9.53 (br, 2 H), 8.48 (s, 2 H), 8.43 (s, 2 H), 8.26 (d, J = 8.5 Hz, 2 H),
7.90 (br, 2 H), 7.53 (d, J = 8.4 Hz, 2 H), 7.08 (d, J = 8.7 Hz, 2 H),
6.99 (d, J = 8.0 Hz, 2 H), 6.55 (s, 1 H), 6.52 (s, 1 H), 5.56 (s, 4 H),
4.23 (t, J = 6.9 Hz, 4 H), 4.19 (t, J = 6.6 Hz, 4 H), 3.80 (d, J =
6.1 Hz, 4 H), 3.79 (d, J = 5.7 Hz, 4 H), 2.15–2.08 (m, 4 H), 1.88–
1.85 (m, 8 H), 1.46–1.30 (m, 12 H), 1.01 (d, J = 6 Hz, 12 H), 1.00
(d, J = 6 Hz, 12 H), 0.93 (t, J = 7.0 Hz, 6 H), 0.86 (t, J = 7.0 Hz,
6 H). 13C NMR (CDCl3): d 162.2, 156.9, 156.4, 147.4, 145.7, 145.1,
133.2, 133.0, 129.7, 129.6, 127.8, 124.1, 123.0, 121.6, 121.1, 119.5,
117.0, 115.6, 113.9, 113.6, 98.5, 98.2, 76.1, 75.9, 69.9, 69.6, 53.8,
30.9, 28.5, 28.2, 27.8, 22.3, 19.2, 19.0, 13.9, 13.7. MS (MALDI-
FT): m/z 1417.8 [M + Na]+. HRMS (MALDI-FT): Calcd. for
C80H103N10O12: 1395.7752. Found: 1395.7771.
4 H), 1.80–1.70 (m, 8 H), 1.48–1.36 (m, 8 H), 1.02 (d, J = 6.9 Hz,
12 H), 0.99 (d, J = 7.2 Hz, 12 H), 0.92 (t, J = 7.5 Hz, 12 H). 13
C
NMR (CDCl3): d 162.4, 162.1, 160.0, 159.9, 147.7, 147.3, 138.0,
137.5, 128.8, 128.7, 127.3, 124.0, 121.7, 117.9, 116.5, 116.4, 111.9,
111.6, 97.5, 97.1, 77.2, 76.4, 76.3, 68.6, 54.5, 31.1, 31.0, 27.9, 27.8,
19.2, 19.1, 18.9, 13.8, 13.7. MS (MALDI-TOF): m/z 1389.5 [M +
Na]+. HRMS (MALDI-FT): Calcd. for C78H99N10O12: 1367.7438.
Found: 1367.7451.
Compound 9
A solution of 40 (0.41 g, 0.34 mmol) and TBAF (89 mg, 0.34 mmol)
in THF (35 mL) was stirred in an ice-bath for 30 min and
then concentrated. The resulting slurry was dissolved in CH2Cl2
(30 mL) and the solution washed with water (15 mL) and brine
(15 mL) and dried over sodium sulfate. The solvent was then
removed and the crude product subjected to flash chromatography
(CH2Cl2/EA 7:1 to 5:1) to give 9 as a pale yellow solid (0.34 g,
95%). 1H NMR (CDCl3): d 9.81 (s, 2 H), 9.46 (s, 2 H), 9.26 (s, 2 H),
8.46 (d, J = 1.5 Hz, 2 H), 8.26 (d, J = 7.5 Hz, 2 H), 7.56 (dd, J1 =
8.7 Hz, J2 = 1.5 Hz, 2 H), 7.38 (t, J = 7.5 Hz, 1 H), 6.97 (d, J =
8.4 Hz, 2 H), 6.56 (s, 2 H), 4.23 (t, J = 6.9 Hz, 4 H), 4.07 (s, 3 H),
3.83–3.79 (m, 8 H), 3.03 (s, 2 H), 2.17–2.07 (m, 4 H), 1.93–1.83
(m, 4 H), 1.51–1.44 (m, 4 H), 1.02 (d, J = 6.3 Hz, 24 H), 0.96 (t,
J = 7.5 Hz, 6 H). 13C NMR (CDCl3): d 162.4, 162.0, 156.7, 155.8,
146.4, 146.1, 136.4, 136.1, 134.8, 128.2, 125.1, 122.6, 120.5, 120.0,
116.8, 115.0, 112.8, 97.6, 82.6, 76.4, 75.7, 75.4, 69.4, 64.2, 30.7,
28.1, 28.1, 19.1, 19.1, 18.9, 13.6. MS (MALDI-TOF): m/z 1088.4
[M + Na]+.
Compound 7
Compound 7 was prepared as a white solid (90%) from the reaction
1
of 29 and 30 according to a procedure similar to that for 17. H
NMR (CDCl3): d 9.66 (s, 2 H), 9.02 (s, 1 H), 8.75 (d, J = 1.5 Hz,
2 H), 7.16 (dd, J1 = 8.4 Hz, J2 = 1.5 Hz, 2 H), 6.80 (d, J =
8.4 Hz, 2 H), 6.51 (s, 1 H), 4.07 (t, J = 6.9 Hz, 4 H), 4.01 (d, J =
6.6 Hz, 4 H), 2.97 (s, 2 H), 2.31–2.22 (m, 2 H), 1.83–1.73 (m, 4 H),
1.51–1.38 (m, 4 H), 1.04 (d, J = 6.9 Hz, 12 H), 0.96 (t, J = 7.5 Hz,
6 H). 13C NMR (CDCl3): d 162.5, 160.1, 148.3, 137.5, 128.3, 127.8,
124.8, 116.3, 114.4, 111.0, 97.2, 84.0, 76.3, 75.6, 68.6, 31.1, 28.0,
19.3, 19.1, 13.9. MS (MALDI-TOF): m/z 653.7 [M + H]+. Anal.
Calcd. for C40H48N2O6: C, 73.59; H, 7.41; N, 4.29. Found: C, 74.07;
H, 7.43; N, 4.19.
Compound 8
Compound 10
Compound 8 was prepared as a white solid (100%) from the
reaction of 36 and sodium azide according to a procedure similar
to that for 6. H NMR (CDCl3): d 9.75 (s, 2 H), 9.06 (s, 1 H),
Compound 10 was prepared quantitatively as a white solid from
the reaction of 47 and NaN3 according to a procedure similar to
1
1
8.60 (s, 2 H), 7.02 (J1 = 8.4 Hz, J2 = 1.8 Hz, 2 H), 6.91 (d, J =
8.4 Hz, 2 H), 6.56 (s, 1 H), 4.33 (s, 4 H), 4.09 (t, J = 6.9 Hz,
4 H), 4.02 (d, J = 6.9 Hz, 4 H), 2.34–2.25 (m, 2 H), 1.84–1.74
(m, 4 H), 1.53–1.40 (m, 4 H), 1.06 (d, J = 6.3 Hz, 12 H), 0.97 (t,
J = 7.5 Hz, 6 H). 13C NMR (CDCl3): d 162.5, 160.1, 147.7, 137.4,
128.7, 127.9, 123.4, 121.4, 116.7, 111.4, 97.3, 76.4, 68.7, 54.7, 31.2,
28.0, 19.3, 19.1, 13.8. MS (MALDI-TOF): m/z 715.4 [M + H]+.
HRMS (MALDI-FT): Calcd. for C38H51N8O6: 715.3926. Found:
715.3912. Anal. Calcd. for C38H50N8O6: C, 63.85; H, 7.05; N, 15.68.
Found: C, 63.50; H, 7.04; N, 15.63.
that for 6. H NMR (CDCl3): d 9.94 (s, 2 H), 9.48 (s, 2 H), 9.30
(s, 2 H), 8.28 (s, 2 H), 8.26 (d, J = 7.8 Hz, 2 H), 7.44–7.38 (m,
3 H), 7.05 (d, J = 8.7 Hz, 2 H), 6.56 (s, 2 H), 4.34 (s, 4 H), 4.23
(t, J = 6.6 Hz, 4 H), 4.06 (s, 3 H), 3.83–3.79 (m, 8 H), 2.17–2.11
(m, 4 H), 1.91–1.84 (m, 4 H), 1.51–1.44 (m, 4 H), 1.03 (d, J =
6.6 Hz, 12 H), 1.02 (d, J = 6.3 Hz, 12 H), 0.96 (t, J = 7.2 Hz,
6 H). 13C NMR (CDCl3): d 162.4, 162.3, 156.5, 155.7, 146.3, 146.0,
134.7, 132.5, 132.3, 128.2, 128.0, 125.0, 122.6, 120.6, 120.0, 116.8,
113.2, 97.6, 75.6, 75.3, 69.3, 64.1, 53.8, 30.7, 28.1, 28.1, 19.1, 19.0,
18.9, 13.6. MS (MALDI-FT): m/z 1149.6 [M + Na]+. HRMS
(MALDI-FT): Calcd. for C61H78N10O11Na [M + Na]+: 1149.5744.
Found: 1149.5745.
Compound 3
A suspension of 8 (0.49 g, 0.68 mmol), 7 (0.45 g, 0.68 mmol),
CuI (26 mg, 0.14 mmol) and DIPEA (0.26 mL, 1.30 mmol)
in CHCl3 (68 mL) and CH3CN (68 mL) was stirred for 24 h
and then concentrated. The resulting slurry was triturated with
CH2Cl2 (50 mL) and the solution washed with saturated NaHCO3
solution (25 mL), water (25 mL) and brine (25 mL) and dried over
sodium sulfate. Upon removal of the solvent, the crude product
was purified by flash chromatography (CH2Cl2/EA 2:3) to give 3
as a white solid (0.79 g, 85%). 1H NMR (CDCl3): d 9.93 (s, 2 H),
9.86 (s, 2 H), 9.23 (s, 1 H), 9.06 (s, 1 H), 8.90 (s, 2 H), 8.80 (s,
2 H), 8.02 (s, 2 H), 7.84 (d, J = 8.4 Hz, 2 H), 7.10 (d, J = 8.1 Hz,
2 H), 6.92 (d, J = 8.7 Hz, 2 H), 6.85 (d, J = 8.4 Hz, 2 H), 6.53 (s,
1 H), 6.51 (s, 1 H), 5.50 (s, 4 H), 4.08-3.98 (m, 16 H), 2.31–2.22 (m,
Compound 4
Compound 4 was prepared as a white solid (25%) from the reaction
of 9 and 10 according to a procedure similar to that for 3. 1H NMR
(CDCl3): d 10.00 (s, 2 H), 9.95 (s, 2 H), 9.48 (s, 2 H), 9.44 (s, 2 H),
9.39 (s, 2 H), 9.26 (s, 2 H), 8.45 (br, 4 H), 8.20 (br, 6 H), 7.87 (br,
2 H), 7.50 (d, J = 8.1 Hz, 2 H), 7.10 (d, J = 7.8 Hz, 2 H), 7.03 (d,
J = 8.4 Hz, 2 H), 6.55 (s, 2 H), 6.54 (s, 2 H), 5.55 (s, 4 H), 4.27–4.20
(m, 8 H), 3.56 (s, 3 H), 3.21 (s, 3 H), 2.14–2.09 (m, 8 H), 1.90–
1.85 (m, 8 H), 1.50–1.42 (m, 8 H), 1.02–0.92 (m, 60 H). 13C NMR
(CDCl3): d 162.8, 162.6, 162.5, 157.3, 156.6, 156.0, 156.0, 146.8,
146.1, 146.0, 135.2, 135.2, 133.3, 130.2, 130.0, 129.7, 128.4, 128.3,
127.5, 125.3, 124.0, 123.1, 122.9, 121.2, 120.8, 120.3, 120.1, 117.6,
This journal is
The Royal Society of Chemistry 2009
Org. Biomol. Chem., 2009, 7, 3243–3250 | 3249
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