Supramolecular Dendrimers
3J = 3.9 Hz, 1 H, PhCH2), 5.09 (d, 3J = 3.6 Hz, 1 H, PhCH2), 5.06 *CHouter), 71.11 (1 C, *CHouter), 70.66 (1 C, *CHouter), 70.65 (1 C,
FULL PAPER
3
3
(d, J = 3.6 Hz, 1 H, PhCH2), 5.02 (d, J = 3.6 Hz, 1 H, PhCH2), *CHouter), 67.80 (1 C, PhCH2O), 67.79 (1 C, PhCH2O), 67.65 (1 C,
3
4.61 (m, 4 H, OCH2), 3.51 (t, J = 6.4 Hz, 2 H, CH2Br), 3.20 (m, PhCH2O), 67.63 (1 C, PhCH2O), 65.98 (1 C, CH2O), 64.92 (1 C,
4 H, NCH2), 2.62 (m, 2 H, CH2COO), 2.15 (3 m, 8 H, CH2), 1.31
CH2O), 51.82 (1 C, O2CCCO2), 39.25 (1 C, CH2N), 39.23 (1 C,
CH2N), 33.04 (1 C, CH2COO), 32.96 (1 C, CH2COO), 31.16, 30.09,
(m, 12 H, CH2) ppm. 13C NMR (CDCl3, 100.5 MHz, room temp.):
δ = 172.08 (1 C, CONH), 172.06 (1 C, CONH), 171.01 (1 C, C=O), 29.07, 28.93, 28.76, 25.84, 25.79, 23.92, 23.91, 23.83 (10 C, CH2)
166.14 (1 C, C=O), 165.95 (1 C, C=O), 165.7 C=O, 1 C, (), 165.73 ppm. MS (FAB, NBA): m/z = 2323 [M]+; MW = 2325.09 g/mol.
(1 C, C=O), 165.61 (1 C, C=O), 165.59 (1 C, C=O), 165.09 (1 C,
C=O), 165.04 (1 C, C=O), 165.04 (1 C, C=O), 163.64 (1 C, C=O),
163.48 (1 C, C=O), 145.31, 145.28, 145.23, 145.01, 144.93, 144.92,
144.91, 144.92, 144.73, 144.68, 144.65, 144.58, 144.53, 143.88,
143.86, 143.12, 143.12, 143.05, 142.99, 142.18, 142.16, 141.91,
141.78, 141.78, 141.03, 140.96, 139.06, 139.05, 138.86, 138.86 (58
C, sp2-C), 134.80 (1 C, PhCCH2), 134.80 (1 C, PhCCH2), 134.51
(2 C, PhCCH2), 134.00 (1 C, p-PhCCO), 133.67 (1 C, p-PhCCO),
133.65 (1 C, p-PhCCO), 130.02, 129.97 (8 C, o-PhCCH2), 128.72,
128.60, 128.58, 128.49, 128.48, 128.47, 128.46, 128.45, 128.44,
128.43, 128.40, 128.39, 128.29, 128.28 (27 C, PhC), 72.71 (1 C,
*CHinner), 72.50 (1 C, *CHinner), 71.26 (2 C, sp3-C), 71.16 (1 C,
*CHouter), 71.11 (1 C, *CHouter), 70.66 (1 C, *CHouter), 70.65 (1 C,
*CHouter), 67.81 (1 C, PhCH2O), 67.79 (1 C, PhCH2O), 67.65 (1 C,
PhCH2O), 67.63 (1 C, PhCH2O), 65.98 (1 C, CH2O), 64.92 (1 C,
CH2O), 51.83 (1 C, O2CCCO2), 39.26 (1 C, CH2N), 39.23 (1 C,
CH2N), 33.04 (1 C, CH2COO), 32.96 (1 C, CH2COO), 31.19, 30.09,
29.07, 28.96, 28.76, 25.84, 25.82, 23.94, 23.91, 23.82 (10 C, CH2)
ppm. MS (FAB, NBA): m/z = 2323 [M]+; MW = 2325.09 g/mol.
IR (ATR): ν = 2976, 2934, 1729, 1656, 1536, 1455, 1393, 1366,
˜
1251, 1150, 1104, 953, 849, 757, 706 cm–1. UV/Vis (CH2Cl2): λmax
= 258, 325, 426 nm.
Monoadduct 3b: Compound 3b was synthesized according to the
general procedure III with monoadduct 33 (160 mg, 68.8 µmol),
cyanuric acid (150 mg, 1.16 mmol) and DBU (10 µL, 68.8 µmol) in
DMF (60 mL). The crude product was purified by column
chromatography (SiO2, gradient dichloromethane/ethyl acetate,
70:30 Ǟ50:50). Yield 44 mg (19 µmol, 27%) as a red brownish so-
1
lid. H NMR (CDCl3, 400 MHz, room temp.): δ = 9.82 (br., 2 H,
3
NH), 8.02 (dd, J = 8.0 Hz, 2 H, 2 H, o-BzHinner), 7.91 (m, 4 H,
o-BzHouter), 7.54 (m, 3 H, p-BzH), 7.40 (m, 6 H, m-BzH), 7.28 (m,
10 H, BnH), 7.17 (m, 4 H, BnH), 7.08 (m, 6 H, BnH), 6.84 (br., 2
3
3
H, NH), 5.92 (d, J = 2.9 Hz, 1 H, CH*), 5.90 (d, J = 2.9 Hz, 1
3
3
H, CH*), 5.86 (d, J = 4.8 Hz, 1 H, CH*), 5.82 (d, J = 2.9 Hz, 1
3
3
H, CH*), 5.81 (d, J = 2.9 Hz, 1 H, CH*), 5.77 (d, J = 4.8 Hz, 1
H, CH*), 5.23 (d, 3J = 3.8 Hz, 1 H, PhCH2), 5.21 (m, 2 H, PhCH2),
5.18 (t, 3J = 7.0 Hz, 1 H, PhCH2), 5.14 (d, 3J = 3.9 Hz, 1 H,
3
3
PhCH2), 5.09 (d, J = 4.1 Hz, 1 H, PhCH2), 5.06 (d, J = 7.7 Hz,
1 H, PhCH2), 5.01 (d, 3J = 7.8 Hz, 1 H, PhCH2), 4.54 (m, 4 H,
OCH2), 4.03 (m, 2 H, CH2NCO), 3.23 (m, 4 H, HNCH2), 2.64 (m,
2 H, CH2COO), 2.23 (2 m, 8 H, CH2), 1.45 (m, 8 H, CH2), 1.32
(m, 4 H, CH2) ppm. 13C NMR (CDCl3, 100.5 MHz, room temp.):
δ = 172.30 (1 C, CONH), 172.26 (1 C, CONH), 171.62 (1 C, C=O),
166.60 (1 C, C=O), 166.37 (1 C, C=O), 165.83 (1 C, C=O), 165.78
(1 C, C=O), 165.71 (1 C, C=O), 165.67 (1 C, C=O), 165.14 (1 C,
C=O), 165.06 (1 C, C=O), 165.03 (1 C, C=O), 163.44 (1 C, C=O),
163.39 (1 C, C=O), 149.21 (2 C, NHCON), 148.31 (1 C,
NHCONH), 145.27, 145.21, 145.18, 145.15, 145.12, 145.06, 145.04,
145.01, 144.90, 144.69, 144.66, 144.63, 144.61, 144.58, 143.87,
143.86, 143.09, 143.03, 143.01, 142.95, 142.19, 142.18, 141.91,
141.87, 140.96, 140.96, 140.95, 139.16, 139.14, 138.82 (58 C, sp2-
C), 134.81 (1 C, PhCCH2), 134.79 (1 C, PhCCH2), 134.51 (1 C,
PhCCH2), 134.49 (1 C, PhCCH2), 133.99 (1 C, p-PhCCO), 133.69
(1 C, p-PhCCO), 133.66 (1 C, p-PhCCO), 130.03, 130.00 (8 C, o-
PhCCH2), 128.63, 128.62, 128.50, 128.48, 128.46, 128.45, 128.32
(27 C, PhC), 72.78 (1 C, *CHinner), 72.67 (1 C, *CHinner), 71.38 (1
C, sp3-C), 71.37 (1 C, sp3-C), 71.18 (1 C, *CHouter), 71.14 (1 C,
*CHouter), 70.72 (2 C, *CHouter), 67.86 (2 C, PhCH2O), 67.70 (2
C, PhCH2O), 66.23 (1 C, CH2O), 64.62 (1 C, CH2O), 51.84 (1 C,
O2CCCO2), 39.36 (2 C, CH2N), 38.55 (1 C, CH2N), 33.05 (1 C,
CH2COO), 33.00 (1 C, CH2COO), 30.16, 30.12, 28.67, 28.48, 27.12,
25.79, 25.74, 23.90, 23.87, 23.63 (10 C, CH2) ppm. MS (FAB,
IR (ATR): ν = 2978, 2934, 1729, 1656, 1536, 1454, 1393, 1366,
˜
1251, 1150, 1104, 954, 849, 760, 706 cm–1. UV/Vis (CH2Cl2): λmax
= 257, 325, 425 nm.
Monoadduct 34: Compound 34 was synthesized according to the
general procedure II with malonate 26 (220 mg, 137 µmol), C60
(150 mg, 208 µmol), I2 (38 mg, 151 µmol) and DBU (27 µL,
178 µmol) in toluene (150 mL). The crude product was purified by
column chromatography (SiO2, toluene/ethyl acetate, 80:20). Yield
111 mg (48 µmol, 35%) as a red brownish solid. 1H NMR (CDCl3,
4
3
400 MHz, room temp.): δ = 8.04 (dd, J = 1.3 Hz, J = 8.3 Hz, 2
H, 2 H, o-BzHinner), 7.91 (m, 4 H, o-BzHouter), 7.55 (m, 3 H, p-
BzH), 7.41 (m, 6 H, m-BzH), 7.29 (m, 10 H, BnH), 7.16 (m, 4 H,
3
BnH), 7.09 (m, 6 H, BnH), 6.51 (t, J = 5.8 Hz, 1 H, NH), 6.37 (t,
3
3J = 5.8 Hz, 1 H, NH), 5.91 (d, J = 2.9 Hz, 1 H, CH*), 5.89 (d,
3
3J = 2.9 Hz, 1 H, CH*), 5.85 (d, J = 3.5 Hz, 1 H, CH*), 5.82 (d,
3
3J = 3.5 Hz, 1 H, CH*), 5.80 (d, J = 2.8 Hz, 1 H, CH*), 5.78 (d,
3
3J = 2.8 Hz, 1 H, CH*), 5.24 (d, J = 3.9 Hz, 1 H, PhCH2), 5.20
3
3
(m, 2 H, PhCH2), 5.17 (d, J = 3.9 Hz, 1 H, PhCH2), 5.12 (d, J =
3
3.9 Hz, 1 H, PhCH2), 5.09 (d, J = 3.6 Hz, 1 H, PhCH2), 5.06 (d,
3J = 3.6 Hz, 1 H, PhCH2), 5.03 (d, 3J = 3.6 Hz, 1 H, PhCH2), 4.61
3
(m, 4 H, OCH2), 3.51 (t, J = 6.4 Hz, 2 H, CH2Br), 3.21 (m, 4 H,
NCH2), 2.62 (m, 2 H, CH2COO), 2.18 (3 m, 8 H, CH2), 1.32 (m,
12 H, CH2) ppm. 13C NMR (CDCl3, 100.5 MHz, room temp.): δ
= 172.07 (1 C, CONH), 172.06 (1 C, CONH), 171.01 (1 C, C=O),
166.13 (1 C, C=O), 165.95 (1 C, C=O), 165.7 C=O, 1 C, (), 165.73
(1 C, C=O), 165.61 (1 C, C=O), 165.59 (1 C, C=O), 165.08 (1 C,
C=O), 165.04 (1 C, C=O), 165.03 (1 C, C=O), 163.64 (1 C, C=O),
163.48 (1 C, C=O), 145.30, 145.28, 145.21, 145.01, 144.94, 144.92,
144.91, 144.90, 144.71, 144.68, 144.66, 144.58, 144.53, 143.87,
143.86, 143.12, 143.10, 143.05, 142.98, 142.18, 142.16, 141.89,
141.78, 141.77, 141.03, 140.97, 139.06, 139.05, 138.86, 138.85 (58
NBA): m/z = 2374 [M]+; MW = 2373.25 g/mol. IR (ATR): ν =
˜
3268, 2945, 2864, 1732, 1540, 1455, 1418, 1382, 1262, 1150, 1092,
1027, 957, 908, 733, 701 cm–1. UV/Vis (CH2Cl2): λmax = 256, 325,
425 nm.
Monoadduct 3d: Compound 3d was synthesized according to the
general procedure III with monoadduct 34 (340 mg, 146 µmol), cy-
anuric acid (189 mg, 1.46 mmol) and DBU (22 µL, 146 µmol) in
C, sp2-C), 134.80 (1 C, PhCCH2), 134.79 (1 C, PhCCH2), 134.51 DMF (60 mL). The crude product was purified by column
(2 C, PhCCH2), 134.00 (1 C, p-PhCCO), 133.67 (1 C, p-PhCCO), chromatography (SiO2, gradient dichloromethane/ethyl acetate,
133.65 (1 C, p-PhCCO), 130.02, 129.97 (8 C, o-PhCCH2), 128.72,
128.60, 128.59, 128.49, 128.48, 128.47, 128.46, 128.45, 128.44,
128.43, 128.40, 128.39, 128.29, 128.28 (27 C, PhC), 72.71 (1 C,
70:30Ǟ50:50). Yield 69 mg (29 µmol, 20%) as a red brownish solid.
1H NMR (CDCl3, 400 MHz, room temp.): δ = 9.81 (br., 2 H, NH),
8.03 (dd, 3J = 8.0 Hz, 2 H, 2 H, o-BzHinner), 7.91 (m, 4 H, o-
*CHinner), 72.51 (1 C, *CHinner), 71.26 (2 C, sp3-C), 71.15 (1 C, BzHouter), 7.54 (m, 3 H, p-BzH), 7.39 (m, 6 H, m-BzH), 7.28 (m,
Eur. J. Org. Chem. 2007, 1942–1956
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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1955