G. Li, Y. Ju et al.
Chemicals: Cholic acid, deoxycholic acid, lithocholic acid, and 4-iodoani-
line were purchased from Sigma and used as received. Trimethylsilylace-
tylene was purchased from Shanghai Reagent Coporation. [PdACTHUNTRGNE(UNG PPh3)4]
was obtained from Pingyang Chemical Company and washed with cold
ethanol prior to use to remove the oxidized impurity. Other reagents and
solvents were received from Beijing Chemical Company without further
purification unless otherwise stated. 1,4-Diethynylbenzene was prepared
and characterized according to a previously published procedure.[22]
OPE2: OPE2 was synthesized as described for OPE1 by using 5 instead
of 4. Yield: 68%; 1H NMR (300 MHz, [D6]DMSO): d=10.08 (s, 2H;
NH), 7.65 (d, J=7.2 Hz, 4H; Ar-H), 7.55 (s, 4H; Ar), 7.49 (d, J=7.2 Hz,
4H; Ar-H), 4.46 (d, J=4.2 Hz, 2H; 12-OH), 4.20 (d, J=3.9 Hz, 2H; 3-
OH), 3.80 (s, 2H; 12-CH), 3.33–3.48 (m, 2H; 3-CH, overlap with the
water signal in [D6]DMSO), 0.85–2.37 (m, 52H; alkyl-H), 0.91 (d, J=
6.0 Hz, 6H; 21-CH3), 0.85 (s, 6H; 19-CH3), 0.61 ppm (s, 6H; 18-CH3);
13C NMR (300 MHz, [D6]DMSO): d=172.6, 140.6, 132.7, 132.0, 123.0,
119.4, 116.5, 92.2, 88.7, 71.6, 70.5, 48.0, 46.7, 46.5, 36.8, 36.2, 35.6, 34.4,
34.1, 33.5, 31.9, 30.8, 29.2, 27.7, 27.5, 26.7, 24.1, 23.6, 17.7, 13.0 ppm; IR
(KBr): n˜ =3412, 2934, 2862, 2214, 1670, 1591, 1520, 1041, 838 cmÀ1; MS
(ESI): m/z: 1080 [M+Na]+; elemental analysis calcd (%) for C70H92N2O6:
C 79.50, H 8.77, N 2.65; found: C 79.00, H 8.52, N 2.94.
N-Cholyl-4-iodoaniline 4: Cholic acid (818 mg, 2.0 mmol), HOBt
(297 mg, 2.2 mmol), and 4-iodoaniline (438 mg, 2.0 mmol) were dissolved
in CH2Cl2/pyridine (12 mL, 5:1 v/v). After stirring at 08C for 10 min,
DCC (453 mg, 2.2 mmol) was added and the resulting reaction mixture
was kept at ambient temperatures for a further 20 h. A white precipitate
was filtered from the purple solution and washed with acetone. The
crude product was purified by column chromatography on neutral Al2O3
(5% MeOH/CH2Cl2) to obtain 4 (926 mg, 76%). 1H NMR (300 MHz,
[D6]DMSO): d=9.58 (s, 1H; NH), 7.52 (d, J=7.2 Hz, 2H; Ar-H), 7.42
(d, J=7.2 Hz, 2H; Ar-H), 3.90 (s, 1H; 12-CH), 3.74 (s, 1H; 7-CH), 3.39–
3.55 (m, 1H; 3-CH, overlap with the water signal in [D6]DMSO), 1.01–
2.39 (m, 27H; alkyl-H), 1.01 (d, J=6.0 Hz, 3H; 21-CH3), 0.87 (s, 3H; 19-
CH3), 0.61 ppm (s, 3H; 18-CH3); 13C NMR (300 MHz, [D6]DMSO): d=
172.5, 139.0, 137.1, 121.4, 85.7, 72.1, 71.1, 67.3, 46.4, 46.1, 41.4, 35.2, 35.1,
34.7, 34.5, 33.7, 31.3, 30.3, 28.3, 27.3, 26.1, 24.6, 23.0, 22.4, 17.2, 12.4 ppm;
HRMS (ESI): m/z calcd for [C30H44INO4+Na]+: 632.2213; found:
632.2200.
OPE3: OPE3 was synthesized as described for OPE1 by using 6 instead
of 4. Yield: 55%; 1H NMR (300 MHz, [D6]DMSO): d=10.07 (s, 2H;
NH), 7.65 (d, J=7.2 Hz, 4H; Ar-H), 7.54 (s, 4H; Ar-H), 7.48 (d, J=
7.2 Hz, 4H; Ar-H), 4.41 (s, 2H; 3-OH), 3.20–3.50 (m, 2H; 3-CH), 1.02–
1.93 (m, 60H; alkyl-H), 0.94 (d, J=5.6 Hz, 6H; 18-CH3), 0.87 (s, 6H; 19-
CH3), 0.61 ppm (s, 6H; 21-CH3); 13C NMR (300 MHz, [D6]DMSO): d=
172.4, 141.1, 136.0, 132.7, 119.9, 118.0, 92.2, 71.0, 57.1, 56.2, 43.0, 42.3,
41.3, 40.5, 36.3, 35.9, 34.5, 32.8, 31.1, 29.1, 27.7, 26.5, 23.7, 23.1, 21.4, 17.0,
11.9 ppm; IR (KBr): n˜ =3481, 3426, 2930, 2850, 2214, 1672, 1585,
1527 cmÀ1; MS (ESI): m/z: 1048 [M+Na]+; elemental analysis calcd (%)
for C70H92N2O4: C 81.99, H 9.04, N 2.73; found: C 81.56, H 9.49, N 2.52.
N-Deoxycholyl-4-iodoaniline 5: Compound 5 was synthesized as de-
scribed for compound 4 by using deoxycholic acid instead of cholic acid.
1
Yield: 77%; H NMR (300 MHz, [D6]DMSO): d=9.58 (s, 1H; NH), 7.52
Acknowledgements
(d, J=7.2 Hz, 2H; Ar-H), 7.42 (d, J=7.2 Hz, 2H; Ar-H), 3.90 (s, 1H; 12-
CH), 3.74 (s, 1H; 7-CH), 3.39–3.55 (m, 1H; 3-CH, overlap with the water
signal in [D6]DMSO), 1.01–2.39 (m, 27H; alkyl-H), 1.01 (d, J=6.0 Hz,
3H; 21-CH3), 0.87 (s, 3H; 19-CH3), 0.61 ppm (s, 3H; 18-CH3); 13C NMR
(300 MHz, [D6]DMSO): d=172.4, 139.8, 137.4, 121.7, 86.7, 71.5, 70.5,
55.4, 48.0, 46.7, 46.5, 42.1, 36.8, 36.2, 35.7, 35.6, 34.3, 34.0, 33.5, 31.8, 30.8,
30.0, 27.7, 27.5, 26.7, 24.1, 23.6, 22.4, 17.6, 13.0 ppm; HRMS (ESI): m/z
calcd for [C30H44INO3+H]+: 594.2444; found: 594.2439.
We gratefully acknowledge the financial support from the National Sci-
ence Foundation of China (20533050, 20772071, and 50673048), 973 Pro-
gram (2006CB806200) and the transregional project (TRR6). We would
also like to thank Prof. Chun Li for help during the circular dichroism ex-
periment.
N-Lithocholyl-4-iodoaniline 6: Compound 6 was synthesized as described
for compound 4 by using lithocholic acid instead of cholic acid. Yield:
80%; H NMR (300 MHz, [D6]DMSO): d=9.95 (s, 1H; NH), 7.60 (d, J=
b) J. A. A. W. Elemans, R. van Hameren, R. J. M. Nolte, A. E.
[2] a) M. J. Plater, J. P. Sinclair, S. Aiken, T. Gelbrich, M. B. Hursthouse,
Lorenzo, M. F. Gianluca, H. O. Omar, N. Francesco, P. Gennaro,
Macromolecules 2006, 39, 5206–5212.
1
7.2 Hz, 2H; Ar-H), 7.41 (d, J=7.2 Hz, 2H; Ar-H), 4.44 (brs, 1H; OH),
3.39–3.55 (m, 1H; 3-CH, overlap with the signal of water in [D6]DMSO),
1.05–2.35 (m, 28H; alkyl-H), 1.01 (d, J=6.0 Hz, 3H; 21-CH3), 0.87 (s,
3H; 19-CH3), 0.61 ppm (s, 3H; 18-CH3); 13C NMR (300 MHz,
[D6]DMSO): d=172.5, 140.0, 137.9, 121.7, 85.7, 71.9, 71.1, 55.00, 54.96,
41.8, 41.3, 39.5, 39.3, 35.0, 34.6, 33.5, 30.4, 29.5, 27.3, 26.2, 25.4, 23.3, 22.4,
19.7, 17.5, 12.0 ppm; HRMS (ESI): m/z calcd for [C30H44INO2+H]+:
578.2495; found: 578.2489.
[4] a) J. Wu, T. Yi, T. Shu, M. Yu, Z. Zhou, M. Xu, Y. Zhou, H. Zhang,
4742; b) P. Xue, R. Lu, D. Li, M. Jin, C. Bao, Y. Zhao, Z. Wang,
[6] M. S. Neralagatta, U. Maitra, Chem. Soc. Rev. 2005, 34, 821–836.
[9] a) F. Brustolin, F. Goldoni, E. W. Meijer, N. A. J. M. Sommerdijk,
Hoeben, M. Masuda, A. P. H. J. Schenning, E. W. Meijer, T. Shimizu,
OPE1: [PdACHTUNGTRENNUNG(Ph3P)4] (46.0 mg, 0.04 mmol) and CuI (7.6 mg, 0.04 mmol)
were added to a stirred solution of 4 (632.2 mg, 1 mmol) and 1,4-diethy-
nylbenzene (64.3 mg, 0.51 mmol) in DMF (10 mL) under nitrogen. The
reaction mixture was stirred under nitrogen at 408C for 20 h, then fil-
tered. The filtrate was evaporated under vacuum and further purified by
chromatography on neutral Al2O3 (CHCl3/CH3OH 15:1). The crude
product was dissolved in a small amount of THF and added dropwise
into acetone. OPE1 was obtained as a light yellow solid by filtration and
was dried under vacuum for 24 h (337.6 mg, 62%). 1H NMR (300 MHz,
[D6]DMSO): d=10.08 (s, 2H; NH), 7.65 (d, J=7.2 Hz, 4H; Ar-H), 7.55
(s, 4H; Ar-H), 7.49 (d, J=7.2 Hz, 4H; Ar-H), 4.32 (d, J=4.2 Hz, 2H; 12-
OH), 4.12 (d, J=3.9 Hz, 2H; 7-OH), 4.05 (d, J=3.8 Hz, 2H; 3-OH), 3.80
(s, 2H; 12-CH), 3.62 (s, 2H; 7-CH), 3.19–3.26 (m, 2H; 3-CH), 1.00–2.38
(m, 48H; alkyl-H), 0.98 (d, J=5.6 Hz, 6H; 18-CH3), 0.81 (s, 6H; 19-
CH3), 0.60 ppm (s, 6H; 21-CH3); 13C NMR (300 MHz, [D6]DMSO): d=
172.6, 140.6, 132.7, 132.0, 120.0, 119.0, 118.7, 92.2, 88.8, 71.5, 71.0, 66.8,
46.6, 46.3, 41.9, 36.3, 35.8, 35.7, 35.5, 34.1, 32.1, 31.9, 29.1, 27.8, 26.8, 23.4,
23.2, 17.0, 12.9 ppm; IR (KBr): n˜ =3428, 2923, 2862, 2215, 1669, 1593,
1520, 1046 cmÀ1; MS (ESI): m/z: 1112 [M+Na]+; elemental analysis calcd
(%) for C70H92N2O8: C 77.17, H 8.51, N 2.57; found: C 76.93, H 8.90, N
2.41.
[10] S. Verma, T. Hauck, M. E. El-Khouly, P. A. Padmawar, T. Canteen-
[11] J. H. Fuhrhop, H. H. David, J. Mathieu, U. Liman, H. J. Winter, E.
[12] DLS measurements may slightly overestimate the size of the parti-
cles due to agglomeration in aqueous solution.
6406
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 6399 – 6407