G.-T. Wang et al. / Tetrahedron 67 (2011) 48e57
55
sodium borohydride (0.57 g, 15.0 mmol). The solution was stirred
for 2 h and then saturated aqueous ammonium chloride solution
added dropwise until no gas was evolved. The mixture was con-
centrated with a rotavapor and the obtained slurry triturated with
ethyl acetate (200 mL). The organic phase was washed with water
(3ꢃ70 mL) and brine (70 mL), and dried over sodium sulfate. After
the solvent was removed in vacuo, the resulting residue was sub-
jected to flash chromatography (dichloromethane/AcOEt 10:1) to
give compound 14b as a white solid (0.76 g, 96%). 1H NMR
4.8.1. Compound 2a. Yellow solid (72%). 1H NMR (300 MHz, CDCl3):
10.89 (s, 2H), 9.09 (s, 2H), 8.46 (s, 2H), 8.24 (s, 2H), 8.02 (s, 2H), 5.38
d
(d, J¼5.1 Hz, 2H), 4.14 (s, 6H), 4.11 (s, 4H), 3.97 (s, 6H), 3.95 (s, 6H),
3.35e3.27 (m, 2H), 2.47e2.29 (m, 4H), 2.03e1.76 (m, 12H),1.59e0.83
(m, 64H), 0.68 (s, 6H). 13C NMR (75 MHz, CDCl3):
d 168.3,161.6, 151.5,
142.2, 142.0, 140.0, 125.2, 123.9, 122.7, 122.4, 115.1, 103.7, 103.1, 80.5,
68.0, 56.7, 56.3, 56.1, 50.1, 42.3, 39.7, 39.5, 39.0, 37.0, 36.8, 36.2, 35.8,
31.9, 31.8, 28.3, 28.2, 28.0, 24.3, 23.8, 22.8, 22.5, 21.1,19.3,18.7,11.8. MS
(MALDI-TOF): m/z 1402.5 [MþNa]þ. Anal. Calcd for C84H122N4O12: C,
73.11; H, 8.91; N, 4.06. Found: C, 72.71; H, 9.03; N, 3.79.
(300 MHz, CDCl3): d 8.92 (s, 1H), 8.05 (s, 1H), 6.34 (s, 1H), 5.39e5.35
(m, 1H), 4.07 (s, 2H), 3.98 (t, J¼6.4 Hz, 2H), 3.91 (t, J¼6.8 Hz, 2H),
3.68 (br, 2H), 3.33e3.25 (m, 1H), 2.44e2.26 (m, 2H), 2.03e1.77 (m,
10H), 1.61e0.85 (m, 58H), 0.68 (s, 3H). 13C NMR (75 MHz, CDCl3):
4.8.2. Compound 2b. Yellow solid (68%). 1H NMR (400 MHz,
CDCl3): d 10.66 (s, 2H), 9.10 (s, 2H), 8.50 (s, 2H), 8.24 (s, 2H), 8.00 (s,
d
167.3, 142.1, 140.0, 139.9, 132.2, 122.2, 118.4, 105.3, 100.1, 80.2,
2H), 5.38 (d, J¼3.9 Hz, 2H), 4.27 (t, J¼6.9 Hz, 4H), 4.11 (s, 4H), 3.94 (s,
6H), 3.92 (s, 6H), 3.35e3.28 (m, 2H), 2.48e2.30 (m, 4H), 2.00e1.77
(m, 16H), 1.60e0.85 (m, 90H), 0.68 (s, 6H); 13C NMR (100 MHz,
69.12, 69.07, 67.9, 56.6, 56.1, 50.0, 42.2, 39.7, 39.4, 39.0, 36.9, 36.7,
36.1, 35.7, 31.9, 31.8 (t), 29.6, 29.4 (t), 29.3, 29.2, 28.3, 28.2, 27.9, 26.1
(d), 24.2, 23.8, 22.8, 22.6 (d), 22.5, 21.0, 19.3, 18.6, 14.08, 14.05, 11.8.
MS (MALDI-FT): m/z 790.7 [M]þ, 813.6 [MþNa]þ. HRMS (MALDI-
FT): calcd for C51H86N2O4Na: 813.6480, found: 813.6474.
CDCl3)
d 168.1, 161.9, 150.7, 142.2, 141.6, 139.9, 125.1, 123.6, 122.6,
122.2, 116.0, 104.1, 102.7, 80.4, 70.2, 67.9, 56.6, 56.3, 56.1, 55.9, 50.0,
42.2, 39.6, 39.4, 38.9, 36.9, 36.7, 36.1, 35.7, 31.80, 31.77, 31.7, 29.3,
29.20, 29.16, 28.2, 28.1, 28.0, 25.7, 24.2, 23.8, 22.7, 22.6, 22.5, 21.0,
19.3, 18.6, 14.0, 11.8. MS (MALDI-FT): 1598.1 [MþNa]þ. HRMS
(MALDI-FT): calcd for C98H150N4O12Na [M]þ: 1598.1142, found:
1598.1142. Anal. Calcd for C98H150N4O12: C, 74.67; H, 9.59; N, 3.55.
Found: C, 74.55; H, 9.47; N, 3.66.
4.7.1. Compound 14a. White solid. 1H NMR (300 MHz, CDCl3):
d
8.84 (s, 1H), 8.01 (s, 1H), 6.35 (s, 1H), 5.39e5.35 (m, 1H), 4.07 (s,
2H), 3.83 (s, 3H), 3.79 (s, 3H), 3.36e3.26 (m, 1H), 2.46e2.29 (m, 2H),
2.03e1.77 (m, 6H), 1.56e0.85 (m, 32H), 0.68 (s, 3H). 13C NMR
(100 MHz, CDCl3):
d 167.6, 142.9, 140.7, 140.1, 132.2, 122.3, 118.1,
104.6, 99.3, 80.4, 68.0, 56.7, 56.3, 56.3, 56.1, 50.0, 42.3, 39.7, 39.5,
39.0, 37.0, 36.8, 36.1, 35.8, 31.9, 31.8, 28.3, 28.2, 28.0, 24.2, 23.8 (d),
22.8, 22.5, 21.0, 19.3, 18.6, 11.8. MS (MALDI-FT): m/z 594.4 [M]þ,
617.4 [MþNa]þ. HRMS (MALDI-FT): calcd for C37H58N2O4Na:
617.4289, found: 617.4282.
4.8.3. Compound 2c. Yellow solid (69%). 1H NMR (300 MHz, CDCl3):
d
10.66 (s, 2H), 9.10 (s, 2H), 8.50 (s, 2H), 8.24 (s, 2H), 8.00 (s, 2H),
5.38 (d, J¼5.1 Hz, 2H), 4.27 (t, J¼6.9 Hz, 4H), 4.11 (s, 4H), 3.94 (s, 6H),
3.92 (s, 6H), 3.35e3.28 (m, 2H), 2.48e2.30 (m, 4H), 2.02e1.80 (m,
16H), 1.60e0.85 (m, 106H), 0.68 (s, 6H). 13C NMR (100 MHz, CDCl3):
d
168.2, 162.0, 150.7, 142.3, 141.7, 140.0, 125.2, 123.6, 122.7, 122.3,
4.7.2. Compound 14c. White solid. 1H NMR (400 MHz, CDCl3):
116.0, 104.1, 102.7, 80.4, 70.2, 68.0, 56.6, 56.3, 56.1, 56.0, 50.0, 42.2,
39.7, 39.4, 38.9, 36.9, 36.7, 36.1, 35.7, 31.9, 31.8, 29.6 (d), 29.5, 29.4,
29.3, 29.1, 28.3, 28.2, 28.0, 25.7, 24.2, 23.8, 22.8, 22.6, 22.5, 21.0,19.3,
18.6, 14.1, 11.8. MS (MALDI-FT): m/z 1710.2 [MþNa]þ. HRMS
(MALDI-FT): calcd for C106H166N4O12Na [M]þ: 1710.2394, found:
1710.2377. Anal. Calcd for C106H166N4O12: C, 75.40; H, 9.91; N, 3.32.
Found: C, 75.12; H, 9.94; N, 3.17.
d
8.91 (s, 1H), 8.05 (s, 1H), 6.34 (s, 1H), 5.39e5.34 (m, 1H), 4.07 (s,
1H), 3.97 (t, J¼6.8 Hz, 2H), 3.91 (t, J¼6.8 Hz, 2H), 3.69 (br, 2H),
3.33e3.25 (m, 1H), 2.44e2.28 (m, 2H), 2.03e1.76 (m, 10H),
1.60e0.85 (m, 74H), 0.68 (s, 3H). 13C NMR (75 MHz, CDCl3):
d 167.3,
142.2, 140.1, 140.0, 132.2, 122.2, 118.4, 105.4, 100.2, 80.2, 69.2, 69.1,
68.0, 56.7, 56.1, 50.0, 42.2, 39.7, 39.5, 39.0, 36.9, 36.7, 36.1, 35.7, 31.9,
31.9, 31.8, 29.8 (d), 29.7 (d), 29.6 (d), 29.4, 29.4, 29.3, 28.3, 28.1, 28.0,
26.2, 26.1, 24.2, 23.8, 22.8, 22.7, 22.5, 21.0, 19.3, 18.6, 14.1, 11.8. MS
(MALDI-FT): m/z 902.8 [M]þ, 925.8 [MþNa]þ. HRMS (MALDI-FT):
calcd for C59H102N2O4Na: 925.7732, found: 925.7719.
4.8.4. Compound 2d. Yellow solid (64%). 1H NMR (400 MHz,
CDCl3): d 10.69 (s, 2H), 9.17 (s, 2H), 8.46 (s, 2H), 8.26 (s, 2H), 8.03 (s,
2H), 5.38 (d, J¼4.4 Hz, 2H), 4.11e4.08 (m, 18H), 3.35e3.29 (m, 2H),
2.46e2.29 (m, 4H), 2.02e1.78 (m,16H),1.60e0.84 (m,114H), 0.68 (s,
4.8. Compounds 2aei
6H). 13C NMR (100 MHz, CDCl3):
d 167.9, 161.5, 151.4, 141.5, 141.1,
139.9, 125.2, 123.7, 122.9, 122.3, 115.2, 104.6, 103.6, 80.2, 69.3, 69.1,
67.9, 56.6, 56.1, 50.0, 42.2, 39.7, 39.4, 39.0, 36.9, 36.7, 36.1, 35.7, 31.9,
31.8, 31.7, 31.6, 29.6, 29.5, 29.4, 29.3, 29.2, 28.3, 28.2, 28.0, 26.2, 25.9,
24.2, 23.8, 22.8, 22.7, 22.6, 22.5, 21.0, 19.3, 18.6, 14.1, 14.0, 11.8. MS
(MALDI-FT): m/z 1794.3 [MþNa]þ. HRMS (MALDI-FT): calcd for
C112H178N4O12Na [M]þ: 1794.3334, found: 1794.3334.
To a stirred solution of compounds 14b (0.28 g, 0.35 mmol) and
15b (51 mg, 0.12 mmol) in chloroform (5 mL), cooled in an ice-
bath, was added EDC$HCl (73 mg, 0.39 mmol) slowly. The solution
was stirred at room temperature for 48 h and then another part of
chloroform (35 mL) was added. The solution was washed with
water (3ꢃ20 mL) and brine (20 mL), and dried over sodium sul-
fate. After the solvent was removed in vacuo, the resulting residue
was subjected to flash chromatography and further recrystallized
from dichloromethane and ethyl acetate. Compound 2e was
obtained as a yellow solid (0.16 g, 66%). 1H NMR (400 MHz, CDCl3):
4.8.5. Compound 2f. Yellow solid (66%). 1H NMR (300 MHz, CDCl3):
d
10.51 (s, 2H), 9.17 (s, 2H), 8.40 (s, 2H), 8.27 (s, 2H), 7.97 (s, 2H), 5.38
(d, J¼3.6 Hz, 2H), 4.28 (t, J¼6.6 Hz, 4H), 4.11 (br, 12H), 3.32 (m, 2H),
2.43e2.31 (m, 4H), 2.04e1.77 (m, 24H), 1.67e0.82 (m, 158H), 0.69
d
10.50 (s, 2H), 9.16 (s, 2H), 8.39 (s, 2H), 8.26 (s, 2H), 7.96 (s, 2H),
(s, 6H). 13C NMR (75 MHz, CDCl3):
d 168.1, 162.2, 150.8, 141.8, 141.3,
5.38 (s, 2H), 4.28 (t, J¼6.8 Hz, 4H), 4.11e4.09 (m, 12H), 3.36e3.28
140.0, 126.0, 123.9, 123.1, 122.4, 116.6, 105.1, 104.4, 80.4, 70.5, 69.7,
69.2, 56.7, 56.2, 50.1, 42.3, 39.5, 36.8, 32.0, 31.9, 31.8, 29.6, 29.42,
29.35, 28.0, 26.2, 25.9, 25.8, 22.8, 22.7, 22.65, 22.57, 19.4, 18.7, 14.1,
14.1, 11.9. MS (MALDI-FT): m/z 2102.7 [MþNa]þ. HRMS (MALDI-FT):
calcd for C134H222N4O12Na [M]þ: 2102.6776, found: 2102.6739.
Anal. Calcd for C134H222N4O12: C, 77.33; H, 10.75; N, 2.69. Found: C,
77.57; H, 10.77; N, 2.49.
(m, 2H), 2.47e2.29 (m, 4H), 2.04e1.76 (m, 24H), 1.67e0.82 (m,
142H), 0.692 (s, 6H). 13C NMR (100 MHz, CDCl3):
d 168.0, 162.1,
150.7, 141.7, 141.3, 140.0, 125.9, 123.9, 123.0, 122.3, 116.6, 105.1,
104.3, 80.4, 70.4, 69.7, 69.1, 68.0, 56.7, 56.1, 50.1, 42.3, 39.7, 39.5,
39.0, 36.8, 36.2, 35.8, 32.0, 31.9, 31.8 (d), 31.7, 29.6, 29.5, 29.4, 29.3
(d), 29.2, 29.0, 28.4, 28.2, 28.0, 26.2, 25.9, 25.8, 24.3, 23.8, 22.8,
22.7, 22.6 (d), 21.0, 19.3, 18.7, 14.1, 14.0, 11.8. MS (MALDI-FT): m/z
1990.6 [MþNa]þ. HRMS (MALDI-FT): calcd for C126H206N4O12Na
[M]þ: 1990.5524, found: 1990.5558.
4.8.6. Compound 2g. Yellow solid (62%). 1H NMR (300 MHz, CDCl3):
d
10.67 (s, 2H), 9.17 (s, 2H), 8.46 (s, 2H), 8.26 (s, 2H), 8.02 (s, 2H),