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54. General procedure for synthesis trimer 9 and 10: A solution of azide (0.6 mmol)
and 2, 4, 6-tris (prop-2-ynyloxy)-1,3,5-triazine 2 (0.2 mmol) in t-BuOH–CH3OH
(18 mL, 5:1 v/v) was stirred at 65 °C for 15 min. Then, CuSO4Á5H2O (5 mol % in
0.5 mL of H2O) and sodium ascorbate (20 mol % in 0.5 mL of H2O) were added.
The reaction mixture was stirred at 65 °C for 6 h, and then the solvent was
evaporated under reduced pressure to afford a crude product. The crude was
dissolved in CH2Cl2, washed with saturated brine, dried with magnesium
sulfate and filtered, followed by the removal of the solvent under vacuum.
Finally, the crude product was purified by column chromatography on silica gel
to obtain pure fan-shaped bile acid trimers with 75% and 83% yields. Compound
9: 1H NMR (300 MHz, CDCl3, d): 0.63 (s, 3 Â 3H, 18-CH3), 0.84 (s, 3 Â 3H, 19-
CH3), 0.92 (d, 3 Â 3H, J = 5.8 Hz, 21-CH3), 3.60 (s, 3 Â 3H, 24-CO2CH3), 3.96 (m,
3 Â 1H, 12-CH), 4.61 (m, 3 Â 1H, 3-CH), 5.52 (s, 3 Â 2H, OCH2), 7.78 (s, 3 Â 1H,
triazole-H); 13C NMR (75 MHz, CDCl3, d): 12.8, 17.4, 23.6, 23.7, 24.8, 25.9, 26.4,
27.5, 28.9, 29.8, 30.6, 30.9, 31.1, 33.6, 34.4, 35.2, 35.8, 37.3, 46.6, 47.3, 48.3,
51.6, 57.0, 61.8, 73.0, 123.2, 141.6, 172.8, 174.8; ESI-MS (+): m/z = 1560.4
[M+Na]+, 1576.8 [M+K]+; ESI-MS (À): m/z = 1572.5 [M+Cl]À; HRMS(ESI): m/z
[M+H]+ calcd for C87H132N12O12: 1538.0166; found: 1538.0160; Compound 10:
1H NMR (300 MHz, CDCl3, d): 0.65 (s, 3 Â 3H, 18-CH3), 0.82 (s, 3 Â 3H, 19-CH3),
0.95 (d, 3 Â 3H, 21-CH3), 3.61 (s, 3 Â 3H, 24-CO2CH3), 3.86 (m, 3 Â 1H, 7-CH),
3.96 (m, 3 Â 1H, 12-CH), 4.54 (m, 3 Â 1H, 3-CH), 5.53 (s, 3 Â 2H, OCH2), 7.84 (s,
3 Â 1H, triazole-H); 13C NMR (75 MHz, CDCl3, d): 12.6, 14.2, 17.4, 21.1, 22.8,
23.4, 23.5, 26.6, 27.7, 28.5, 30.7, 31.0, 31.2, 32.5, 34.1, 35.0, 35.4, 36.9, 39.4,
41.8, 46.6, 47.3, 51.6, 57.1, 60.5, 68.2, 73.1, 76.7, 123.7, 141.6, 172.8, 174.8; ESI-
MS (+): m/z = 1606.9 [M+Na]+, 1624.7 [M+K]+; ESI-MS (À): m/z = 1585.2
[MÀH]À; HRMS(ESI): m/z [M+H]+ calcd for C87H132N12O15: 1586.0013; found:
1586.0008.
52. Data for compound 2 see Ref. 36.
53. General procedure for synthesis bile acid methyl ester (5, 6) and azide (7, 8) see
Ref. 46. Compound 5: 1H NMR (300 MHz, CDCl3, d): 0.68 (s, 3H, 18-CH3), 0.91 (s,
3H, 19-CH3), 0.96 (d, 3H, J = 5.8 Hz, 21-CH3), 3.61 (m, 1H, 3-CH), 3.66 (s, 3H, 24-
CO2CH3), 3.98 (m, 1H, 12-CH); 13C NMR (75 MHz, CDCl3, d): 12.7, 17.2, 23.1,
23.6, 26.1, 27.1, 27.4, 28.6, 30.8, 31.0, 33.6, 34.1, 35.1, 35.2, 35.9, 36.4, 42.0,
46.4, 47.2, 48.2, 51.4, 71.7, 73.1, 174.7; ESI-MS(+): m/z = 429.5 [M+Na]+;
Compound 6: 1H NMR (300 MHz, CDCl3, d): 0.68 (s, 3H, 18-CH3), 0.89 (s, 3H, 19-
CH3), 0.98 (d, 3H, J = 5.8 Hz, 21-CH3), 3.47 (m, 1H, 3-CH), 3.66 (s, 3H, 24-
CO2CH3), 3.84 (m, 1H, 7-CH), 3.96 (m, 1H, 12-CH); 13C NMR (75 MHz, CDCl3, d):
12.5, 17.3, 22.5, 23.2, 26.4, 27.5, 28.1, 30.4, 30.9, 31.1, 34.6, 34.8, 35.3, 39.5,
41.5, 41.6, 46.4, 47.0, 51.5, 68.5, 71.9, 73.1, 76.1, 174.8; ESI-MS(+): m/z = 445.8
[M+Na]+, 461.5 [M+K]+; Compound 7: 1H NMR (300 MHz, CDCl3, d): 0.68 (s, 3H,
18-CH3), 0.94 (s, 3H, 19-CH3), 0.97 (d, 3H, J = 5.8 Hz, 21-CH3), 3.65 (s, 3H, 24-
CO2CH3), 3.94 (m, 3H, 3-CH), 3.98 (m, 1H, 12-CH); 13C NMR (75 MHz, CDCl3, d):
12.5, 17.1, 23.3, 23.4, 24.1, 25.9, 26.3, 27.1, 28.7, 29.7, 30.0, 30.7, 30.8, 33.04,
34.3, 34.9, 35.6, 37.1, 46.3, 47.1, 48.1, 51.3, 58.6, 72.9, 174.5; ESI-MS(+): m/
z = 454.0 [M+Na]+; Compound 8: 1H NMR (300 MHz, CDCl3, d): 0.69 (s, 3H, 18-
CH3), 0.93 (s, 3H, 19-CH3), 0.97 (d, 3H, J = 5.8 Hz, 21-CH3), 3.66 (s, 3H, 24-
CO2CH3), 3.87 (m, 3H, 3-H), 3.90 (m, 1H, 7-CH), 3.98 (m, 1H, 12-CH); 13C NMR
(75 MHz, CDCl3, d): 12.5, 17.3, 22.8, 23.2, 24.5, 26.1, 27.4, 28.4, 29.6, 30.5, 30.8,
31.0, 33.0, 34.1, 35.1, 35.2, 36.7, 39.4, 41.9, 46.5, 47.2, 51.5, 58.7, 68.4, 72.9,
76.6, 174.7; ESI-MS(+): m/z = 470.3 [M+Na]+; ESI-MS(À): m/z = 483.6 [M+Cl]À.