Z. Chen et al. / Tetrahedron: Asymmetry 19 (2008) 2051–2057
2057
4
.2.4. General synthesis of receptors 1 and 2
Compound 7 (0.40 g, 0.56 mmol) or 8 (0.40 g, 0.54 mmol) was
solution of receptor 1 or 2, respectively. Association constants were
calculated by means of a non-linear least-square curve fitting with
ORIGIN 7.0 (Origin-Lab Corporation).
dissolved in 2 mL dry chloroform, after adding trifluoroacetic acid
0.30 g, 2.6 mmol), the mixture was stirred for 1 h at room temper-
(
ature. The solvent and excess trifluoroacetic acid were evaporated
in reduced pressure to afford the TFA salt as pale yellow oil. The
Acknowledgement
3
TFA salt was then dissolved in 10 mL of chloroform, 1 mL Et N
was added and stirred for 10 min. The mixture was then poured
into water and extracted with chloroform; the organic layer was
We thank the National Natural Science Foundation for financial
support (Grant No. 20572080).
dried over anhydrous Na
under reduced pressure. The residue was then purified on a column
of silica gel using CHCl /MeOH/NH O (100:10:1) as eluent to
2 4
SO and the solvent was evaporated
References
3
3
ꢃH
2
obtain pure products 1 and 2, respectively.
1.
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Receptor 1: the pure product was obtained as a pale yellow so-
2
D
0
lid (0.32 g) in 93.2% yield, mp 74–76 °C, ½
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¼ ꢀ114:2 (c 0.061,
ꢀ1
CHCl
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); IR (KBr, cm ):
840, 1937, 1647, 1551, 1525, 1445, 1384, 1330, 1256, 1155,
116, 1027, 887, 867, 844, 789, 733. 1H NMR (CDCl
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9
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1
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3
1196; (i) Izatt, R. M.; Pawlak, K.; Bradshaw, J. S.; Bruening, R. L. Chem. Rev. 1995,
(
ppm): 8.40 (s, 2H, An-H), 8.20 (d, J = 8.7 Hz, 4H, An-H), 8.00 (d,
J = 7.8 Hz, 4H, An-H), 7.62 (s, 1H, CONH), 7.52–7.28 (m, 8H, An-
H), 7.17 (s, 1H, CONH), 4.67 (s, 2H, An-CH ), 4.63 (s, 2H, An-CH ),
.19 (br s, 1H, chiral H), 3.11–2.72 (m, 8H, CH ), 2.11–1.81 (m,
). C NMR (CDCl3, 75 MHz) d (ppm): 175.0, 173.0, 131.6,
9
1
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31.2, 130.3, 129.5, 127.7, 126.5, 125.3, 124.1, 54.6, 49.4, 49.1,
6.1, 45.4, 45.2, 38.8, 33.0, 31.4. MS m/z (%): 612 (M +1, 100%). Ele-
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(
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3
.
.
(a) Ma, F.; Shen, L.; Ai, X.; Zhang, C. Org. Lett. 2007, 9, 125–127; (b) Qing, G. Y.;
He, Y. B.; Zhao, Y.; Hu, C. G.; Liu, S. Y.; Yang, X. Eur. J. Org. Chem. 2006, 1574–
1580; (c) Qin, H.; He, Y.; Hu, C.; Chen, Z.; Hu, L. Tetrahedron: Asymmetry 2007,
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mental Anal. Calcd for C39
Found: C, 76.32; H, 6.81; N, 11.32.
Receptor 2: the pure product was obtained as a pale yellow so-
41 5 2
H N O : C, 76.55; H, 6.77; N, 11.45.
2
D
0
lid (0.28 g) in 81.1% yield, mp 82–84 °C, ½
aꢂ
¼ þ109 (c 0.064,
4476.
ꢀ1
CHCl
3
); IR (KBr, cm ):
648, 1547, 1446, 1384, 1331, 1260, 1202, 1178, 1158, 1107,
031, 949, 887, 842, 790.4, 733.5. 1H NMR (CDCl
, 300 MHz) d
m 3284, 3055, 2932, 2852, 1941, 1809,
4
(a) Wang, H.; Chan, H. W.; Lee, A. W. Org. Biomol. Chem. 2008, 6, 929–934; (b)
Qing, G. Y.; He, Y. B.; Chen, Z. H.; Wu, X. J.; Meng, L. Z. Tetrahedron: Asymmetry
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Tetrahedron: Asymmetry 2005, 16, 3042–3048; (d) Xu, K. X.; Wu, X. J.; He, Y. B.;
Liu, S. Y.; Qing, G. Y.; Meng, G. Y. Tetrahedron: Asymmetry 2005, 16, 833–839.
1
1
3
(
ppm): 8.39 (s, 2H, An-H), 8.31 (d, J = 7.8 Hz, 4H, An-H), 7.99 (d,
J = 8.1 Hz, 4H, An-H), 7.67 (s, 2H, CONH), 7.55–7.42 (m, 8H, An-
H), 4.72 (s, 4H, An-CH ), 3.26 (m, 4H, CH ), 3.09 (br s, 1H, chiral
H), 2.99–2.87 (m, 8H, CH ), 2.08–1.66 (m, 4H, CH
CDCl3, 75 MHz) d (ppm):169.8, 167.9, 129.1, 126.4, 125.7, 125.3,
5. (a) Gunnaugsson, T.; Glynn, M.; Tocci, G. M.; Kruger, P. E.; Pfeffer, F. M. Coord.
Chem. Rev. 2006, 250, 3094–3117; (b) Liu, S. Y.; Fang, L.; He, Y. B.; Chan, W. H.;
Yeung, K. T.; Cheng, Y. K.; Yang, R. H. Org. Lett. 2005, 7, 5825–5828; (c) Arimori,
S.; Bell, M. L.; Oh, C. S.; James, T. D. Org. Lett. 2002, 4, 4249.
6. (a) Peczuh, M. W.; Hamilton, A. D. Chem. Rev. 2000, 100, 2479–2494; (b) Zhang,
T.; James, T. D. Org. Lett. 2007, 9, 1627–1629.
2
2
1
3
2
2
). C NMR
(
1
4
24.2, 122.6, 122.1, 121.3, 120.1, 118.9, 53.9, 49.3, 43.5, 43.0,
7.
(a) Liu, Y.; Song, Y.; Chen, Y.; Li, X. Q.; Ding, F.; Zhong, R. Q. Chem. Eur. J. 2004,
4, 3685–3696; (b) Shinoda, S.; Okazaki, T.; Player, T. N.; Misaki, H.; Hori, K.;
1.0, 40.5, 33.5, 32.6, 27.7, 26.0, 24.3, 23.7. MS m/z (%): 640
1
+
(
M +1, 100%). Elemental Anal. Calcd for C41
H
45
N
5
O
2
: C, 76.95; H,
Tsukube, H. J. Org. Chem. 2005, 70, 1835–1843.
8.
(a) Gonzalez-Alvarez, A.; Afonso, I.; Diaz, P.; Garcia-Espana, E.; Gotor, V. Chem.
Commun. 2006, 1227–1229; (b) Barzzicalupi, C.; Bencini, A.; Bianchi, A.;
Borsari, L.; Giorgi, C.; Valtancoli, B. J. Org. Chem. 2005, 70, 4257–4266.
7
.10; N, 10.95. Found: C, 76.82; H, 7.15; N, 10.88.
Synthesis of complex 1-Cu2 : compound 1 (0.20 g, 0.33 mmol)
+
was dissolved in 10 mL dry methanol, Copper perchloride (0.15 g,
.40 mmol) in 5 mL of methanol was added dropwise to the solu-
9. (a) Zhao, J.; Fyles, T. M.; James, T. D. Angew. Chem., Int. Ed. 2004, 43, 3461–3464;
(b) Zhao, J.; Davidson, M. G.; Mahon, M. F.; Kociok-Kohn, G.; James, T. D. J. Am.
Chem. Soc. 2004, 126, 16179–16186; (c) Yang, W.; Yan, J.; Springsteen, G.;
Deeter, S.; Wang, B. Bioorg. Med. Lett. 2003, 13, 1019–1022.
0
tion. The blue solid was precipitated and collected by filtration.
The ESI-MS of complex 1-Cu2 was taken in methanol and
+
1
0. (a) Han, M. S.; Kim, D. H. Angew. Chem., Int. Ed. 2002, 41, 3809–3811; (b)
Fabbrizzi, L.; Marcotte, N.; Stomeo, F.; Tagnietti, A. Angew. Chem., Int. Ed. 2002,
41, 3811–3814; (c) Shao, N.; Jin, J. Y.; Cheung, S. M.; Yang, R. H.; Chan, W. H.;
Mo, T. Angew. Chem., Int. Ed. 2006, 45, 4944–4948; (d) O’Neil, E. J.; Smith, B. D.
Coord. Chem. Rev. 2006, 250, 3068–3080.
shows a peak at 874 (m/z), which demonstrating a structure of
II
[
Cu (l)](ClO
4
)
2
.
4
.3. Tetrabutylammonium salts
11. Wu, J. S.; Wang, F.; Liu, W. M.; Wang, P. F.; Wu, S. K.; Wu, X.; Zhang, X. H. Sens.
Actuators, B 2007, 125, 447–452.
1
2. (a) Lavigne, J. J.; Anslyn, E. V. Angew. Chem., Int. Ed. 1999, 38, 3666–3669; (b)
The tetrabutylammonium salts were prepared by adding
equiv of tetrabutylammonium hydroxide in methanol to a solu-
Gray, C. W.; Houston, T. A. J. Org. Chem. 2002, 67, 5426–5428.
2
13. Lee, D. H.; Kim, S. Y.; Hong, J. Angew. Chem., Int. Ed. 2004, 43, 4777–4780.
4. (a) Jose, D. A.; Mishra, S.; Ghosh, A.; Shrivastav, A.; Mishra, S.; Das, A. Org. Lett.
007, 9, 1979–1982; (b) Li, C.; Numata, M.; Takeuchi, M.; Shinka, S. Angew.
Chem., Int. Ed. 2005, 44, 6371–6374.
1
tion of the dicarboxyl acid and 1 equiv to the monocarboxyl acid
derivatives in methanol. The mixture was stirred at room temper-
ature for 4 h and evaporated to dryness under reduced pressure.
The residue was dried at high vacuum for 24 h and then stored
in a desiccator.
2
15. (a) Zhang, T.; Anslyn, E. V. Org. Lett. 2006, 8, 1649–1652; (b) Yang, W.; Yan, J.;
Fang, H.; Wang, B. Chem. Commun. 2003, 792–793.
16. Hayashida, O.; Ogawa, N.; Uchiyama, M. J. Am. Chem. Soc. 2007, 129, 13698–
3705.
1
17. (a) Kim, H. J.; Asif, R.; Chung, D. S.; Hong, J. I. Tetrahedron lett. 2003, 44, 4335–
4338; (b) Folmer-Andersen, J. F.; Lynch, V. M.; Anslyn, E. V. J. Am. Chem. Soc.
4
.4. Binding studies
2005, 127, 7986–7987.
1
8. (a) Liu, X. X.; Zheng, Y. S. Tetrahedron Lett. 2006, 47, 6357–6360; (b) Ma, F.; Ai,
L.; Shen, X.; Zhang, C. Org. Lett. 2007, 9, 125–127; (c) Chen, Z. H.; He, Y. B.; Hu,
C. G.; Huang, X. H.; Hu, L. Aust. J. Chem. 2008, 61, 310–315.
9. (a) Cheung, S. M.; Chan, W. H. Tetrahedron 2006, 62, 8379–8383; (b) Moletti, A.;
Coluccini, C.; Pasini, D.; Taglietti, A. Dalton Trans. 2007, 1588–1592; (c)
Shiraishi, Y.; Kohno, Y.; Hirai, T. J. Phys. Chem. B 2005, 109, 19139–19147; (d)
Shiraishi, Y.; Kohno, Y.; Hirai, T. Ind. Eng. Chem. Res. 2005, 44, 847–851.
The study of binding properties was carried out in the aqueous
2
Tris–HCl buffer (0.05 M. pH 7.4, v(MeOH):v(H O) = 1:1, 0.1 M
1
NaCl). The fluorescence and UV–vis titration were performed with
ꢀ
2+
5
ꢀ1
a series of 5 ꢁ 10 mol L solutions of the receptors. The complex
2+
2+
1
-Cu or 2-Cu was tested by adding 1.0 equiv of Cu to the