K.-X. Xu et al. / Tetrahedron: Asymmetry 16 (2005) 3042–3048
3047
naph-3,4,5,6-H), 4.59 (s, 4H, OCH2), 3.46–3.42 (m, 4H,
CH2NH), 2.83–2.76 (m, 4H, CH2CH2CH2), 1.71–1.49
(m, 8H, CH2NH2).
acid (1 equiv) in methanol. The mixture was stirred at
room temperature for 2 h and evaporated to dryness un-
der reduced pressure. The resulting syrup was dried at
high vacuum and 50 ꢁC for 24 h, checked by NMR
and stored in a desiccator.
4.2.3. Syntheses of compounds 1 and 2. To a stirred and
ice cooled solution of N-Boc-L-tryptophan (0.30 g,
1.25 mmol) in anhydrous chloroform (10 mL) was
4.4. Binding studies
added
1,10-carbonyldiimidazole
(CDI)
(0.24 g,
1.5 mmol), and the mixture was stirred for 2 h. Then a
solution of either 2,7-bis(aminoethylenecarbamoyl-
methoxy)naphthalene 4a (0.18 g, 0.5 mmol) or 2,7-
bis(3-aminopropylenecarbamoylmethoxy)naphthalene
4b (0.20 g, 0.5 mmol) in anhydrous chloroform (10 mL)
was added dropwise to the stirred mixture. The mixture
was stirred for 48 h under Ar at room temperature. The
mixture was washed successively with 1 M HCl
(3 · 20 mL), saturated Na2CO3 (3 · 20 mL), saturated
NaCl (3 · 20 mL), and then dried over anhydrous
Na2SO4. Solvent was evaporated under reduced pres-
sure. The crude product was purified by column chro-
matography on silica gel using CHCl3/CH3OH (50/1)
as eluant to obtain pure products 1 and 2, respectively.
The studies on the binding properties of 1 and 2 were
carried out in CHCl3 or DMSO. The fluorescence titra-
tion was performed with a series of 2.60 · 10ꢀ5 M
solutions of receptor 1 or 2 containing different
amounts of chiral anions (the excited wavelength was
359 or 361 nm, the excitation and emission slit width
were 5 nm). Association constants were calculated by
means of a non-linear least-square curve fitting method
with Origin 7.0 (Origin-Lab Corporation). 1H NMR
studies were recorded as adding equivalent racemic,
D- or L-dibenzoyl tartrate anions into receptors (2.0 ·
10ꢀ3 M).
Acknowledgement
Compound 1: Yield: 76%;Mp: 124–126
ꢁC;
20
½a ¼ ꢀ16.8 (c 0.05, CHCl3); 1H NMR (300 MHz,
We thank the National Natural Science Foundation for
financial support (Grant No. 20372054).
D
CDCl3): d 8.52 (br, 2H, Ind-NH), 7.71 (d, 2H,
J = 9.6 Hz, naph-3,6-H), 7.57 (d, 2H, J = 7.8 Hz, Ind-
7-H), 7.16–7.04 (m, 12H, Ind-2,4,5,6-H, naph-1,4,5,8-
H), 6.93 (s, 2H, CONH), 6.33 (br, 2H, CONH), 5.16
(br, 2H, NHBoc), 4.50 (s, 4H, OCH2), 4.35 (br, 2H,
C*H), 3.26 (s, 8H, NCH2CH2N), 3.18–3.03 (m, 4H,
CH2–Ind), 1.41 (s, 18H, CH3); 13C NMR (150 MHz,
CDCl3): d (ppm) 28.5, 36.7, 40.0, 55.7, 67.3, 77.1,
107.3, 110.6, 111.5, 116.7, 119.0, 120.0, 122.4, 123.4,
127.6, 129.9, 135.7, 136.4, 156.2, 161.3, 169.5;IR
(KBr/cmꢀ1): 3415, 2925, 1655, 1515, 1436, 1385, 1165,
1057, 746;ESI-MS m/z (%): 955 ((M+Na)+,100);Ele-
mental analysis calcd (%) for C50H60N8O10: C 64.36,
H 6.48, N 12.01;found C 64.11, H 6.39, N 11.92.
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D
8.45 (br, 2H, Ind-NH), 7.75 (d, 2H, J = 9.3 Hz, naph-
3,6-H), 7.62 (d, 2H, J = 8.1 Hz, Ind-7-H), 7.32 (d, 2H,
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CONH), 5.20 (br, 2H, NHBoc), 4.58 (s, 4H, OCH2),
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116.7, 119.1, 119.8, 122.3, 123.5, 125.5, 127.7, 129.9,
135.6, 136.4, 155.6, 156.2, 168.7, 172.5;IR (KBr/
cmꢀ1): 3411, 2926, 1661, 1539, 1436, 1367, 1210, 1164,
1057, 746;ESI-MS m/z (%): 983 ((M+Na)+, 100);Ele-
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4.3. Tetrabutylammonium salts
All tetrabutylammonium salts were prepared by adding
2 equiv of tetrabutylammonium hydroxide in methanol
to a solution of the corresponding dibenzoyl tartaric