Fourfold Metathesis Reactions in Calixarene Dimers
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3
J 8.8 Hz plus small unresolved long-range couplings, 8H; CH CH2), 4.20
are gratefully acknowledged. We also thank Prof. J. Okuda, (Inst. f. Anorg.
Chemie) for generous access to the NMR facilities, Prof. M. Schmidt
(Institut f¸r Physikalische Chemie) for the possibility to measure MALDI-
TOF mass spectra and Dr. B. Mathiasch (Institut f¸r Anorganische
Chemie, all from Universit‰t Mainz) for his assistance with the variable-
temperature NMR experiments.
2
and 2.83 (2d, J 11.7 Hz, 16H; ArCH2Ar), 3.90 3.75(m, 16H; OCH 2),
3.65(t, 3J 7.8 Hz, 16H; OCH2), 2.08 1.79 (m, 32H; CH2), 1.75 1.55(m,
16H; CH2), 1.45 1.10 (m, 80H; CH 2), 0.93 ppm (t, 3J 7.3 Hz, 24H; CH3);
1H NMR ([D6]benzene, 258C): d 10.01 (s, 8H; NH), 8.13 (s, 16H; CH
CHcalix), 7.68 (d, 3J 7.8 Hz plus small unresolved long-range couplings, 8H;
CH), 7.30 6.90 (m, under solvent peak; CH NH), 6.62 (d, 3J 7.8 Hz plus
small unresolved long-range couplings, 8H; CH), 6.31 (brd, small
unresolved long-range coupling, 8H; CHcalix), 5.77 (m, 8H; CH CH2),
5.04 (br dd, 3J 17 Hz plus small unresolved long-range couplings, 8H;
[1] For topology in general: a) Molecular Catenanes, Rotaxanes and Knots
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CH CH2), 4.99 (br dd, 3J 10.1 Hz plus small unresolved long-range
2
couplings, 8H; CH CH2), 4.56 and 3.28 (2d, J 11.6 Hz, 16H; ArCH2Ar),
3.90 3.60 (m, 32H; OCH2), 2.07 (quintet, 3J 7.1 Hz, 16H; CH2), 1.94 (q,
3J 7.2 Hz, 16H; CH2), 1.60 1.45(m, 16H; CH 2), 1.40 (quintet, 3J 7.5Hz,
16H; CH2), 1.30 1.05(m, 64H; CH 2), 0.98 ppm (t, 3J 7.5Hz, 24H; CH 3);
13C NMR ([D6]DMSO, 258C): d 158.96, 152.25, 151.06, 140.94, 138.63,
134.33, 133.25, 129.21, 118.12, 114.53, 110.07, 107.26, 104.12, 74.71, 67.04,
33.02, 30.54, 29.29, 28.55, 28.15, 28.13, 27.88, 25.25, 22.25, 13.89 ppm; FD
MS: m/z: 1747.1 [M1] .
Compounds 3 5: Benzene (p.a., 50 mL) was added to a solution of
calix[4]arene 2 (0.204 g, 0.117 mmol) in dry dichloromethane (1.00 L).
After approximately 15min
a solution of Grubbs× catalyst (0.019 g,
0.0234 mmol) in dry dichloromethane (25mL) was added. The reaction
mixture was stirred for two days at room temperature. DMSO (p.a.,
150 mL) was then added, and after 12 h, the solution was washed with water
(4 Â 100 mL), dried over magnesium sulfate and evaporated to dryness. The
residue was passed through a silica column (chloroform as eluant). The
mixture of compounds was then hydrogenated (H2 (1 atm), Pd/C, THF,
[6] R. Jaenisch, A. J. Levine, J. Mol. Biol. 1973, 73, 199 212.
¬
¬
[7] a) V. Balzani, M. Gomez-Lopez, J. F. Stoddart, Acc. Chem. Res. 1998,
31, 405 414; b) J.-P. Sauvage, Acc. Chem. Res. 1998, 31, 611 619;
30 358C, 5h) until the signal of CH CH protons at 5.5 ppm had
disappeared and the products were separated by flash chromatography
(gradient hexane/ethyl acetate 10:1 to ethyl acetate) to yield 3 5 (see
Table 1 for selected spectroscopic data). Compound 3 (yield 5 12%): m.p.
(chloroform/methanol) > 3008C (decomp.), 265 290 ph. tr.; for selected
ƒ
c) J.-P. Collin, C. Dietrich-Buchecker, P. Gavina, M. C. Jimenez-
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1H NMR data see Table 1; MALDI-TOF MS: m/z: 3389.0 [M1] .
Compound 4 (yield 26 32%): m.p. (chloroform/methanol) > 330 (de-
comp.), 207 230 and 295 330 ph. tr.; for selected 1H NMR data see
Table 1; MALDI-TOF MS: m/z:3390.3 [M2] , 3411.3 [MNa ]. Com-
pound 5 (yield 10 15%): > 3308C (decomp); MALDI-TOF MS: m/z:
3411.5[ MNa ].
X-ray structure analysis: Single crystals of 3 (Figure 5) suitable for an X-ray
analysis were obtained from chloroform/methanol. However, the best
crystal diffracted to a resolution of just 1.65ä. Nevertheless, the structure
could be solved after numerous attempts by the Shake-and-Bake method
(SHELXD, a program for the solution of macromolecular structures; G. M.
Sheldrick, University of Gˆttingen, 1999). It clearly shows the dimeric
capsule, but due to the disorder in the four C14H28 chains between the
oxygen atoms and the low resolution of the data it was impossible to decide
how the urea residues are connected. Refinement was performed on F 2
(SHELXL, a program for the refinement of crystal structures; G. M.
Sheldrick, University of Gˆttingen, 1997). All non-hydrogen atoms were
kept isotropically and hydrogen atoms were not included. Space group P21/
c, a 22.319(2), b 39.251(6), c 29.259(3) ä, b 109.465(8)8, V
24167(5) ä3, Z 4, m 0.08mmÀ1 (MoKa), crystal dimensions 0.5 Â 0.5 Â
0.4 mm3, 131365measured intensities, 38492 independent reflections
(Rint 0.20), 669 parameters, 149 restraints, R 0.42, highest peak and
deepest hole in the final difference map: 1.35, À0.67 eäÀ3. CCDC-204634
contains the supplementary crystallographic data for this paper. These data
ving.html (or from the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK; fax: (44)1223-336033; or depos-
it@ccdc.cam.uk).
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460; b) C. A. Hunter J. Am. Chem. Soc. 1992, 114, 5303 5311;
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[13] For a short review, see: J. Rebek, Jr., Chem. Commun. 2000, 637 643.
[14] Dimerization constants were estimated to be in the range of 106
108 mÀ1, see: R. K. Castellano, S. L. Craig, C. Nuckolls, J. Rebek, Jr., J.
Am. Chem. Soc. 2000, 122, 7876 7882.
[15] a) M. O. Vysotsky, I. Thondorf, V. Bˆhmer, Angew. Chem. 2000, 112,
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Vysotsky, V. Bˆhmer, Org. Lett. 2000, 2, 3571 3574.
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Weck, B. Mohr, J.-P. Sauvage, R. H. Grubbs, J. Org. Chem. 1999, 64,
5463 5471; c) T. J. Kidd, D. A. Leigh, A. J. Wilson, J. Am. Chem. Soc.
1999, 121, 1599 1600; d) D. A. Leigh, P. J. Lusby, S. J. Teat, A. J.
Wilson, J. K. Y. Wong, Angew. Chem. 2001, 113, 1586 1591; Angew.
Chem. Int. Ed. 2001, 40, 1538 1543.
MD simulations: MD simulations of 3 5 (in which the n-pentyl groups at
the narrow rim were replaced by ethyl groups) have been carried out by
using the AMBER6 force field for 9 ns in a rectangular box of chloroform
molecules. For details of the protocol see ref. [30].
[17] C. Dietrich-Buchecker, G. Rapenne, J.-P. Sauvage, Chem. Commun.
1997, 2053 2054.
Acknowledgement
[18] For further interesting nanostructures synthesized by metathesis
reactions, see: a) T. D. Clark, K. Kobayashi, M. R. Ghadiri, Chem.
Eur. J. 1999, 5, 782 791; b) M. S. Wendland, S. C. Zimmerman, J. Am.
Chem. Soc. 1999, 121, 1389 1390.
Financial support for these studies from the Deutsche Forschungsgemein-
schaft (Bo523/14 1, Th520/5 1) and the Fonds der Chemischen Industrie
Chem. Eur. J. 2003, 9, 3375 3382
¹ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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