1
the pure product as a pale white solid (0.31 g, 47%); H NMR
3J = 8.5 Hz, ArH), 7.41 (2H, s, -NH-), 7.27–7.05 (26H, m, ArH),
6.67 (4H, d, 3J = 8.8 Hz, ArH), 4.36 (3H, s, -NCH3), 4.31 (4H, m,
-CH2-), 3.90 (4H, m, -CH2-), 3.73 (8H, m, -CH2-), 1.26 (36H, s,
tBu); 13C NMR (125 MHz, CDCl3, 298 K): d 158.2, 155.9, 153.5,
148.4, 147.2, 146.4, 143.7, 142.3, 135.6, 134.0, 131.7, 131.1, 130.6,
127.3, 125.7, 124.2, 122.3, 117.6, 114.5, 110.0, 69.8, 69.6, 64.7,
64.1, 63.6, 49.2, 43.3, 31.4; 19F NMR (282 MHz, CDCl3, 298 K):
d -148.42; ESI-MS (m/z): [M - BF4]+ 1486.7782, C96H104N5O10
(calc. 1487.7778).
(300 MHz, DMSO-d6, 298 K): d 10.49 (2H, s, -NH-), 9.23 (2H,
d, J = 1.8 Hz, ArH), 8.79 (1H, t, J1 = 2.1 Hz, J2 = 3.7 Hz
4
4
4
3
3
ArH), 7.69 (4H, d, J = 9.1 Hz, ArH), 6.97 (4H, d, J = 9.1 Hz,
ArH), 4.65 (4H, t, -OH-), 4.10–4.07 (4H, m, -CH2-), 3.76–3.73
(4H, m, -CH2-), 3.52–3.49 (8H, m, -CH2-); 13C NMR (75 MHz,
DMSO-d6, 298 K): d 163.4, 155.5, 151.2, 134.9, 132.3, 130.7, 122.4,
114.9, 72.9, 69.4, 67.7, 60.7; ESI-MS (m/z): [M + Na]+ 548.2004,
C27H31N3O8Na (calc. 548.2003).
Synthesis of 3-I. Compound 8 (0.30 g, 0.57 mmol) was
dissolved in excess iodomethane (5 mL) and acetone (20 mL)
and was refluxed under N2 for 48 h. After this time, diethyl ether
(50 mL) was added and the filtration was isolated to give the pure
Synthesis of 4-Cl. A solution of 4-BF4 (0.260 g, 0.165 mmol)
in chloroform (50 mL) was washed with saturated NH4Cl(aq)
(5 ¥ 50 mL). The organic phase was dried over magnesium sulfate,
filtered and the solvent removed in vacuo to give the pure product as
a yellow solid (0.250 g, 99%); 1H NMR (500 MHz, CDCl3, 298 K):
d 11.82 (4H, s, -NH-), 10.44 (1H, s, ArH), 9.15 (2H, s, ArH), 7.85
(4H, d, 3J = 8.5 Hz, ArH), 7.24–7.07 (26H, m, ArH), 6.85 (4H, d,
3J = 9.1 Hz, ArH), 4.37 (3H, s, -CH3-), 4.34–4.32 (4H, m, -CH2-),
4.07–4.05 (4H, m, -CH2-), 3.83–3.81 (4H, m, -CH2-), 3.79–3.77
(4H, m, -CH2-), 1.24 (36H, s, tBu); 13C NMR (125 MHz, CDCl3,
298 K): d 207.0, 158.6, 155.8, 153.5, 148.4, 147.2, 146.1, 143.7,
142.3, 135.5, 135.1, 131.7, 131.4, 131.1, 130.6, 127.3, 125.7, 124.2,
122.5, 117.5, 114.5, 69.6, 67.5, 64.1, 63.6, 48.9, 34.3, 31.3; ESI-MS
(m/z): [M - Cl]+ 1487.7320, C96H105N5O10 (calc. 1487.7856).
1
product as a yellow solid (0.35 g, 92%); H NMR (300 MHz,
DMSO-d6, 298 K): d 11.09 (2H, s, -NH-), 9.68 (2H, s, ArH),
3
9.23 (1H, s, ArH), 7.77 (4H, d, J = 9.1 Hz, ArH), 7.02 (4H, d,
3J = 9.1 Hz, ArH), 4.65 (2H, t, -OH-), 4.49 (3H, s, -CH3-), 4.12–
4.09 (4H, m, -CH2-), 3.76–3.73 (4H, m, -CH2-), 3.53–3.48 (8H, m,
-CH2-); 13C NMR (125 MHz, CD3OD, 298 K): d 160.7, 157.7,
148.3, 142.7, 133.5, 132.1, 123.7, 115.8, 73.8, 70.7, 68.9, 62.2, 49.9;
ESI-MS (m/z): [M - I]+ 540.2354, C28H34N3O8 (calc. 540.2340).
Synthesis of 3-Cl. A solution of 3-I (0.35 g, 0.52 mmol) in
2 : 1 MeOH/MeCN (20 mL) was run through a chloride activated
amberlite column using the same solvent as the eluent to give the
Synthesis of 11-Cl by clipping method. 2 (0.0670 g, 0.103 mmol)
and 4-Cl (0.156 g, 0.103 mmol) were dissolved in dry
dichloromethane (20 mL) and stirred under N2 for 30 min. Grubbs’
catalyst 2nd generation (5 mg) was then added and the mixture
was stirred for 48 h. The solvent was removed in vacuo and
the residue was purified by column chromatography using 96 : 4
CH2Cl2/MeOH as the eluent to give the pure product as a yellow
solid (0.121 g, 55%).
1
pure product as a bright yellow solid (0.30 g, 99%); H NMR
(300 MHz, DMSO-d6, 298 K): d 11.25 (2H, s, -NH-), 9.84 (1H, s,
ArH), 9.70 (2H, s, ArH), 7.82 (4H, d, 3J = 9.1 Hz, ArH), 7.01 (4H,
d, 3J = 9.1 Hz, ArH), 4.66 (2H, t, -OH), 4.49 (3H, s, -CH3-), 4.12–
4.09 (4H, m, -CH2-), 3.76–3.73 (4H, m, -CH2-), 3.53–3.48 (8H,
m, -CH2-); 13C NMR (75 MHz, CD3OD, 298 K): d 160.5, 157.6,
148.3, 142.4, 135.6, 132.2, 123.5, 115.7, 73.8, 70.7, 68.9, 62.2, 49.7;
ESI-MS (m/z): [M - Cl]+ 540.2343, C28H34N3O8 (calc. 540.2340).
Synthesis of 11-Cl by stoppering method. A solution of 2
(0.0617 g, 0.0993 mmol) and 3-Cl (0.0572 g, 0.0993 mmol) in
1 : 1 CH2Cl2/MeCN (20 mL) was stirred under N2 for one hour.
Isocyanate stopper 9 (0.0943 g, 0.199 mmol) and dibutyltin
dilaurate (Sn catalyst) (0.0630 g, 0.0995 mmol) were then added
and the mixture was stirred under N2 for 72 h. After this time
the solvent was removed in vacuo and the residue was purified by
column chromatography column using 25 : 1 CH2Cl2/MeOH as
the eluent to give the pure product as a yellow solid (44.7 mg,
21%); 1H NMR (500 MHz, CDCl3, 298 K): d 10.08 (2H, s, -NH-),
9.93 (1H, s, ArH), 9.12 (1H, s, NO2-ArH), 8.99 (2H, s, NO2-ArH),
Synthesis of 10. A solution of isocyanate stopper 9 (0.990
g, 2.09 mmol), pyridyl thread 8 (0.501 g, 0.950 mmol) and
dibutyltin dilaurate (Sn catalyst) (0.198 g, 0.310 mmol) in 1 : 1
CH2Cl2/MeCN (150 mL) was stirred under N2 for 72 h. The
solvent was then removed in vacuo and the residue was purified
by column chromatography using ethyl acetate as the eluent to
1
give the pure product as a yellow solid (1.02 g, 73%); H NMR
(500 MHz, CDCl3, 298 K): d 9.12 (4H, s, -NH-), 8.44 (1H,
s, ArH), 7.56 (2H, s, ArH), 7.37 (4H, d, 3J = 8.3 Hz, ArH),
3
7.27–7.08 (26H, m, ArH), 6.62 (4H, d, J = 8.8 Hz, ArH), 4.28
3
(4H, m, -CH2-), 3.91 (4H, m, -CH2-), 3.74 (8H, m, -CH2-), 1.25
8.97 (2H, s, ArH), 8.56 (2H, s, -NH-), 7.71 (4H, d, J = 8.8 Hz,
(36H, s, Bu); 13C NMR (125 MHz, CDCl3, 298 K): d 163.3,
ArH), 7.32–7.09 (34H, m, ArH), 6.75 (4H, d, 3J = 9.3 Hz, ArH),
t
3
155.6, 153.5, 150.3, 148.4, 147.1, 143.7, 142.2, 135.6, 134.4, 131.7,
131.7, 131.0, 130.6, 130.1, 127.3, 125.7, 124.2, 122.7, 117.5, 114.5,
69.6, 69.4, 67.3, 63.7, 63.6, 34.2, 31.3; ESI-MS (m/z): [M + Na]+
1494.7449, C95H101N5O10Na (calc. 1494.7441).
6.45 (4H, d, J = 8.8 Hz, ArH), 6.18–6.17 (2H, m, CH CH),
3
6.15 (4H, d, J = 8.8 Hz, ArH), 4.49 (3H, s, -CH3), 4.37–4.35
(4H, m, -CH2-), 4.25–4.23 (4H, m, -CH2-), 4.14–4.13 (4H, m,
-CH2-), 4.00–3.99 (4H, m, -CH2-), 3.83–3.77 (20H, m, -CH2-),
1.26 (36H, s, -CH3); 13C NMR (125 MHz, CDCl3, 298 K): d 164.3,
158.3, 156.7, 153.5, 153.3, 152.0, 148.5, 148.3, 147.1, 145.4, 143.7,
142.2, 136.9, 135.6, 135.1, 133.5, 131.7, 131.1, 130.6, 129.7, 129.0,
127.2, 125.9, 125.6, 124.1, 117.5, 115.5, 115.2, 114.8, 114.5, 114.4,
70.8, 69.7, 69.5, 69.4, 68.1, 67.6, 65.0, 64.2, 63.6, 49.2, 41.4, 34.2,
31.3; ESI-MS (m/z): [M - Cl]+ 2109.0201, C128H140N8O20 (calc.
2109.0133).
Synthesis of 4-BF4. Pyridine stoppered thread 10 (0.265 g,
0.180 mmol) and trimethyloxonium tetrafluoroborate (0.040 g,
0.270 mmol) were dissolved in dry dichloromethane and stirred
under N2 for 48 h. After this time, methanol (10 mL) was added
to the reaction mixture and the solvent was removed in vacuo.
The residue was purified by column chromatography using 10 : 1
CH2Cl2/MeOH as the eluent to give the pure product as a yellow
solid (0.260 g, 92%); 1H NMR (300 MHz, CDCl3, 298 K): d 10.53
(2H, s, -NH-), 9.94 (1H, s, ArH), 9.14 (2H, s, ArH), 7.70 (4H, d,
Synthesis of 11-PF6. A solution of 11-Cl (0.085 g, 0.040 mmol)
in chloroform (5 mL) was washed with 0.1 M NH4PF6(aq)
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 12180–12190 | 12189
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