L.-Y. You et al. / Tetrahedron 65 (2009) 9494–9504
9503
1.30–1.29 (m, 24H), 0.89–0.85 (m, 12H). 13C NMR (125 MHz, CDCl3):
1845.2 [MþNa]þ. HRMS (MALDI-FT): Calcd for C97H159N14O19
:
d
¼167.4, 166.7, 166.0, 158.3, 132.6, 109.2, 106.8, 67.4, 52.3, 47.0, 46.3,
1824.1901 [MþH]þ. Found: 1824.1903.
40.7, 31.5 (d), 28.7, 27.5, 26.6, 26.5, 22.5 (d), 14.0, 13.9. MS (ESI): m/z
733.6 [MþH]þ, 755.7 [MþNa]þ. Anal. Calcd for C40H68N4O8: C,
65.54; H, 9.35; N, 7.64. Found: C, 65.41; H, 9.25; N, 7.65.
4.1.23. Compound 4d. 1H NMR (300 MHz, CDCl3):
d
¼10.34 (s, 4H),
8.64 (s, 2H), 8.45–8.44 (br, 2H), 8.31 (s, 2H), 8.12 (d, J¼7.5 Hz, 2H), 7.48
(s, 2H), 7.30 (t, J¼7.5 Hz, 1H), 6.44 (s, 2H), 4.86 (s, 4H), 4.78 (s, 4H),
4.22–4.16 (m, 11H), 3.45 (q, J¼3.3 Hz, 4H), 3.34–3.14 (m, 16H), 1.59–
1.25 (m, 168H), 0.96–0.84 (m, 30H). 13C NMR (125 MHz, CDCl3):
4.1.18. Compound 18. A solution of 17 (0.50 g, 2.3 mmol) and hy-
drazine monohydrate (1.5 mL) in methanol (10 mL) was stirred at
60 ꢁC for 6 h and then concentrated. The crude product was
recrystallized from MeOH to give 18 as a white solid (0.26 g, 52%).1H
d
¼167.9, 167.5, 167.3, 164.2, 161.2, 161.1, 159.2, 158.4, 156.9, 136.0, 135.2,
125.6,124.9,118.3,114.2,97.7, 68.0,67.7, 65.0, 47.3, 46.5, 40.6, 39.7, 31.9,
31.6, 29.6, 29.5, 29.3, 28.8, 27.6, 27.1, 27.0, 26.9, 22.7, 20.2,14.1,13.8. MS
(MALDI-TOF): m/z 2521.8 [MþNa]þ. HRMS (MALDI-TOF): Calcd for
C145H254N14O19Na [MþNa]þ: 2518.9232. Found: 2518.9259.
NMR (300 MHz, DMSO-d6):
d
¼9.39 (s, 2H), 7.48 (d, J¼7.8 Hz, 2H),
7.18 (t, J¼7.8, 7.8 Hz,1H), 4.51 (s, 4H), 3.77 (s, 3H).13C NMR (125 MHz,
DMSO-d6):
d
¼165.3, 154.8, 130.8, 129.3, 123.2, 62.3. MS (ESI): m/z
225.0 [MþH]þ, 246.9 [MþNa]þ. Anal. Calcd for C9H12N4O3: C, 48.21;
H, 5.39; N, 24.99. Found: C, 48.25; H, 5.17; N, 24.95.
4.1.24. Compound 5. 1H NMR (300 MHz, CDCl3):
d
¼10.85 (s, 2H),
10.17–10.16 (br, 2H), 8.02–8.01 (br, 4H), 7.72 (s, 2H), 7.05 (s, 4H),
6.70 (s, 2H), 4.34 (s, 8H), 4.14 (d, J¼4.5 Hz, 8H), 4.03 (s, 6H), 3.34 (t,
J¼7.5 Hz, 8H), 3.20 (t, J¼7.5 Hz, 8H), 1.58–1.51 (m, 16H), 1.37–1.21
4.1.19. Compound 3. To a stirred solution of 18 (100 mg, 0.11 mmol),
cooled in an ice-bath, in CHCl3 (2 mL) and THF (1 mL) were added
EDCI (30 mg, 0.15 mmol), HOBt (20 mg, 0.15 mmol), and 16 (12 mg,
0.05 mmol). The solution was stirred at rt for 26 h and then con-
centrated. After workup, the resulting residue was subjected to
column chromatography (AcOEt/CH2Cl2 1:1) to give 3 as a ropy yel-
(m, 48H), 0.91–0.79 (m, 24H). 13C NMR (125 MHz, CDCl3):
d
¼168.6,
167.6, 162.0, 158.1, 151.3, 135.1, 122.8, 114.6, 107.1, 106.7, 67.1, 56.5,
47.3, 46.4, 40.3, 31.6, 31.4, 28.7, 27.7, 26.6, 22.5 (d), 14.0, 13.9. MS
(MALDI-TOF): m/z 1677.6 [MþNa]þ. HRMS (MALDI-FT): Calcd for
C88H142N12O18Na [MþNa]þ: 1678.0457. Found: 1678.0483.
low oil (35 mg, 32%). 1H NMR (300 MHz, CDCl3):
d¼10.78 (d,
J¼6.9 Hz, 2H), 10.66 (d, J¼6.9 Hz, 2H), 9.02 (s, 2H), 8.20 (d, J¼7.5 Hz,
2H), 7.59 (t, J¼5.4, 5.4 Hz, 2H), 7.35 (t, J¼7.8, 7.8 Hz, 1H), 6.52 (s, 2H),
4.29–4.14 (m, 11H), 3.50–3.44 (m, 4H), 3.32–3.18 (m, 16H), 2.50 (t,
J¼6.9, 6.9 Hz, 4H), 2.40 (t, J¼6.9, 6.9 Hz, 4H), 2.18–1.82 (m,16H),1.59–
1.36 (m, 20H),1.25 (br, 84H), 0.96–0.82 (m, 30H). 13C NMR (125 MHz,
4.1.25. Compound 20. To a solution of 19 (1.00 g, 7.70 mmol) in
CHCl3 (15 mL), cooled in an ice-bath, were added 2-chloroacetic
acid (0.73 g, 7.70 mmol), EDCI (1.80 g, 9.30 mmol), and HOBt
(0.20 g, 1.50 mmol). The solution was stirred for 41 h then washed
with saturated NaHCO3 solution (15 mL), water (15 mL), and brine
(15 mL) and dried over sodium sulfate. Upon removal of the solvent,
the crude product was purified by column chromatography (AcOEt/
PE 5:2) to give 20 as a colorless oil (1.20 g, 75%). 1H NMR (300 MHz,
CDCl3):
d
¼171.9, 171.2, 164.0, 160.7, 160.1, 159.8, 159.0, 156.7, 137.0,
135.0, 125.33, 125.1, 116.0, 112.1, 96.3, 70.0, 69.4, 64.6, 47.9, 47.9, 46.0
(d), 39.5, 32.4, 32.1, 31.8, 31.7 (d), 29.7, 29.4, 29.3 (d), 29.2, 29.1, 28.8,
28.7, 27.8, 27.1, 26.9, 22.6 (d), 22.0, 21.7, 20.3, 14.1 (d), 13.8. MS
(MALDI-TOF): m/z 2010.5 [MþNa]þ. HRMS (MALDI-TOF): Calcd for
C117H202N10O15Na [MþNa]þ: 2010.5243. Found: 2010.5225.
CDCl3):
d
¼7.71 (s, 1H), 4.07 (s, 4H), 3.43 (q, J¼7.2 Hz, 2H), 3.28 (q,
J¼7.2 Hz, 2H), 1.22–1.13 (m, 6H). MS (EI): m/z 206 [M]þ.
4.1.20. Compound 4a. 1H NMR (300 MHz, CDCl3):
d
¼10.34 (s, 4H),
4.1.26. Compound 32. 1H NMR (300 MHz, CDCl3):
d
¼7.72 (s,1H), 4.07
8.44–8.39 (m, 4H), 8.27 (s, 2H), 7.96 (d, J¼7.5 Hz, 2H), 7.85 (s, 2H),
7.16 (t, J¼7.2 Hz, 1H), 6.48 (s, 2H), 4.79 (s, 4H), 4.75 (s, 4H), 4.16–4.11
(m, 11H), 3.41–3.22 (m, 20H), 1.63–1.53 (m, 4H), 1.42–1.31 (m, 4H),
(s, 4H), 3.33 (t, J¼7.2, 7.2 Hz, 2H), 3.16 (t, J¼7.8, 7.8 Hz, 1H), 1.55–154
(br, 4H), 1.26 (br, 36H), 0.88 (t, J¼6.9, 6.9 Hz, 4H). 13C NMR (125 MHz,
CDCl3):
d
¼166.8,166.2, 47.2, 46.5, 42.6, 41.6, 32.1, 29.8, 29.7, 29.6, 28.9,
1.23–0.89 (m, 30H). 13C NMR (125 MHz, CD3OD):
d
¼168.2, 168.1,
27.8, 27.2, 27.1, 22.9, 14.3. MS (ESI): m/z 485.4 [M]ꢀ. HRMS (ESI): Calcd
for C28H56N2O2Cl [MþH]þ: 487.4025. Found: 487.4013.
167.6,167.1,165.0,164.8,164.4,159.0,157.7,156.2,133.4,133.2,126.3,
123.4, 116.4, 114.7, 97.9, 67.1, 66.9, 63.0, 40.5, 39.9, 39.7, 38.9, 30.5,
19.3, 12.3, 11.3, 11.2. MS (MALDI-TOF): m/z 1397.1 [MþNa]þ. HRMS
(MALDI-TOF): Calcd for C65H94N14O19Na [MþNa]þ: 1397.6712.
Found: 1397.6728.
4.1.27. Compound 24. To a stirred solution of 23 (2.30 g, 13.1 mmol)
in CH2Cl2 (30 mL), cooled in an ice-bath, were added EDCI (2.5 g,
13.1 mmol), DMAP (0.3 g, 2.4 mmol), and di-n-butylamine (2.00 mL,
11.8 mmol). The solution was stirred for 27 h, then washed with sat-
urated NaHCO3 solution (30 mL), water (30 mL), and brine (30 mL)
and dried over sodium sulfate. Upon removal of the solvent, the crude
product was purified by column chromatography (AcOEt/PE 1:5) to
give 24 as colorless oil (2.40 g, 70%). 1H NMR (300 MHz, CDCl3):
4.1.21. Compound 4b. 1H NMR (300 MHz, CDCl3):
d¼10.36 (s, 2H),
10.24 (s, 2H), 8.70 (s, 2H), 8.46 (s, 2H), 8.40 (s, 2H), 8.15 (d, J¼7.8 Hz,
2H), 7.41 (t, J¼5.4 Hz, 2H), 7.32 (t, J¼7.8 Hz, 1H), 6.45 (s, 2H), 4.87 (s,
4H), 4.80 (s, 4H), 4.23–4.18 (m, 11H), 3.49–3.43 (m, 4H), 3.37–3.19
(m, 16H), 1.62–1.17 (m, 40H), 0.94–0.83 (m, 30H). 13C NMR
d
¼5.55 (s, 1H), 3.92 (d, J¼4.5 Hz, 2H), 3.30 (t, J¼7.5 Hz, 2H), 3.12 (t,
(125 MHz, CDCl3):
d
¼167.9, 167.6, 167.5, 167.4, 164.5, 162.5, 162.2,
J¼7.5 Hz, 2H), 1.56–1.42 (m, 13H), 1.36–1.21 (m, 4H), 0.94–0.87 (m,
159.2, 158.3, 156.8, 135.4, 134.7, 125.6, 124.4, 117.7, 114.2, 97.8, 67.9,
67.7, 64.6, 46.9, 46.0, 40.7, 39.8, 31.5, 30.8, 30.7, 29.7, 29.6, 20.2, 20.1
(d), 13.8, 13.7. MS (MALDI-TOF): m/z 1621.5 [MþNa]þ, 1638.6
[MþK]þ. HRMS (MALDI-TOF): Calcd for C81H126N14O19Na [MþNa]þ:
1621.9216. Found: 1621.9239.
6H). 13C NMR (125 MHz, CDCl3):
d¼167.4, 155.6, 79.1, 46.4, 45.6, 41.9,
30.6, 29.5, 28.1,19.9(d),13.6,13.5.MS(ESI):m/z309.0[MþNa]þ. HRMS
(ESI): Calcd for C15H30N2O3Na [MþNa]þ: 309.2149. Found: 309.2158.
4.1.28. Compound 29. 1H NMR (300 MHz, CDCl3):
d¼7.72 (s, 1H),
4.06 (s, 2H), 4.05 (s, 2H), 3.30 (t, J¼7.8 Hz, 2H), 3.16 (t, J¼7.8 Hz, 2H),
4.1.22. Compound 4c. 1H NMR (300 MHz, CDCl3):
d¼10.35 (s, 4H),
1.55–1.53 (m, 4H), 1.29 (br, 12H), 0.91–0.85 (m, 6H). 13C NMR
8.59 (s, 2H), 8.45 (s, 2H), 8.30 (s, 2H), 8.07 (d, J¼7.5 Hz, 2H), 7.58 (t,
J¼5.4 Hz, 2H), 7.25 (t, J¼7.5 Hz, 1H), 6.45 (s, 2H), 4.84 (s, 4H), 4.78 (s,
4H), 4.21–4.16 (m,11H), 3.47–3.17 (m, 20H),1.63–1.20 (m, 72H), 0.95–
(125 MHz, CDCl3):
d
¼166.8, 166.2, 47.1, 46.4, 42.6, 41.6, 31.7 (d),
28.8, 27.7, 26.8, 26.7, 22.7 (d), 14.2, 14.1. MS (ESI): m/z 319.2 [MþH]þ,
341.2 [MþNa]þ. HRMS (ESI): Calcd for C16H32N2O2Cl [MþH]þ:
319.2147. Found: 319.2162.
0.81 (m, 30H). 13C NMR (125 MHz, CDCl3):
161.8, 161.7, 159.2, 158.4, 156.8, 135.7, 134.9, 125.6, 124.6, 117.9, 114.2,
97.7, 67.9, 67.7, 64.8, 47.2, 46.4, 40.7, 39.8, 31.6, 31.5 (d), 31.4, 28.7, 27.6,
26.7, 26.6, 26.5, 22.6, 22.5, 20.2, 14.0 (d), 13.8. MS (MALDI-TOF): m/z
d
¼167.9, 167.5, 164.3,
4.1.29. Compound 25. To a stirred solution of 24 (1.74 g, 6.10 mmol)
in CH2Cl2 (10 mL) was added TFA (4 mL) slowly. The solution was