2
884
M. H. Düker et al. / Tetrahedron Letters 52 (2011) 2881–2884
2
.
(a) Wudl, F. Acc. Chem. Res. 1984, 17, 227–232; (b) Bryce, R. M. Adv. Mater. 1999,
1, 11–23; (c) Bendikov, M.; Wudl, F.; Perepichka, D. F. Chem. Rev. 2004, 104,
891–4945.
Canevet, D.; Sallé, M.; Zhang, G.; Zhang, D.; Zhu, D. Chem. Commun. 2009, 2245–
269.
(a) Bryce, M. R.; Devonport, W.; Goldberg, L. M.; Wang, C. Chem. Commun. 1998,
45–951; (b) Bryce, M. R. J. Mater. Chem. 2000, 10, 589–598; (c) Nielsen, M. B.;
2J = 13.0 Hz, 2H), 6.56 (br s, 4H), 6.79 (br s, 4H); 13C NMR (90 MHz, CDCl
d = 10.4, 14.0, 22.5, 23.4, 28.2, 29.7, 29.8, 30.2, 31.3, 36.2, 39.3, 77.1, 108.5,
111.3, 127.6, 128.0, 128.2, 133.2, 134.3, 135.4, 155.2; UV–vis (CH Cl ):
max = 311 (36400), 333 (33000), 386 sh (11400 dm mol cm ) nm; MS
3
):
1
4
2
2
3
ꢁ1
ꢁ1
3
4
.
.
k
+
+
+
2
(ESI+): m/z (%) 1640 (M , 40), 1663 ([M+Na] , 100), 1679 ([M+K] , 80); HR-MS
+
104 4
(MALDI, matrix: DCTB): m/z calcd for C80H O S16 (M ) 1640.3461, found
9
1640.3704.
Lomholt, C.; Becher, J. Chem. Soc. Rev. 2000, 29, 153–164; (d) Becher, J.;
Jeppesen, J. O.; Nielsen, K. Synth. Met. 2003, 133–134, 309–315; (e) Nielsen, M.
B.; Diederich, F. Chem. Rev. 2005, 105, 1837–1867.
17. (a) Simonsen, K. B.; Svenstrup, N.; Lau, J.; Simonsen, O.; Mørk, P.; Kristensen, G.
J.; Becher, J. Synthesis 1996, 407–418; (b) Svenstrup, N.; Rasmussen, K. M.;
Hansen, T. K.; Becher, J. Synthesis 1994, 809–812.
5
.
.
(a) Pease, A. R.; Jeppesen, J. O.; Stoddart, J. F.; Luo, Y.; Collier, C. P.; Heath, J. R.
Acc. Chem. Res. 2001, 34, 433–444; (b) Moonen, N. N. P.; Flood, A. H.; Fernández,
J. M.; Stoddart, J. F. Top. Curr. Chem. 2005, 262, 99–132.
For comprehensive reviews and monographs on calixarenes, see: (a) Böhmer,
V. Angew. Chem., Int. Ed. Engl. 1995, 34, 713–745; (b) Asfari, Z.; Böhmer, V.;
Harrowfield, J.; Vicens, J. Calixarenes 2001; Kluwer Academic Publishers:
Dordrecht, 2001; (c) Gutsche, C. D. Calixarenes. An Introduction, 2nd ed.; RSC:
Cambridge, 2008.
18. General procedure for the synthesis of 1: bis-cyanoethyl TTF derivative 5
(0.22 mmol) was dissolved in dry DMF (10 mL) and degassed by 2–3 freeze-
pump-thaw cycles; then CsOH (0.46 mmol, 0.32 mL) was added as a 1.5 m
solution in MeOH at 0 °C. The mixture was allowed to warm to rt and stirred
for 30 min, changing its color from orange to dark brown–red. Calixarene 4
(0.1 mmol) was dissolved in dry THF (3 mL), and the solution was degassed by
a freeze-pump-thaw cycle. Afterward the calixarene solution was added in one
portion to the previously prepared thiolate solution at ꢁ20 °C, and then the
mixture was allowed to warm to rt gradually. The reaction mixture turned
6
7
.
For reviews on application of calixarenes, see: (a) Ikeda, A.; Shinkai, S. Chem.
Rev. 1997, 97, 1713–1734; (b) Casnati, A.; Sansone, F.; Ungaro, R. Acc. Chem. Res.
orange–yellow,
a yellow precipitate appeared for some derivatives. The
2
003, 36, 246–254; (c) Baldini, L.; Casnati, A.; Sansone, F.; Ungaro, R. Chem. Soc.
reaction was allowed to stir for additional 30 min at rt, and then THF was
removed under vacuum. The product was precipitated by addition of MeOH
and filtered off. The residue was finally purified by flash chromatography (FC)
on silica gel.
Rev. 2007, 36, 254–266; (d) Lhoták, P. Top. Curr. Chem. 2005, 255, 65–95; (e)
Rebek, J., Jr. Chem. Commun. 2000, 637–643; (f) Bogdan, A.; Rudzevich, Y.;
Vysotsky, M. O.; Böhmer, V. Chem. Commun. 2006, 2941–2952; (g) Sansone, F.;
Baldini, L.; Casnati, A.; Ungaro, R. New J. Chem. 2010, 34, 2715–2728.
(a) Azov, V. A.; Gómez, R.; Stelten, J. Tetrahedron 2008, 64, 1909–1917; (b)
Skibi n´ ski, M.; Gómez, R.; Lork, E.; Azov, V. A. Tetrahedron 2009, 65, 10348–
19. The structure was solved and refined using SHELX: Sheldrick, G. M. Acta Cryst.
2008, A64, 112–122.
8
.
.
20. Crystallographic data for 4:
C
44
H52Cl
4
O
4
,
M = 786.66, monoclinic, a =
1
0354.
(a) Regnouf-de-Vains, J.-B.; Sallé, M.; Lamartine, R. J. Chem. Soc., Perkin Trans 2
997, 2461–2462; (b) Lee, M. H.; Cao, Q.-Y.; Kim, S. K.; Sessler, J. L.; Kim, J. S. J.
Org. Chem. 2011, 76, 870–874.
0. (a) Zhao, B.-T.; Blesa, M.-J.; Mercier, N.; Le Derf, F.; Sallé, M. J. Org. Chem. 2005,
0, 6254–6257; (b) Zhao, B.-T.; Blesa, M.-J.; Mercier, N.; Le Derf, F.; Sallé, M.
14.021(2) Å, b = 17.163(3) Å, c = 17.520(3) Å, b = 100.600(2)°, V = 4144.1(12)
3
9
Å , T = 100(2) K, space group P2
independent reflections2 (Rint = 0.0291). The final
(I>2 (I)). The final wR(F ) values were 0.1142 (I>2
were 0.0556 (all data). The final wR(F ) values were 0.1257 (all data). GOF on F
was 1.032. The data for the structure have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication number CCDC-
813254. Copies of the data can be obtained, free of charge, on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, (fax: +44 (0)1223 336033 or e-
mail: deposit@ccdc.cam.ac.uk).
1
/c, Z = 4, 43438 reflections measured, 12758
values were 0.0437
(I)). The final R values2
1
R
1
r
r
1
2
1
7
New J. Chem. 2005, 1164–1167; (c) Blesa, M.-J.; Zhao, B.-T.; Allain, M.; Le Derf,
F.; Sallé, M. Chem. Eur. J. 2006, 12, 1906–1914; (d) Lyskawa, J.; Sallé, M.;
Balandier, J.-Y.; Le Derf, F.; Levillain, E.; Allain, M.; Viel, P.; Palacin, S. Chem.
Commun. 2006, 2233–2235; (e) Zhao, B.-T.; Blesa, M.-J.; Le Derf, F.; Canevet, D.;
Benhaoua, C.; Mazari, M.; Allain, M.; Salle, M. Tetrahedron 2007, 63, 10768–
1
1
2
21. Desiraju, G. R. Chem. Commun. 2005, 2995–3001; Steiner, T. Angew. Chem., Int.
Ed. 2002, 41, 48–76.
0777; (f) Zhao, B.-T.; Chen, J.-Q.; Qu, G.-R. Chinese J. Org. Chem. 2007, 27,
424–1427; (g) Lyskawa, J.; Canevet, D.; Allain, M.; Salle, M. Tetrahedron Lett.
010, 51, 5868–5872.
22. (a) Jørgensen, M.; Lerstrup, K. A.; Bechgaard, K. J. Org. Chem. 1991, 56, 5684–
5688; (b) Blanchard, P.; Svenstrup, N.; Becher, J. Chem. Commun. 1996, 615–
616; (c) Spanggaard, H.; Prehn, J.; Nielsen, M. B.; Levillain, E.; Allain, M.; Becher,
J. J. Am. Chem. Soc. 2000, 122, 9486–9494; (d) Le Derf, F.; Levillain, E.; Trippé, G.;
Gorgues, A.; Sallé, M.; Sebastian, R.-M.; Caminade, A.-M.; Majoral, J.-P. Angew.
Chem., Int. Ed. 2001, 40, 224–227; (e) Bouguessa, S.; Hervé, K.; Golhen, S.;
Ouahab, L.; Fabre, J.-M. New J. Chem. 2003, 27, 560–564.
23. (a) Lhoták, P.; Shinkai, S. J. Phys. Org. Chem. 1997, 105, 273–285; (b) Araki, K.;
Shimizu, H.; Shinkai, S. Chem. Lett. 1993, 205–208; (c) Araki, K.; Hayashida, H.
Chem. Lett. 2000, 20–21; (d) Araki, K.; Hayashida, H. Tetrahedron Lett. 2000, 41,
1209–1213; (e) Arduini, A.; Pochini, A.; Secchi, A. Eur. J. Org. Chem. 2000, 2325–
2334; (f) Arduini, A.; Giorgi, G.; Pochini, A.; Secchi, A.; Ugozzoli, F. J. Org. Chem.
2001, 66, 8302–8308.
1
1
1. (a) Zhao, B.-T.; Zhou, Z.; Yan, Z.-N.; Belhadj, E.; Le Derf, F.; Salle, M. Tetrahedron
Lett. 2010, 51, 5815–5818; (b) Zhao, B.-T.; Guo, W.-B.; Hu, P.-Z. Heterocycles
2
010, 81, 1661–1667.
2. (a) Nielsen, K. A.; Cho, W.-S.; Lyskawa, J.; Levillain, E.; Lynch, V. M.; Sessler, J. L.;
Jeppesen, J. O. J. Am. Chem. Soc. 2006, 128, 2444–2451; (b) Nielsen, K. A.; Sarova,
G. H.; Martín-Gomis, L.; Fernández-Lázaro, F.; Stein, P. C.; Sanguinet, L.;
Levillain, E.; Sessler, J. L.; Guldi, D. M.; Sastre-Santos, Á.; Jeppesen, J. O. J. Am.
Chem. Soc. 2008, 130, 460–462; (c) Nielsen, K. A.; Martín-Gomis, L.; Sarova, G.
H.; Sanguinet, L.; Gross, D. E.; Fernández-Lázaro, F.; Stein, P. C.; Levillain, E.;
Sessler, J. L.; Guldi, D. M.; Sastre-Santos, Á.; Jeppesen, J. O. Tetrahedron 2008, 64,
8
449–8463; (d) Park, J. S.; Le Derf, F.; Bejger, C. M.; Lynch, V. M.; Sessler, J. L.;
Nielsen, K. A.; Johnsen, C.; Jeppesen, J. O. Chem. Eur. J. 2010, 16, 848–854.
3. Frei, M.; Diederich, F.; Tremont, R.; Rodriguez, T.; Echegoyen, L. Helv. Chim. Acta
24. (a) Arduini, A.; McGregor, W. M.; Paganuzzi, D.; Pochini, A.; Secchi, A.;
Ugozzoli, F.; Ungaro, R. J. Chem. Soc., Perkin Trans 2 1996, 839–846; (b) Arena,
G.; Contino, A.; Longo, E.; Spoto, G.; Arduini, A.; Pochini, A.; Secchi, A.; Massera,
C.; Ugozzoli, F. New J. Chem. 2004, 28, 56–61; (c) Pescatori, L.; Arduini, A.;
Pochini, A.; Secchi, A.; Massera, C.; Ugozzoli, F. Org. Biomol. Chem. 2009, 7,
3698–3708.
1
1
2
006, 89, 2040–2057.
4. Only a few calix[4]arenes with rigid upper bridges have been reported: (a)
Ikeda, A.; Shinkai, S. J. Chem. Soc., Perkin Trans 1 1993, 2671–2673; (b) Ikeda, A.;
Yoshimura, M.; Lhotak, P.; Shinkai, S. J. Chem. Soc., Perkin Trans 1 1996, 1945–
1
950.
25. For a review on determination of binding constants using NMR, see: Fielding, L.
Tetrahedron 2000, 56, 6151–6170.
1
1
5. See Supplementary data for additional details.
6. Characterization data of compound 1a: orange–yellow powder (59%); mp: 145–
26. (a) Jeppesen, J. O.; Takimiya, K.; Jensen, F.; Brimert, T.; Nielsen, K.; Thorup, N.;
Becher, J. J. Org. Chem. 2000, 65, 5794–5805; (b) Jeppesen, J. O.; Becher, J. Eur. J.
Org. Chem. 2003, 3245–3266; (c) Nielsen, M. B.; Jeppesen, J. O.; Lau, J.; Lomholt,
C.; Damgaard, D.; Jacobsen, J. P.; Becher, J.; Stoddart, J. F. J. Org. Chem. 2001, 66,
3559–3563.
1
1
50°C;
R
f
= 0.76 (CH
2
Cl
2
/PE, 1:1);
3
H NMR (360 MHz, CDCl ): d = 0.88 (t,
3
3
J = 6.8 Hz, 12H), 1.02 (t, J = 7.6 Hz, 12H), 1.23–1.31 (m, 16H), 1.35–1.44 (m,
3
8
H), 1.58–1.67 (m, 8H), 1.88–2.01 (m, 8H), 2.82 (t, J = 7.4 Hz, 8H), 3.01 (d,
2 2
2
3
J = 13.0 Hz 2H), 3.15 (d, 2 J = 13.0 Hz, 2H), 3.55 (d, J = 15.2 Hz, 4H), 3.78 (t,
2
J = 7.2 Hz, 8H), 4.14 (d, J = 15.2 Hz, 4H), 4.30 (d, J = 13.0 Hz, 2H), 4.37 (d,