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109.9, 106.3, 97.7, 97.4, 70.5, 69.1, 69.0, 68.8, 61.5, 41.8,
31.9, 31.8, 29.4, 29.3, 29.2, 28.9, 25.9, 25.8, 25.7, 22.6,
21.6, 14.1. MS (MALDI-TOF): m/z 1148 [M+H]+, 1136
[M+Na]+. HRMS (MALDI-TOF): calcd for C66H108N5O9
[M+H]+: 1114.8147. Found: 1114.8142.
to the procedure described above for 12. 1H NMR (CDCl3,
400 MHz): d 10.04 (s, 1H), 10.02 (s, 1H), 9.88 (s, 1H),
9.75 (s, 1H), 9.65 (s, 1H), 9.61 (s, 1H), 9.09 (s, 1H), 9.02
(s, 1H), 8.95 (s, 1H), 8.25 (d, J¼5.4 Hz, 1H), 6.87 (d, J¼
5.4 Hz, 1H), 6.53 (s, 2H), 6.49 (s, 1H), 4.20–4.03 (m,
14H), 3.46 (s, 2H), 3.43–3.35 (m, 4H), 1.91–1.80 (m,
20H), 1.45–1.12 (m, 70H), 0.88–0.82 (m, 21H). 13C NMR
(CDCl3, 300 MHz): d 167.8, 163.8, 163.0, 162.9, 154.1,
153.9, 153.7, 153.6, 152.8, 152.7, 152.5, 145.0, 142.4,
142.3, 126.3, 126.1, 126.0, 125.1, 122.6, 122.3, 121.6,
115.5, 115.1, 114.9, 106.1, 97.9, 97.6, 97.4, 70.4, 70.3,
69.1, 69.0, 68.7, 42.8, 40.8, 31.8, 31.7, 29.6, 29.4, 29.3,
29.2, 29.1, 29.0, 28.8, 25.8, 25.7, 22.6, 14.4, 14.0, 12.9.
MS (MALDI-TOF): m/z 1490 [M+H]+, 1513 [M+Na]+,
1529 [M+K]+. HRMS (MALDI-TOF): calcd for
C89H145N6O12 [M+H]+: 1490.0921. Found: 1490.0915.
4.1.8. Compound 1. A solution of compound 14 (0.22 g,
0.20 mmol), fullerene (0.14 g, 0.20 mmol), and iodine
(50 mg, 0.20 mmol) in dry toluene was heated under reflux
for 10 min and then cooled to room temperature. DBU
(0.034 mL) was added with a syringe and the mixture stirred
for 12 h. Upon removal of the solvent in vacuo, the resulting
residue was subjected to column chromatography (toluene/
dichloromethane 20:1) to give compound 1 as a purple solid
(0.11 g, 35%). 1H NMR (CDCl3, 300 MHz): d 9.93 (s, 1H),
9.78 (s, 1H), 9.72 (s, 1H), 9.15 (s, 1H), 9.04 (s, 1H), 8.85 (s,
1H), 8.25 (t, J¼2.4 Hz, 1H), 6.88 (dd, J1¼1.2 Hz, J2¼
6.3 Hz, 1H), 6.57 (s, 1H), 6.55 (s, 1H), 4.22–4.06 (m,
12H), 3.78 (br s, 2H), 2.02–1.86 (m, 12H), 1.46–1.30 (m,
54H), 0.89–0.84 (m, 15H). 13C NMR (CDCl3, 300 MHz):
d 162.6, 159.3, 158.8, 158.7, 154.9, 154.5, 145.3, 145.2,
145.1, 144.8, 144.7, 144.6, 143.8, 143.0, 142.9, 142.8,
142.3, 142.1, 141.1, 76.7, 76.6, 76.5, 31.8, 31.7, 29.6,
29.4, 29.3, 29.2, 29.1, 25.9, 22.6, 22.5, 14.1, 14.0. MS
(MALDI-TOF): m/z 1854 [M+Na]+. HRMS (MALDI-
TOF): calcd for C126H105N5O9Na [M+Na]+: 1854.7310.
Found: 1854.7805.
4.1.12. Compound 2. It was prepared as a purple solid
(20%) from the reaction of compound 17 with fullerene ac-
cording to the procedure described above for the preparation
of 1. 1H NMR (CDCl3, 400 MHz): d 10.27 (s, 1H), 9.80 (s,
1H), 9.75 (s, 1H), 9.62 (s, 1H), 9.17 (s, 1H), 9.10 (s, 1H),
8.92 (s, 1H), 8.80 (s, 1H), 8.10 (s, 1H), 7.97 (br, 1H), 7.36
(br s, 1H), 6.64 (s, 1H), 6.58 (s, 1H), 6.54 (s, 1H), 4.61 (br,
2H), 4.64 (br, 2H), 4.23–4.11 (m, 14H), 1.86–1.90 (m,
20H), 1.47–1.26 (m, 6H), 0.86–0.77 (m, 21H). 13C NMR
(CDCl3, 300 MHz): d 158.6, 154.3, 148.5, 145.2, 145.1,
144.7, 144.6, 144.5, 143.8, 143.1, 143.0, 142.9, 142.2,
142.0, 140.9, 138.4, 128.5, 126.9, 125.0, 121.2, 120.5,
110.4, 97.6, 70.6, 70.4, 69.5, 69.2, 63.9, 56.0, 43.1, 31.8,
31.8, 31.7, 29.6, 29.5, 29.4, 29.3, 29.2, 25.9, 25.7, 25.5,
22.7, 22.6, 14.2, 14.0. MS (MALDI-TOF): m/z 2208
[M+H]+, 2230 [M+Na]+, 2246 [M+K]+. HRMS (MALDI-
TOF): calcd for C149H144N6O12 [M+H]+: 2208.0764. Found:
2208.0759.
4.1.9. Compound 15. To a solution of compound 7 (1.11 g,
5.00 mmol) and triethylamine (0.8 mL, 8.00 mmol) in chlo-
roform (80 mL) was added a solution of compound 9
(2.20 g, 5.00 mmol) in chloroform (20 mL). The mixture
was heated under reflux for 3 h and then cooled to room tem-
perature. After workup, the crude product was purified by
column chromatography (dichloromethane/AcOEt 10:1) to
1
afford 15 as a white solid (2.51 g, 80%). H NMR (CDCl3,
400 MHz): d 9.73 (s, 1H), 9.65 (s, 1H), 8.91 (s, 1H), 8.28
(d, J¼5.4 Hz, 1H), 6.86 (d, J¼5.4 Hz, 1H), 6.54 (s, 1H),
4.29 (t, J¼6.9 Hz, 2H), 4.21–4.12 (m, 4H), 2.00–1.84 (m,
6H), 1.49–1.29 (m, 30H), 0.89–0.86 (m, 9H). 13C NMR
(CDCl3, 300 MHz): d 160.9, 160.6, 156.8, 153.7, 145.9,
142.5, 133.6, 131.4, 125.3, 114.2, 106.4, 97.9, 70.5, 70.2,
68.9, 31.7, 31.6, 31.7, 29.3, 29.2, 29.1, 29.0, 28.8, 25.8,
25.7, 22.6, 22.5, 14.7, 14.4, 14.0. MS (ESI): m/z 628
[M+H]+. HRMS (ESI): calcd for C36H58N3O6 [M+H]+:
628.4300. Found: 628.4320.
4.1.13. Compound 19. To a stirred solution of compound 18
(5.00 g, 20.0 mmol) in methanol (100 mL) were added
iodine (5.12 g, 20.0 mmol) and silver sulfate (6.26 g,
20.0 mmol). The suspension was stirred for 1 h and then
the solid was filtered off. The filtrate was concentrated under
reduced pressure and the resulting residue triturated in ethyl
acetate (100 mL). The organic phase was washed with water
(50 mLꢀ2), brine (50 mL) and dried over sodium sulfate.
Upon removal of the solvent under reduced pressure, the re-
sulting residue was recrystallized from ethyl acetate to give
1
19 as a dark brown solid (6.79 g, 90%). H NMR (CDCl3,
4.1.10. Compound 16. Itwaspreparedasawhitesolidin96%
yield by the palladium-catalyzed hydrogenation of 15 accord-
ing to the procedure described above for 11. 1H NMR
(CD3OD, 400 MHz): d 9.81 (s, 1H), 8.55 (d, J¼6.9 Hz, 1H),
8.24 (s, 1H), 7.78 (d, J¼6.9 Hz, 1H), 7.02 (s, 1H), 4.60 (t,
J¼6.9 Hz, 2H), 4.51 (t, J¼6.9 Hz, 2H), 4.31 (t, J¼6.6 Hz,
2H), 2.02–1.90 (m, 6H), 1.56–1.27 (m, 30H), 0.93–0.85 (m,
9H). 13C NMR (CDCl3, 300 MHz): d 164.7, 162.1, 160.8,
159.0, 140.1, 132.9, 130.0, 128.9, 115.3, 114.4, 111.2,
100.5, 73.9, 72.6, 71.9, 33.4, 33.4, 31.0, 30.9, 30.8, 30.9,
30.8, 30.8, 30.5, 30.1, 27.3, 27.1, 24.2, 24.1, 14.8. MS (ESI):
m/z 598 [M+H]+, 638 [M+K]+. HRMS (ESI): calcd for
C36H60N3O4 [M+H]+: 598.4507. Found: 598.4578.
400 MHz): d 8.08 (d, J¼2.1 Hz, 1H), 7.76 (dd, J1¼2.4 Hz,
J2¼8.7 Hz, 1H), 6.83 (d, J¼8.7 Hz, 1H), 4.06 (t, J¼
6.6 Hz, 2H), 1.83–1.76 (m, 2H), 1.59–1.27 (m, 10H), 0.87
(t, J¼6.9 Hz, 3H). 13C NMR (CDCl3, 300 MHz): d 152.3,
142.4, 133.7, 116.5, 80.2, 69.9, 31.7, 29.2, 29.1, 28.8,
25.8, 25.7, 22.6, 14.0. MS (EI): m/z 377 [M]+. HRMS
(EI): calcd for C14H20NO3I: 377.0488. Found: 377.0488.
4.1.14. Compound 20. A suspension of compound 19
(3.75 g, 10.0 mmol), imidazole (0.80 g, 12.0 mmol), potta-
sium carbonate (3.45 g, 25.0 mmol), cupric iodide (0.10 g,
0.50 mmol), and proline (0.10 g, 1.00 mmol) in DMF
(20 mL) was stirred at 100 ꢂC for 40 h and then concentrated
under reduced pressure. The residue was washed with water
and the solid filtered. The solid was triturated in ethyl
acetate (100 mL). The organic phase was washed with water
4.1.11. Compound 17. It was prepared as a white solid
(78%) from the reaction of compounds 13 and 16 according