A kinetically stabilized [1.1]paracyclophane: Isolation and x-ray structural analysis

Angewandte Chemie - International Edition

Volumn 37, Issue 6, 1998, Pages 817-819

  Kawai, Hidetoshi ^a   Suzuki, Takanori ^a   Ohkita, Masakazu ^a   Tsuji, Takashi ^a  

^a HOKKAIDO UNIVERSITY   (Japan)

Author keywords

Arenes; Cyclopanes; Photochemistry; Strained molecules

Indexed keywords

EID: 0031901621     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19980403)37:6<817::AID-ANIE817>3.0.CO;2-Z     Document Type: Article

References (25)

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3. A. Guijarro, M. Yus, Tetrahedron 1995, 51, 231; H. J. Reich, I. L. Reich, K. E. Yelm, J. E. Holladay, D. Gschneidner, J. Am. Chem. Soc. 1993, 115, 6625.
4. A. Guijarro, M. Yus, Tetrahedron 1995, 51, 231; H. J. Reich, I. L. Reich, K. E. Yelm, J. E. Holladay, D. Gschneidner, J. Am. Chem. Soc. 1993, 115, 6625.
5. M. Regitz in The Chemistry of Diazonium and Diazo Groups (Ed.: S. Patai), Wiley, Chichester, 1975, chap. 17.
6. L. M. Baigrie, H. R. Seiklay, T. T. Tidwell, J. Am. Chem. Soc. 1985, 107, 5391; L. M. Baigrie, D. Lenoir, H. R. Seiklay, T. T. Tidwell, J. Org. Chem. 1985, 50, 2105; R. Häner, T. Laube, D. Seebach, J. Am. Chem. Soc. 1985, 107, 5396.
7. L. M. Baigrie, H. R. Seiklay, T. T. Tidwell, J. Am. Chem. Soc. 1985, 107, 5391; L. M. Baigrie, D. Lenoir, H. R. Seiklay, T. T. Tidwell, J. Org. Chem. 1985, 50, 2105; R. Häner, T. Laube, D. Seebach, J. Am. Chem. Soc. 1985, 107, 5396.
8. L. M. Baigrie, H. R. Seiklay, T. T. Tidwell, J. Am. Chem. Soc. 1985, 107, 5391; L. M. Baigrie, D. Lenoir, H. R. Seiklay, T. T. Tidwell, J. Org. Chem. 1985, 50, 2105; R. Häner, T. Laube, D. Seebach, J. Am. Chem. Soc. 1985, 107, 5396.
9. H. J. Reich, Org. React. 1993, 44, 1; A. L. Cossey, L. Lombardo, L. N. Mander, Tetrahedron, 1980, 21, 4383; L. Lombardo, L. N. Mander, J. Org. Chem. 1983, 48, 2298.
10. H. J. Reich, Org. React. 1993, 44, 1; A. L. Cossey, L. Lombardo, L. N. Mander, Tetrahedron, 1980, 21, 4383; L. Lombardo, L. N. Mander, J. Org. Chem. 1983, 48, 2298.
11. H. J. Reich, Org. React. 1993, 44, 1; A. L. Cossey, L. Lombardo, L. N. Mander, Tetrahedron, 1980, 21, 4383; L. Lombardo, L. N. Mander, J. Org. Chem. 1983, 48, 2298.
12. H. J. Reich, J. M. Renga, J. Org. Chem. 1975, 40, 3313.
13. To our knowledge, the preparation of α-selenylated carboxamides through the reaction of ketene with selenylamines was previously unknown.
14. As with 1a and 1b, a product resulting from the aromatization of only one of the Dewar-benzene moieties of 1c was not detected in the photolysate.
15. [2]
16. The photochemical transformation of 2 into 3 represents the first direct preparation of a p,p′-benzene dimer. To our knowledge [2.2]paracyclophanes do not undergo such a transannular [4+4] addition under irradiation. Apparently, the photochemical reactivity of 2 is dictated by the geometrical constraint imposed upon it: the face-to-face arrangement of two bent benzene rings in close proximity. For photoadditions of aromatic compounds, see J. J. McCullough, Chem. Rev. 1987, 87, 811.
17. The rate of this cycloreversion is comparable to those for known p,p′-benzene dimers: N. C. Yang, M. Chen, P. Chen, J. Am. Chem. Soc. 1984, 106, 7310; H. Gan, J. L. King, N. C. Yang, Tetrahedron Lett. 1989, 30, 1205.
18. The rate of this cycloreversion is comparable to those for known p,p′-benzene dimers: N. C. Yang, M. Chen, P. Chen, J. Am. Chem. Soc. 1984, 106, 7310; H. Gan, J. L. King, N. C. Yang, Tetrahedron Lett. 1989, 30, 1205.
19. -3. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Center as supplementary publication no. CCDC-100696. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ (fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
20. There exists some ambiguity concerning the bending angles α and β since the nonbridgehead aromatic carbon atoms are displaced from the mean plane by 0.004-0.011 Å and the plane of the methylene bridge is not exactly orthogonal to that formed by the bridgehead and the adjacent aromatic carbon atoms.
21. S. Grimme, J. Am. Chem. Soc. 1992, 114, 10542; M. von Arnim, S. D. Peyerimhoff, Theor. Chim. Acta 1993, 85, 43, and references herein.
22. S. Grimme, J. Am. Chem. Soc. 1992, 114, 10542; M. von Arnim, S. D. Peyerimhoff, Theor. Chim. Acta 1993, 85, 43, and references herein.
23. Paracyclophanes so far prepared are not sufficiently stable to be isolated. D. S. van Es, F. J. J. de Kanter, W. H. de Wolf, F. Bickelhaupt, Angew. Chem. 1995, 107, 2728; Angew. Chem. Int. Ed. Engl. 1995, 34, 2553, and references therein.
24. Paracyclophanes so far prepared are not sufficiently stable to be isolated. D. S. van Es, F. J. J. de Kanter, W. H. de Wolf, F. Bickelhaupt, Angew. Chem. 1995, 107, 2728; Angew. Chem. Int. Ed. Engl. 1995, 34, 2553, and references therein.
25. A weak NOE was also observed between the N-methyl and the aromatic protons. Therefore, the amide groups seem to flip-flop more or less freely in solution with respect to the aromatic rings.