10.1002/chem.201801540
Chemistry - A European Journal
FULL PAPER
anhydrous THF (6 mL). The mixture was stirred at 60°C for 12h
(overnight) under argon. The resulting anion was then transferred with a
canula to a solution of difluoro-BODIPY (1equiv) in anhydrous THF (6
mL). The solution was stirred at 60°C for 15 min under argon. Water was
added, and the solution was extracted with CH2Cl2 which contains MeOH.
The organic phase was washed with water (3), dried over MgSO4 and
evaporated under vacuum. The product was purified by silica gel
chromatography
a green compound (0.234 g, 99%). 1H NMR (300 MHz, CDCl3) δ (ppm):
8.14 (d, J=16.2 Hz, 2 H), 7.80 (d, J=8.2 Hz, 2 H), 7.55 (d, J=8.6 Hz, 4 H),
7.11 (d, J=16.1 Hz, 2 H), 7.09 (d, J=8.2 Hz, 2 H), 6.71 (d, J=8.6 Hz, 4 H),
6.61 (s, 2 H), 3.25 (s, 4 H), 3.02 (s, 12 H), 2.24 (s, 12 H), 1.43 (s, 6 H).
13C NMR (75 MHz, CDCl3) δ (ppm): 152.05, 150.53, 138.94, 137.82,
135.56, 134.89, 134.36, 130.89, 130.86, 128.71, 125.44, 117.62, 117.04,
111.97, 94.17, 89.38, 48.74, 43.75, 40.15, 14.98. ESI-HRMS, m/z calcd
for C47H53BIN6: 839.3472 [M+H]+; found: 839.3497 [M+H]+.
5a. Ethylmagnesiumbromide 1 M solution in THF (0.59 mL, 0.59 mmol),
3-dimethylamino-1-propyne (73 µL, 0.68 mmol), BODIPY 4a (74 mg, 0.13
mmol. Chromatography (from 98/2 to 94/6 CH2Cl2/MeOH) to afford a
purple compound (44.1 mg, 49%). 1H NMR (300 MHz, CDCl3) δ (ppm):
8.12 (d, J=16.2 Hz, 1 H), 7.85 (d, J=8.1 Hz, 2 H), 7.55 (s, 1 H), 7.34 (d,
J=8.6 Hz, 1 H), 7.10 (d, J=8.3 Hz, 2 H), 7.02 (d, J=16.4 Hz, 1 H), 6.90 (d,
J=8.5 Hz, 1 H), 6.60 (s, 1 H), 6.08 (s, 1 H), 3.37 (s, 2 H), 3.36 (s, 2 H),
2.78 (s, 3 H), 2.34 (s, 12 H), 1.47 (s, 3 H), 1.44 (s, 3 H). 13C NMR (75
MHz, CDCl3) δ (ppm): 155.65, 153.66, 151.60, 141.10, 140.39, 138.84,
138.25, 134.98, 132.53, 130.57, 130.33, 130.01, 127.90, 127.20, 122.01,
121.45, 117.90, 117.39, 94.64, 88.88, 48.55, 43.44, 16.42, 15.12, 14.95.
ESI-HRMS, m/z calcd for C36H38BClIN4O: 715.1873 [M+H]+; found:
715.1798 [M+H]+.
General procedure C: carboxylation of the styryl BODIPY
derivatives.
To a solution of 8-(4-iodophenyl)-BODIPY derivative (1 eq., 0.2 mmol) in
absolute ethanol (10 mL) and triethylamine (10 mL) was added
Pd(PPh3)2Cl2 (5%mol, 0.01 mmol). The resulting mixture was stirred at
70°C for 12h (night) under a slow bubbling CO gas flux. The crude
product was washed with water (3) and extracted with CH2Cl2. Organics
layers were dried over Na2SO4 and evaporated under vacuum. The
product was purified by silica gel chromatography.
6a. Compound 5a (39.6 mg, 0.05 mmol), Pd(PPh3)2Cl2 (2.3 mg, 0.003
mmol). Chromatography (from 96/3/1 to 94/5/1 CH2Cl2/MeOH/Et3N) to
afford a purple compound (35.4 mg, 97%). 1H NMR (200 MHz, CDCl3) δ
ppm: 8.19 (d, J=8.0 Hz, 2 H), 8.04 (d, J=15.8 Hz, 1 H), 7.40-7.60 (m, 4 H),
7.18 (d, J=8.5 Hz, 1 H), 7.05 (d, J=16.2 Hz, 1 H), 6.60 (s, 1 H), 6.07 (s, 1
H), 4.44 (q, J=7.1 Hz, 2 H), 3.53 (s, 4 H), 2.76 (s, 3 H), 2.45 (s, 12 H),
1.31-1.55 (m, 9 H). ESI-HRMS, m/z calcd for C39H43BClN4O3: 661.3118
[M+H]+; found: 661.3138 [M+H]+.
5b. Ethylmagnesiumbromide
1 M in THF (1 mL, 1.0 mmol), 3-
dimethylamino-1-propyne (125.7 µL, 1.17 mmol), BODIPY 4b[26] (0.2 g,
0.29 mmol). Chromatography (from 96/4 to 92/8 CH2Cl2/MeOH) to afford
a green compound (0.21 g, 88%) 1H NMR (300 MHz, CDCl3) δ (ppm):
8.09 (2d, J=16.0 Hz, 2 H), 7.84 (d, 7.9 Hz, 2 H), 7.51 (2d, J=8.3 Hz,
J=8.2 Hz, 4 H), 7.06-7.21 (m, 4 H), 6.80 (d, J=8.3 Hz, 2 H), 6.69 (d, J=8.9
Hz, 2 H), 6.65 (s, 1 H), 6.61 (s, 1 H), 3.35 (s, 4 H), 3.04 (s, 6 H), 2.29 (s,
12 H), 1.47 (2s, 6 H). 13C NMR (75 MHz, CDCl3) δ (ppm): 158.81, 153.02,
151.26, 150.90, 140.13, 139.11, 138.06, 135.66, 135.41, 133.83, 131.32,
130.85, 128.94, 128.88, 128.57, 125.02, 118.53, 118.14, 117.63, 116.35,
112.08, 94.44, 48.50, 43.33, 40.23, 15.19, 15.09. ESI-HRMS, m/z calcd
for C45H48BIN5O: 812.2999 [M+H]+; found: 812.2970 [M+H]+.
6b. Compound 5b (146.0 mg, 0.18 mmol) Pd(PPh3)2Cl2 (7.6 mg, 0.01
mmol). Chromatography (from 100/0 to 90/10 CH2Cl2/MeOH) to afford a
green compound (87.4 mg, 64%). 1H NMR (300 MHz, CDCl3) δ (ppm):
8.18 (d, J=7.9 Hz, 2 H), 8.08 (2d, J=16.9 Hz, J=16.5 Hz, 2 H), 7.49 (2d,
J=9.6 Hz, J=8.6 Hz, 6 H), 7.16 (d, J=16.2 Hz, 1 H), 7.11 (d, J=16.2 Hz, 1
H), 6.84 (d, J=8.3 Hz, 2 H), 6.69 (d, J=8.9 Hz, 2 H), 6.65 (s, 1 H), 6.61 (s,
1 H), 4.43 (q, J=7.1 Hz, 2 H), 3.37 (s, 2 H), 3.35 (s, 2 H), 3.04 (s, 6 H),
2.31 (s, 12 H), 1.44 (t, J=7.2 Hz, 6 H), 1.41 (s, 3 H).13C NMR (75 MHz,
CDCl3) δ (ppm): 166.15, 159.00, 153.15, 151.24, 150.96, 140.58, 140.18,
139.08, 135.90, 135.78, 133.98, 131.14, 130.85, 130.57, 130.06, 129.19,
128.95, 128.89, 128.45, 124.95, 118.40, 118.20, 117.66, 116.42, 116.31,
112.13, 88.04, 61.31, 48.50, 43.25, 40.22, 15.04, 14.92, 14.30. ESI-
HRMS, m/z for calcd C48H53BN5O3: 758.4244 [M+H]+; found: 758.4251
[M+H]+.
5c. Ethylmagnesiumbromide 1 M in THF (0.85 mL, 0.86 mmol), 3-
dimethylamino-1-propyne (0.105 mL, 0.98 mmol), BODIPY 4c (0.200 g,
0.24 mmol) Chromatography (from 98/2/0 to 94/6/1 CH2Cl2/MeOH/Et3N)
to afford a green compound (0.192 mg, 83%). 1H NMR (300 MHz, CDCl3)
δ (ppm): 8.22 (d, J=16.3 Hz, 2 H), 7.83 (d, J=8.2 Hz, 2 H), 7.19 (d, J=8.2
Hz, 2 H), 7.11-7.16 (m, 4 H), 7.10 (s, 2 H), 6.90 (d, J=8.2 Hz, 2 H), 6.63
(s, 2 H), 3.93 (s, 6 H), 3.24 (q, J=7.1 Hz, 8 H), 3.20 (s, 4 H), 2.16 (s, 12
H), 1.45 (s, 6 H), 1.08 (t, J=7.1 Hz, 12 H). 13C NMR (75 MHz, CDCl3) δ
(ppm): 152.96, 151.98, 140.35, 139.53, 138.01, 136.14, 135.41, 134.19,
131.24, 131.15, 130.75, 120.56, 120.41, 119.46, 118.00, 110.14, 94.38,
89.99, 55.29, 48.85, 45.88, 43.92, 15.09, 12.14. ESI-HRMS, m/z calcd
for C53H65BIN6O2: 955.4310 [M+H]+; found: 955.4445 [M+H]+.
6c. General procedure C: 5c (52.7 mg, 0.06 mmol), Pd(PPh3)2Cl2 (2.3
mg, 0.003 mmol). Chromatography (from 99/0.5/0.5 to 97/2.5/0.5
CH2Cl2/MeOH/Et3N) to afford a green compound (48.9 mg, 98%). 1H
NMR (200 MHz, CDCl3) δ (ppm): 8.16 (2d, J=16.8 Hz, J=7.4 Hz, 4 H),
7.48 (d, J=8.0 Hz, 2 H), 7.14-7.25 (m, 4 H), 7.09 (s, 2 H), 6.91 (d, J=8.4
Hz, 2 H), 6.64 (s, 2 H), 4.44 (q, J=7.0 Hz, 2 H), 3.93 (s, 6 H), 3.15-3.35
5d. Ethylmagnesiumbromide 1 M in THF (0.90 mL, 0.91 mmol), 3-
dimethylamino-1-propyne (0.11 mL, 1.04 mmol) BODIPY 4d (0.20 g, 0.26
mmol) Chromatography (from 98/2 to 94/6 CH2Cl2/MeOH) to afford a
green compound (0.218 g, 95%). 1H NMR (200 MHz, CDCl3) δ (ppm):
8.22 (d, J=16.3 Hz, 2 H), 7.83 (d, J=8.0 Hz, 2 H), 7.06-7.25 (m, 8 H), 6.90
(d, J=8.1 Hz, 2 H), 6.64 (s, 2 H), 3.97 (s, 6 H), 3.20 (s, 4 H), 2.86 (s, 12
H), 2.17 (s, 12 H), 1.45 (s, 6 H). 13C NMR (75 MHz, CDCl3) δ (ppm):
152.00, 143.31, 139.60, 138.05, 136.30, 135.41, 134.11, 131.28, 131.25,
130.75, 121.07, 119.50, 118.03, 117.71, 109.63, 94.40, 90.03, 55.21,
48.88, 43.97, 43.07, 15.09. ESI-HRMS, m/z calcd for C49H57BIN6O2:
899.3684 [M+H]+; found: 899.3663 [M+H]+.
(m, 12 H), 2.23 (s, 12 H), 1.35-1.52 (m, 9 H), 1.08 (t, J=6.9 Hz, 12 H). 13
C
NMR (50 MHz, CDCl3) δ (ppm): 166.03, 152.72, 151.96, 140.29, 140.10,
135.28, 132.19, 131.99, 131.94, 131.89, 131.08, 130.17, 129.01, 128.60,
128.35, 120.27, 119.73, 118.27, 111.57, 61.40, 55.70, 48.12, 45.84,
42.28, 29.66, 15.03, 14.32, 12.40. ESI-HRMS, m/z calcd for
C56H70BN6O4: 901.5555 [M+H]+; found: 901.5587 [M+H]+.
6d. Compound 5d (81.3 mg, 0.09 mmol), Pd(PPh3)2Cl2 (3.8 mg, 0.005
mmol). Chromatography (from 98/2 to 94/6 CH2Cl2/MeOH/Et3N) to afford
a green compound (72.1 mg, 94%). 1H NMR (400 MHz, CDCl3) δ (ppm):
8.18 (2d, J=16.4 Hz, J=8.1 Hz, 4 H), 7.48 (d, J=8.2 Hz, 2 H), 7.20 (d,
J=8.2 Hz, 2 H), 7.14 (d, J=16.2 Hz, 2 H), 7.12 (s, 2 H), 6.90 (d, J=8.2 Hz,
2 H), 6.64 (s, 2 H), 4.44 (q, J=7.1 Hz, 2 H), 3.96 (s, 6 H), 3.27 (s, 4 H),
5e. Ethylmagnesiumbromide 1 M in THF (0.67 mL, 0.68 mmol), 3-
dimethylamino-1-propyne (0.10 mL, 0.90 mmol), BODIPY 4e (0.20 g,
0.28 mmol). Chromatography (from 98/2 to 92/8 CH2Cl2/MeOH) to afford
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