. 1989, 25, 278-284.
12. K. A. Lukin, S. I. Kozhushkov, N. S. Zefirov, Magn. Reson. Chem. 1991, 29, 774-776.
13. R. Boese, T. Haumann, E. D. Jemmis, B. Kiran, S. Kozhushkov, A. de Meijere, Liebigs Ann. 1996, 913-920.
14. a) H.-D. Beckhaus, C. Rüchardt, S. I. Kozhushkov, V. N. Belov, S. P. Verevkin. A. de Meijere, J. Am. Chem. Soc. 1995, 117, 11 854-11 860;
15. b) V. A. Luk'yanova, S. M. Pimenova, V. P. Kolesov, T. S. Kuznetsova, O. V. Kokoreva, S. I. Kozhushkov, N. S. Zefirov, Zh. Fz. Khim. 1993, 67, 1145-1148; Russ. J. Phys. Chem. Engl. Transl. 1993, 67, 1023-1025.
16. b) V. A. Luk'yanova, S. M. Pimenova, V. P. Kolesov, T. S. Kuznetsova, O. V. Kokoreva, S. I. Kozhushkov, N. S. Zefirov, Zh. Fz. Khim. 1993, 67, 1145-1148; Russ. J. Phys. Chem. Engl. Transl. 1993, 67, 1023-1025.
17. K. P. Meurer, F. Vögtle, Top. Curr. Chem. 1985, 127 1-76.
18. a) A. de Meijere, S. I. Kozhushkov, T. Spaeth, N. S. Zefirov, J. Org. Chem. 1993, 58, 502;
19. b) A. de Meijere, S. I. Kozhushkov, T. Spaeth, Org. Synth. 1999, accepted for checking.
20. A. de Meijere, S. I. Kozhushkov, N. S. Zefirov, Synthesis 1993, 681-683.
21. For the rules of this nomenclature, see I. Ugi, Z. Naturforsch. B 1965, 20, 405-409.
22. S. Bernasconi, A. Comini, A. Corbella, P. Gariboldi, M. Sisti, Synthesis 1980, 385-387.
23. According to the rule established by Helmchen et al., the first eluting amide 6b should have an S configuration in the acid moiety, and its diastereomer 6 a should have an R configuration, in complete agreement with the assignment from the crystal structure analysis: a) G. Helmchen, H. Völter, W. Schühle, Tetrahedron Lett. 1977, 1417-1420; b) G. Helmchen, G. Nill, D. Flockerzi, W. Schühle, M. S. K. Youssef, Angew. Chem. 1979, 91, 64-65; Angew. Chem. Int. Ed. Engl. 1979, 18, 62-63; c) G. Helmchen, G. Nill, D. Flockerzi, M. S. K. Youssef, Angew. Chem. 1979, 91, 65-66; Angew. Chem. Int. Ed. Engl. 1979, 18, 63-64.
24. According to the rule established by Helmchen et al., the first eluting amide 6b should have an S configuration in the acid moiety, and its diastereomer 6 a should have an R configuration, in complete agreement with the assignment from the crystal structure analysis: a) G. Helmchen, H. Völter, W. Schühle, Tetrahedron Lett. 1977, 1417- 1420; b) G. Helmchen, G. Nill, D. Flockerzi, W. Schühle, M. S. K. Youssef, Angew. Chem. 1979, 91, 64-65; Angew. Chem. Int. Ed. Engl. 1979, 18, 62-63; c) G. Helmchen, G. Nill, D. Flockerzi, M. S. K. Youssef, Angew. Chem. 1979, 91, 65-66; Angew. Chem. Int. Ed. Engl. 1979, 18, 63-64.
25. According to the rule established by Helmchen et al., the first eluting amide 6b should have an S configuration in the acid moiety, and its diastereomer 6 a should have an R configuration, in complete agreement with the assignment from the crystal structure analysis: a) G. Helmchen, H. Völter, W. Schühle, Tetrahedron Lett. 1977, 1417- 1420; b) G. Helmchen, G. Nill, D. Flockerzi, W. Schühle, M. S. K. Youssef, Angew. Chem. 1979, 91, 64-65; Angew. Chem. Int. Ed. Engl. 1979, 18, 62-63; c) G. Helmchen, G. Nill, D. Flockerzi, M. S. K. Youssef, Angew. Chem. 1979, 91, 65-66; Angew. Chem. Int. Ed. Engl. 1979, 18, 63-64.
26. According to the rule established by Helmchen et al., the first eluting amide 6b should have an S configuration in the acid moiety, and its diastereomer 6 a should have an R configuration, in complete agreement with the assignment from the crystal structure analysis: a) G. Helmchen, H. Völter, W. Schühle, Tetrahedron Lett. 1977, 1417- 1420; b) G. Helmchen, G. Nill, D. Flockerzi, W. Schühle, M. S. K. Youssef, Angew. Chem. 1979, 91, 64-65; Angew. Chem. Int. Ed. Engl. 1979, 18, 62-63; c) G. Helmchen, G. Nill, D. Flockerzi, M. S. K. Youssef, Angew. Chem. 1979, 91, 65-66; Angew. Chem. Int. Ed. Engl. 1979, 18, 63-64.
27. According to the rule established by Helmchen et al., the first eluting amide 6b should have an S configuration in the acid moiety, and its diastereomer 6 a should have an R configuration, in complete agreement with the assignment from the crystal structure analysis: a) G. Helmchen, H. Völter, W. Schühle, Tetrahedron Lett. 1977, 1417- 1420; b) G. Helmchen, G. Nill, D. Flockerzi, W. Schühle, M. S. K. Youssef, Angew. Chem. 1979, 91, 64-65; Angew. Chem. Int. Ed. Engl. 1979, 18, 62-63; c) G. Helmchen, G. Nill, D. Flockerzi, M. S. K. Youssef, Angew. Chem. 1979, 91, 65-66; Angew. Chem. Int. Ed. Engl. 1979, 18, 63-64.
28. 2) = 0.141 for all data (153 parameters), conventional R(F) = 0.0524 for 587 reflections with I ≥ 2σ(I). GOF = 1.033. The absolute configuration was assigned on the basis of the known R configuration of 5; the Flack parameter for the reported configuration is 0(5) and for the inverted model 1(5). Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-112810. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
29. K. A. Lukin, S. I. Kozhushkov, A. A. Andrievsky, B. I. Ugrak, N. S. Zefirov, J. Org. Chem. 1991, 56, 6176-6179.
30. P. K. Kadaba, Synthesis 1971, 316-317.
31. Recent review: L. R. Subramanian, K.-P. Zeller, Methoden Org. Chem. (Houben-Weyl) 1997-, Vol. E, 17a, pp. 256-308.
32. N. S. Zefirov, K. A. Lukin, S. F. Politanskii, M. A. Margulis, Zh. Org. Khim. 1987, 23, 1799-1800; J. Org. Chem. USSR Engl. Transl. 1987, 23, 1603-1604.
33. N. S. Zefirov, K. A. Lukin, S. F. Politanskii, M. A. Margulis, Zh. Org. Khim. 1987, 23, 1799-1800; J. Org. Chem. USSR Engl. Transl. 1987, 23, 1603-1604.
34. P. E. Eaton, K. A. Lukin, J. Am. Chem. Soc. 1993, 115, 11 370-11 375.
35. a) R. Paulissen, A. J. Hubert, P. Teyssie, Tetrahedron Lett. 1972, 1465-1466;
36. b) review: Y. V. Tomilov, V. A. Dokichev, U. M. Dzhemilev, O. M. Nefedov, Usp. Khim. 1993, 62, 847-886; Russ. Chem. Rev. Engl. Transl. 1993, 62, 799-838.
37. b) review: Y. V. Tomilov, V. A. Dokichev, U. M. Dzhemilev, O. M. Nefedov, Usp. Khim. 1993, 62, 847-886; Russ. Chem. Rev. Engl. Transl. 1993, 62, 799-838.
38. W. A. König, The Practice of Enantiomer Separation by Capillary Gas Chromatography, Hüthig, Heidelberg, 1987.
39. M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. de Frees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzales, J. A. Pople, Gaussian 94, rev. E2, Gaussian Inc., Pittsburgh, PA, 1994.
40. A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100.
41. C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1987, 37, 785-789.
42. R. G. Parr, W. Yang, Density Functional Theory of Atoms and Molecules, Oxford University Press, New York, 1989.
43. W. J. Hehre, L. Radom, P. v. R. Schleyer, J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley Interscience, New York, 1986.
44. S. Grimme, Chem. Phys. Lett. 1996, 259, 128.
45. [29]
46. R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 3.
47. A. Schaefer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571.
48. A. Schaefer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829.
49. C. Djerassi, Optical Rotatory Dispersion-Applications to Organic Chemistry, McGraw Hill Inc., New York, 1960.
50. Despite the fact that this suggested nomenclature may lead to an association with the σ-aromatic character of the cyclopropane ring (see D. Cremer, Tetrahedron 1988, 44, 7427-7454), aromaticity is not a precondition for the rotatory strengths of compounds of type 2, as the spiro-annelated cyclopropane subunits are perpendicular with respect to each other.