0.720 mmol) and tetraaldehyde 9 (0.091 g, 0.120 mmol) in 1,2-
dichloroethane (2.5 ml) NaBH(OAc)3 (0.152 g, 0.720 mmol) and AcOH
(30 ml, 0.480 mmol) were added. The reaction mixture was stirred at r.t.
overnight, quenched with 1 N NaOH solution and extracted with
methylene chloride. The combined organic phases were washed with brine,
dried (MgSO4) and concentrated in vacuo. The crude residue was flash-
chromatographed (5–25% of methanol in dichloromethane to give 1
(0.240 g, 78%) as an amorphous solid. 1: Rf: 0.38 (20% methanol in
dichloromethane); [a]D: 70 (c = 1.0, CHCl3); 1H NMR (400 MHz, TCDE,
110 uC) d 0.60 (3 H, s, CH3-18), 0.72 (3 H, bd, CH3-21), 0.78 (3 H, s, CH3-
19), 1.84 (3 H, s, COCH3), 2.72 (2 H, CH2CH2NH), 3.30 (3 H, s, OCH3),
3.55–3.97 (8 H, m, CH2OCH3, ArOCH2, ArCH2Ar, HNCH2Ar, 4.53 (1 H,
m, H-3), 4.91 (1 H, bs, H-12), 7.13 (2 H, s, ArH); 13C NMR (400 MHz,
TCDE, 110 uC) d 10.7, 16.2, 19.2, 19.3, 20.9, 21.1, 21.7, 23.9, 24.2, 24.9,
25.2, 25.6, 30.7, 31.5, 32.3, 32.9, 33.1, 33.2, 33.7, 34.2, 40.3, 43.6, 45.4, 46.5,
47.8, 48.0, 56.6, 69.6, 70.5,72.4, 74.1, 121.4, 130.4 (62), 132.1 (62), 155.8,
167.9, 168.2. HRESI-MS (m/z): calcd. for C156H236N4O24 [M + 2H]2+
1275.8763; found 1275.8676.
6 The thickness of a phosphatidylcholine/phosphatidylglicerol membrane
˚
bilayer model is around 30–35 A.
7 W. Verboom, S. Datta, Z. Asfari, S. Harkema and D. N. Reinhaudt,
J. Org. Chem., 1992, 57, 5394–5398.
8 A. Arduini, S. Fanni, G. Manfredi, A. Pochini, R. Ungaro, A. R. Sicuri
and F. Ugozzoli, J. Org. Chem., 1995, 60, 1448–1453.
9 A. F. Abdel-Magid, K. G. Carson, B. D. Harris, C. A. Marynoff and
R. D. Shah, J. Org. Chem., 1996, 61, 3849–3862.
10 L. C. Groenen, B. H. M. Ruel, A. Casnati, P. Timmerman,
W. Verboom, S. Harkema, A. Pochini, R. Ungaro and
D. N. Reinhaudt, Tethraedron Lett., 1991, 32, 2675–2687.
11 N. R. Clement and J. M. Gould, Biochemistry, 1981, 20, 1534–1538.
12 S. Otto, M. Osifchin and S. L. Regen, J. Am. Chem. Soc., 1999, 121,
10440–10441 and references cited therein.
13 The pseudo-first order rate constants were obtained by non-linear
regression analysis of the fluorescence or the Na+ NMR peak areas vs.
time data and the fit error on the rate constant was always less than 1%.
14 F. De Riccardis, M. Di Filippo, D. Garrisi, I. Izzo, F. Mancin,
L. Pasquato, P. Scrimin and P. Tecilla, Chem. Commun., 2002,
3066–3067.
15 The formation of pores by the assembly of hydrophobic calix[4]arene
amide has been reported: V. Sidorov, F. W. Kotch, G. Abdrakhmanova,
R. Mizani, J. C. Fettinger and J. T. Davis, J. Am. Chem. Soc., 2002, 124,
2267–2278.
16 A ionophore based on a resorcin[4]arene-cholic acid ether assembly has
been reported. In this case, however, only the cone-like rccc isomer was
prepared. N. Yoshino, A. Satake and Y. Kobuke, Angew. Chem. Int.
Ed., 2001, 40, 457–459.
1 R. MacKinnon, Angew. Chem. Int. Ed., 2004, 43, 4265–4277.
2 I. Tabushi, Y. Kuroda and K. Yokota, Tetrahedron Lett., 1982, 23,
4601–4604.
3 For recent and general reviews, see: G. W. Gokel and
A. Mukhopadhyay, Chem. Soc. Rev., 2001, 30, 274–286; S. Matile,
A. Som and N. Sorde´, Tetrahedron, 2004, 60, 6405–6435.
4 A. D. Pechulis, R. J. Thompson, J. P. Fojtik, H. M. Schwartz,
C. A. Lisek and L. L. Frye, Bioorg. Med. Chem., 1997, 5, 1893–1901.
5 V. Bo¨hmer, Angew. Chem. Int. Ed., 1995, 34, 713–745.
1356 | Chem. Commun., 2005, 1354–1356
This journal is ß The Royal Society of Chemistry 2005