Self-assembling cyclophanes and catenanes possessing elements of planar chirality

Chemistry - A European Journal

Volumn 4, Issue 2, 1998, Pages 299-310

  Ashton, Peter R ^a   Boyd, Sue E ^a   Menzer, Stephan ^b   Pasini, Dario ^a   Raymo, Françisco M ^a,d   Spencer, Neil ^a   Stoddart, J Fraser ^a,d   White, Andrew J P ^b   Williams, David J ^b   Wyatt, Paul G ^c  

^a UNIVERSITY OF BIRMINGHAM   (United Kingdom)

^b IMPERIAL COLLEGE LONDON   (United Kingdom)

^c GLAXOSMITHKLINE   (United Kingdom)

^d UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Catenanes; Chirality; Pseudorotaxanes; Self assembly; Template synthesis

Indexed keywords

EID: 0031976621     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3765(19980210)4:2<299::AID-CHEM299>3.0.CO;2-Z     Document Type: Article

References (35)

1. a) P. R. Ashton, A. S. Reder, N. Spencer, J. F. Stoddart, J. Am. Chem. Soc. 1993, 115, 5286-5287;
2. b) P. R. Ashton, I. Iriepa, M. V. Reddington, N. Spencer, A. M. Z. Slawin, J. F. Stoddart, D. J. Williams, Tetrahedron Lett. 1994, 35, 4835-4838;
3. c) M. Asakawa, P. R. Ashton, S. E. Boyd, C. L. Brown, S. Menzer, D. Pasini, J. F. Stoddart, M. S. Tolley, A. J. P. White, D. J. Williams, P. G. Wyatt, Chem. Eur. J. 1997, 3, 463-481.
4. a) E. L. Eliel, S. H. Wilen, Stereochemistry of Organic Compounds, Wiley, New York, 1994, pp. 1166-1176;
5. b) V. Prelog, G. Helmchen, Angew. Chem. 1982, 94, 614-631; Angew. Chem. Int. Ed. Engl. 1982, 21, 567-583. According to Prelog and Helmchen, axial and planar chirality may be looked upon alternatively as a type of helicity.
6. b) V. Prelog, G. Helmchen, Angew. Chem. 1982, 94, 614-631; Angew. Chem. Int. Ed. Engl. 1982, 21, 567-583. According to Prelog and Helmchen, axial and planar chirality may be looked upon alternatively as a type of helicity.
7. M. Asakawa, W. Deahen, G. L'abbé, S. Menzer, J. Nouwen, F. M. Raymo, J. F. Stoddart, D. J. Williams, J. Org. Chem. 1996, 61, 9591-9595.
8. a) P. L. Anelli, P. R. Ashton, R. Ballardini, V. Balzani, M. Delgado, M. T. Gandolfi, T. T. Goodnow, A. E. Kaifer, D. Philp, M. Pietraszkiewicz, L. Prodi, M. V. Reddington, A. M. Z. Slawin, N. Spencer, J. F. Stoddart, C. Vicent, D. J. Williams, J. Am. Chem. Soc. 1992, 114, 193-218;
9. b) M. Asakawa, P. R. Ashton, S. E. Boyd, C. L. Brown, R. E. Gillard, O. Kocian, F. M. Raymo, J. F. Stoddart, A. J. P. White, D. J. Williams, J. Org. Chem. 1997, 62, 26-37.
10. For a similar example of cyclophanes possessing planar chirality and existing in chiral and achiral forms ([2.2](1,5)naphthalenophane, in which two 1,5-disubstituted naphthalene units are bridged by bismethylene spacers) see: M. V. Haenel, Chem. Ber. 1978, 111, 1789-1797.
11. R. G. Harvey, J. Pataki, C. Cortez, P. Di Raddo, C. Xi Yang, J. Org. Chem. 1991, 56, 1210-1217.
12. C. L. Brown, D. Philp, N. Spencer, J. F. Stoddart, Isr. J. Chem. 1992, 32, 61-67.
13. 4J is very small and will not correlate), therefore this doublet was assigned to the H-2/6 proton resonances. Accordingly, the doublet at δ = 8.74 must be attributed to the H-4/8 proton resonances.
14. The position of the inside hydroquinone ring proton resonance was located by means of a saturation transfer experiment by irradiating the alongside hydroquinone ring proton resonance at δ = 6.30.
15. c values.
16. -1.
17. 3 at 90°C for 18 h.
18. 6 in the region 7-9 δ at low temperatures did not allow us to follow the behavior of other probe protons (for example, the protons attached to the naphthalene spacers of the cyclophane), which could be more sensitive to the changes in the NMR environment within the pairs of enantiomers II and III.
19. 2 bonds within each bipyridinium unit, are 16° for the inside and 26° for the alongside unit.
20. The N ⋯ N axes of each bipyridinium unit are inclined by ca. 11° with respect to each other.
21. The vector linking the centroid of the alongside hydroquinone ring with the centroid of the bond linking the pyridinium rings of the inside bipyridinium unit forms an angle of 73° with the vector defined by the centroids of the bonds linking the pyridinium rings of the inside and alongside bipyridinium unit. Furthermore, the two hydroquinone rings are not coplanar and their mean planes form an angle of ca. 14°.
22. The term spontaneous resolution indicates that only one of the two possible enantiomers of a racemic form is present in the crystal. In principle, the crown ether can also exist in different stereochemical forms that are in fast equilibrium at room temperature, the conditions under which the crystals were grown.
23. The length and breadth of the tetracationic cyclophane, as defined by the distances between the centroids of the two naphthalene rings and between the centers of the bonds linking the pyridyl rings within each bipyridinium unit, are 10.7 Å and 6.9 Å, respectively.
24. P. R. Ashton, T. T. Goodnow, A. E. Kaifer, M. V. Reddington, A. M. Z. Slawin, N. Spencer, J. F. Stoddart, C. Vicent, D. J. Williams, Angew. Chem. 1989, 101, 1404-1408; Angew. Chem. Int. Ed. Engl. 1989, 28, 1396-1399.
25. P. R. Ashton, T. T. Goodnow, A. E. Kaifer, M. V. Reddington, A. M. Z. Slawin, N. Spencer, J. F. Stoddart, C. Vicent, D. J. Williams, Angew. Chem. 1989, 101, 1404-1408; Angew. Chem. Int. Ed. Engl. 1989, 28, 1396-1399.
26. 2 bonds within each bipyridinium unit, are 14° for the inside and 13° for the alongside unit.
27. G. Chang, W. C. Guida, W. C. Still, J. Am. Chem. Soc. 1989, 111, 4379-4386.
28. A change of 180° in diherdral angle corresponds to flipping the naphthalene spacer from (R) to (S) chirality or vice versa. As a result, by monitoring the energy change on variation of this dihedral angle, the energy profile of the process involving the reversal of the local chirality associated with one of the naphthaene spacers can be derived.
29. B. S. Furniss, A. J. Hannaford, P. W. G. Smith, A. R. Tatchell, Practical Organic Chemistry, Longman, New York, 1989.
30. K. A. Connors, Binding Constants, Wiley, New York, 1987.
31. SHELXTL PC version 5.03, Siemens Analytical X-Ray Instruments, Madison, WI, 1994.
32. F. Mahamadi, N. G. K. Richards, W. C. Guida, R. Liskamp, M. Lipton, D. Caufield, G. Chang, T. Hendrickson, W. C. Still, J. Comput. Chem. 1990, 11, 440-467.
33. E. Polak, G. Ribiere, Rev. Fr. Inf. Rech. Oper. 1969, 16-R1, 35-43.
34. S. J. Weiner, P. A. Kollman, D. A. Case, V. C. Singh, C. Ghio, G. Alagona, S. Profeta, Jr. P. Weiner, J. Am. Chem. Soc. 1984, 106, 765-784.
35. W. C. Still, A. Tempczyk, R. C. Hawley, T. Hendrickson, J. Am. Chem. Soc. 1990, 112, 6127-6129.