1360
A. Granzhan, M.-P. Teulade-Fichou / Tetrahedron 65 (2009) 1349–1360
C
47
H
60FeN
6
Oꢂ5HClꢂ2H
2
O (999.2): C, 56.50; H, 6.96; N, 8.41; Cl,
2PY) correspond to the isosbestic points, found from the corre-
sponding spectrophotometric titrations.
17.74. Found: C, 56.71; H, 6.71; N, 8.27; Cl, 17.93; purity (HPLC
D
peak area) 94%; a peak corresponding to BisNP-1(FC ) (m/z¼780
þ
[M ]) was also detected by HPLC (5% peak area).
Acknowledgements
4
.7.3. Synthesis of BisNP-1PY
To a suspension of BisNP-1NH
We thank Dr. Elena Tulyakova (Universit a¨ t W u¨ rzburg) for the
calculation of the binding constants and Mrs. Marianne Bombled
2
35HCl (75.0 mg, 100
m
mol) in
ꢁ
MeOH (25 mL), ion-exchange resin (IRA-420, OH ) was added
and the suspension was shaken until the salt dissolved. The
mixture was filtered and the resin was thoroughly washed with
MeOH. The filtrate was concentrated to a volume of 5 mL and
molecular sieves (3 Å) were added. To the gently stirred mixture,
(Institut Curie) for help with characterization of the macrocycles.
The generous financial support by the Centre National de la
Recherche Scientifique (CNRS) is gratefully appreciated.
References and notes
a solution of the aldehyde 22 (27.0 mg, 100
MeOH (1 mL) and CHCl (1 mL) was added dropwise. After stir-
ring for 18 h at room temperature, NaBH (20 mg, 530 mol) was
added and, after reacting for 1 h, the mixture was diluted with
CH Cl (5 mL), filtered, the filtrate was evaporated in vacuo, and
the residue was purified by flash chromatography (SiO , eluent:
CH Cl –MeOH–aq 28% NH 80:20:1 to 80:20:3) to give BisNP-
PY (60.0 mg, 73%) as yellow oil. H NMR (CDCl
mmol) in a mixture of
3
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m
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3
. Paris, T.; Vigneron, J.-P.; Lehn, J.-M.; Cesario, M.; Guilhem, J.; Pascard, C.
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1379–1381.
2
2
2
4
2
2
3
1
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gneron, J.-P.; Lehn, J.-M. In Molecular Recognition and Inclusion; Coleman, A. W.,
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1
3
):
d
¼1.38–1.48
(
2
8
m, 2H), 1.57–1.66 (m, 4H), 2.36 (t, J¼7 Hz, 2H), 2.46 (t, J¼6.8 Hz,
H), 2.52 (t, J¼6.9 Hz, 2H), 2.61 (t, J¼5 Hz, 4H), 2.79–2.85 (m,
H), 3.13 (t, J¼7.6 Hz, 2H), 3.69 (t, J¼5 Hz, 4H), 3.78 (s, 4H), 3.86
7. Bahr, M.; Gabelica, V.; Granzhan, A.; Teulade-Fichou, M.-P.; Weinhold, E. Nucleic
(
s, 4H), 7.19 (dd, J¼8.4, 1 Hz, 4H), 7.29 (d, J¼8.4 Hz, 2H), 7.33 (d,
Acids Res. 2008, 36, 5000–5012.
8. Gokel, G. W.; Barbour, L. J.; De Wall, S. L.; Meadows, E. S. Coord. Chem. Rev. 2001,
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J¼8.4 Hz, 2H), 7.50 (s, 2H), 7.53 (s, 2H), 7.74 (d, J¼7.8 Hz, 1H),
.95–8.19 (m, 8H); 13C NMR (CDCl
): ), 29.3 (CH ),
¼27.0 (CH
9.9 (CH ), 33.2 (CH ), 47.5 (CH ), 48.3 (CH ), 49.0 (CH ), 49.8
CH ), 52.0 (CH ), 53.3 (CH ), 53.8 (CH ), 54.5 (CH ), 69.8 (CH ),
23.4 (CH), 124.6 (CH), 124.7 (CH), 124.8 (CH), 125.0 (C ), 125.7
CH), 125.8 (CH), 125.9 (CH), 126.4 (C ), 126.5 (3CH), 127.1 (CH),
27.5 (CH), 127.8 (CH), 127.9 (CH), 128.5 (C ), 129.7 (C ), 130.9
), 137.3 (C ), 137.4 (C ); MS
7
2
(
1
(
1
3
d
2
2
9
. Clares, M. P.; Lodeiro, C.; Fern a´ ndez, D.; Parola, A. J.; Pina, F.; Garc ı´ a-Espa n˜ a, E.;
2
2
2
2
2
Soriano, C.; Tejero, R. Chem. Commun. 2006, 3824–3826.
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2
2
2
2
2
2
Parola, A. J.; Pina, J.; de Melo, J. S.; Soriano, C.; Garcia-Espa n˜ a, E. Inorg. Chem.
q
2004, 43, 6114–6122.
q
1
1. Alarc o´ n, J.; Albelda, M. T.; Belda, R.; Clarez, M. P.; Delgado-Pinar, E.; Fr ı´ as, J. C.;
q
q
Garc ı´ a-Espa n˜ a, E.; Gonz a´ les, J.; Soriano, C. Dalton Trans. 2008, 6530–6538.
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13. Firouzabadi, H.; Iranpoor, N.; Karimi, B. Synlett 1999, 321–323.
(
(
C
q
), 131.4 (C
q
), 132.5 (2C
q
), 136.8 (C
q
q
q
þ
2þ
þ
ESI ): m/z (%)¼413 (63) [Mþ2H] , 825 (100) [MþH] . To pre-
1
1
4. Still, I. W. J.; Natividad-Preyra, R.; Toste, F. D. Can. J. Chem. 1999, 77, 113–121.
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pare the hydrochloride salt, the amine was dissolved in MeOH,
treated with excess concentrated aq HCl, the suspension was
evaporated, and the residue was recrystallized from water to
1
6. Benito, J. M.; G o´ mez-Garc ı´ a, M.; Ortiz Mellet, C.; Baussanne, I.; Defaye, J.; Garc ı´ a
Fern a´ ndez, J. M. J. Am. Chem. Soc. 2004, 126, 10355–10363.
ꢀ
give BisNP-1PY36HCl as white solid, mp (decomp.) 305–308 C;
17. Boon, J. M.; Lambert, T. N.; Smith, B. D.; Beatty, A. M.; Ugrinova, V.; Brown, S. N.
purity (HPLC peak area) 96%. Anal. Calcd (%) for
J. Org. Chem. 2002, 67, 2168–2174.
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Vidmar, T. J. J. Med. Chem. 1992, 35, 1233–1245.
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1
C
55
H
64
N
6
Oꢂ5HClꢂ2H
2
O (1043.5): C, 63.31; H, 7.05; N, 8.05; Cl,
16.99. Found: C, 63.42; H, 6.77; N, 7.94; Cl, 16.90.
1
20. Navarro, A.-E.; Spinelli, N.; Moustrou, C.; Chaix, C.; Mandrand, B.; Brisset, H.
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.8. Spectrophotometric and spectrofluorimetric titrations
2
Absorption spectra were recorded with a double-beam spectro-
2
photometer (UVIKON XL) in 1-mL quartz cells with a path length of
cm, whereas fluorescence spectra were recorded with a HORIBA
Jobin-Yvon FluoroMax-3 fluorimeter in 1-mL quartz cells with
a cross-section of 1 cmꢂ0.5 cm, using bandwidths of 2 nm. All
measurements wereperformed in sodium cacodylatebuffer (10 mM
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2
7. Oida, S.; Tajima, Y.; Konosu, T.; Nakamura, Y.; Somada, A.; Tanaka, T.; Habuki, S.;
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J. A.; Smithers, M. J.; Whittamore, P. R. O. J. Med. Chem. 1995, 38, 1608–1628.
NaAsO
PY36HCl (1 mM) was prepared in a mixture DMSO–H
Stock solutions of BisNP-1PY35HCl (1 mM), dipotassium phthalate
OP, 0.1 M), and disodium terephthalate (Na TP, 0.1 M) were
2
Me
2
, 10 mM NaCl, pH 6.0). Stock solution of BisNP-
2
9. Davis, W. L.; Shago, R. F.; Langner, E. H. G.; Swarts, J. C. Polyhedron 2005, 24,
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2
2
O (1:1 v/v).
1
3
(K
2
2
3
3
2. Ribou, A.-C.; Vigo, J.; Salmon, J.-M. J. Photochem. Photobiol., A 2002, 151, 49–55.
3. Barrett, E. S.; Dale, T. J.; Rebek, J., Jr. Chem. Commun. 2007, 4224–4226.
prepared in deionized water. The excitation wavelengths for fluo-
rimetric titrations (348 nm for BisNP-1PY and 350 nm for BisNP-
34. Hagiya, K.; Mitsui, S.; Taguchi, H. Synthesis 2003, 823–828.