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fied through column chromatography over silica (eluent: CH2Cl2/
rated. The crude product was purified through column chromatog-
raphy over silica with petroleum ether/CH2Cl2 (1:2) as the eluent to
give 3e as a yellow solid (36 mg, yield: 56%). 1H NMR (600 MHz,
CDCl3): d=8.40 (d, J=15.0 Hz, 1H), 8.04 (d, J=7.2 Hz, 2H), 7.96 (t,
J=15.0 Hz, 1H), 7.56 (t, J=7.8 Hz, 1H), 7.47 (t, J=7.8 Hz, 2H), 7.34
(t, J=7.8 Hz, 2H), 7.32 (d, J=9.0 Hz, 1H), 7.11 (t, J=7.8 Hz, 1H),
7.02 (d, J=7.8 Hz, 2H), 6.55 (d, J=2.4 Hz, 1H), 6.51 (dd, J1 =9.0,
J2 =2.4 Hz, 1H), 3.47 (q, J=7.2 Hz, 4H), 1.24 ppm (t, J=7.2 Hz, 6H);
13C NMR (CDCl3, 150 MHz): 193.7, 166.3, 164.4, 160.5, 159.3, 154.9,
141.3, 136.1, 135.3, 133.0, 131.5, 131.3, 129.2, 127.2, 126.2, 118.6,
112.3, 110.2, 107.5, 99.9, 47.9, 15.3 ppm; HRMS: m/z calcd for
C28H25NO4: 440.1856 [M+H]+; found: 440.1857.
petroleum ether, 2:1) to give 3a as a yellow solid (58 mg, yield:
1
20%). H NMR (600 MHz, CDCl3): d=8.24 (d, J=15.0 Hz, 1H), 8.09
(d, J=6.6 Hz, 2H), 7.79 (s, 1H), 7.64 (d, J=15.0 Hz, 1H), 7.56 (t, J=
7.2 Hz, 1H), 7.49 (t, J=7.8 Hz, 2H), 7.33 (d, J=9.0 Hz, 1H), 6.62 (dd,
J1 =8.4, J2 =2.4 Hz, 1H), 6.52 (d, J=2.4 Hz, 1H), 3.45 (q, J=7.2 Hz,
4H), 1.24 ppm (t, J=7.2 Hz, 6H); 13C NMR (CDCl3, 150 MHz):193.6,
163.0, 159.5, 154.8, 148.9, 142.6, 141.3, 135.4, 132.8, 131.5, 131.4,
126.0, 118.1, 112.4, 111.9, 99.9, 47.9, 15.3 ppm; HRMS: m/z calcd for
C22H21NO3: 348.1594 [M+H]+; found: 348.1598.
Synthesis of 3b: 4-Chloro-7-diethylaminocoumarin-3-aldehyde
(1b, 2.331 g, 8.34 mmol) and 1-phenyl-2-(triphenylphosphoranyli-
dene)ethanone (2, 4.119 g, 10.84 mmol) were dissolved in dichloro-
methane (50 mL). The mixture was stirred under an N2 atmosphere
at room temperature overnight, and then evaporated. The crude
product was purified through column chromatography over silica
(eluent: CH2Cl2/petroleum ether, 5:1) to give 3b as a red solid
(2.41 g, yield: 76%). 1H NMR (600 MHz, CDCl3): d=8.49 (d, J=
15.0 Hz, 1H), 8.18 (d, J=15.0 Hz, 1H), 8.10 (t, J=7.2 Hz, 2H), 7.76–
7.75 (q, 1H), 7.58 (t, J=7.2 Hz, 1H), 7.50 (t, J=7.2 Hz, 2H), 6.70 (dd,
J1 =9.0 Hz, J2 =2.4 Hz, 1H), 6.51 (s, 1H), 3.47 (q, J=7.2 Hz, 4H),
1.25 ppm (t, J=7.2 Hz, 6H); 13C NMR (CDCl3, 150 MHz):193.6, 161.7,
157.5, 155.0, 154.0, 141.2, 138.3, 135.6, 131.5, 131.4, 130.9, 128.7,
115.8, 113.0, 111.0, 99.7, 48.1, 15.3 ppm; HRMS: m/z calcd for
C22H20ClNO3: 382.1204 [M+H]+; found: 382.1199.
Synthesis of probe 3 f: Compound 3b (300 mg, 0.79 mmol), 3,4-di-
methoxythiophenol (267.6 mg, 1.57 mmol), and triethylamine
(220 mL, 1.57 mmol) were dissolved in acetonitrile (20 mL). The mix-
ture was stirred at room temperature for 2 h, and then evaporated.
The crude product was purified through column chromatography
1
over silica to give 3 f as a red solid (232 mg, yield : 57%). H NMR
(600 MHz, CDCl3): d=8.50 (d, J=15.6 Hz, 1H), 8.31 (d, J=15.0 Hz,
1H), 8.04 (d, J=7.2 Hz, 2H), 7.96 (d, J=9.6 Hz, 1H), 7.55 (t, J=
7.2 Hz, 1H), 7.47 (t, J=7.2 Hz, 2H), 6.94 (d, J=2.4 Hz, 1H), 6.90 (dd,
J1 =8.4, J2 =1.8 Hz, 1H), 6.70 (d, J=8.4 Hz, 1H), 6.58 (d, J=9.0 Hz,
1H), 6.49 (s, 1H), 3.82 (s, 3H), 3.78 (s, 3H), 3.44 (q, J=7.2 Hz, 4H),
1.23 ppm (t, J=7.2 Hz, 6H); 13C NMR (CDCl3, 150 MHz): 193.6,
162.1, 158.0, 157.0, 154.5, 152.4, 152.0, 141.2, 135.3, 132.4, 131.4,
131.3, 128.3, 128.2, 126.9, 120.5, 117.3, 114.9, 113.3, 112.4, 99.8,
59.0, 58.8, 47.8, 15.4 ppm; HRMS: m/z calcd for C30H29NO5S:
516.1839 [M+H]+; found: 516.1841.
Synthesis of 3c: Compound 3b (133 mg, 0.35 mmol) and n-BuNH2
(76.62 mg, 1.05 mmol) were dissolved in anhydrous DMF (10 mL) in
a 50 mL round bottom flask. The mixture was stirred at 60–708C
for 2 h. The solvent was removed by rotary evaporation and the
residue was purified by chromatography on silica gel with EtOAc/
petroleum ether (1:2) as the eluent to give 3c as a yellow solid
(91 mg, 64% yield). 1H NMR (600 MHz, CDCl3): d=8.21 (d, J=
15.0 Hz, 1H), 8.10 (d, J=7.2 Hz, 2H), 8.04 (d, J=15.0 Hz, 1H), 7.53
(d, J=7.2 Hz, 1H), 7.48–7.46 (m, 3H), 6.56 (dd, J1 =9.0, J2 =3.0 Hz,
1H), 6.46 (d, J=3.0 Hz, 1H), 5.35 (t, 1H), 3.71 (dd, J1 =12.6, J2 =
7.2 Hz, 2H), 3.41 (q, J=7.2 Hz, 4H), 1.74–1.70 (m, 2H), 1.46–1.40
(m, 2H), 1.21 (t, J=7.2 Hz, 6H), 0.94 ppm (t, J=7.2 Hz, 3H);
13C NMR (CDCl3, 150 MHz): 191.1, 161.5, 157.2, 155.4, 151.4, 139.2,
137.7, 132.2, 128.6, 128.5, 123.7, 119.6, 108.6, 103.6, 98.0, 94.2, 49.5,
44.9, 33.5, 20.0, 13.8, 12.6 ppm; HRMS: m/z calcd for C26H30N2O3:
413.2329 [M+H]+; found: 413.2337.
Synthesis of probe 3g: [PdCl2(PPh3)2] (16 mg, 0.0228 mmol), CuI
(8.7 mg, 0.0456 mmol), and phenylacetylene (60 mL, 0.2736 mmol)
were added to a solution of 3b (174 mg, 0.456 mmol) in dry THF
(10 mL) and Et3N (0.5 mL) under argon. The resulting solution was
heated at reflux overnight. The mixture was then cooled, diluted
with water, and extracted with CH2Cl2. The organic fractions were
then combined and dried over anhydrous Na2SO4. Removal of sol-
vent in vacuo and purification of the residue by column chroma-
tography on silica gel with dichloromethane/petroleum ether (4:1)
1
as the eluent to give 3g as a red solid (132 mg, 64.7%). H NMR
([D6]DMSO, 600 MHz): d=8.27 (d, J=15.0 Hz, 1H), 8.19 (d, J=
15.0 Hz, 1H), 7.98 (d, J=7.2 Hz, 2H), 7.83 (d, J=9.0 Hz, 1H), 7.73
(d, J=7.8 Hz, 2H), 7.69 (t, J=7.2 Hz, 1H), 7.62 (m, 5H), 6.85 (d, J=
9.0 Hz, 1H), 6.60 (s, 1H), 3.50 (q, J=6.6 Hz, 4H), 1.17 ppm (t, J=
6.6 Hz, 6H); 13C NMR ([D6]DMSO, 150 MHz): 193.3, 162.1, 158.7,
155.4, 141.6, 141.4, 140.7, 136.2, 135.4, 134.3, 132.5, 132.4, 132.2,
131.4, 126.7, 123.7, 117.3, 113.7, 111.3, 111.3, 99.7, 85.8, 47.8,
15.7 ppm; HRMS: m/z calcd for C30H25NO3: 448.1907 [M+H]+;
found: 448.1906.
Synthesis of 3d: Compound 3b (120 mg, 0.23 mmol), ethanethiol
(29 mg, 0.466 mmol), and triethylamine (320 mL, 2.33 mmol) were
dissolved in acetonitrile (15 mL). The mixture was stirred at room
temperature for 15 min, and then evaporated. The crude product
was purified through column chromatography over silica with pe-
troleum ether/EtOAc (5:1) as the eluent to give 3d as a red solid
(32 mg, yield : 25%). 1H NMR (600 MHz, CDCl3): d=8.44 (s, 2H),
8.11 (d, J=6.6 Hz, 2H), 8.01 (d, J=9.0 Hz, 1H), 7.56 (t, J=7.2 Hz,
1H), 7.49 (t, J=7.2 Hz, 2H), 6.64 (dd, J1 =9.0, J2 =2.4 Hz, 1H), 6.48
(d, J=2.4 Hz, 1H), 3.45 (q, J=7.2 Hz, 4H), 2.96 (q, J=7.2 Hz, 2H),
1.27 (t, J=7.2 Hz, 3H), 1.24 ppm (t, J=7.2 Hz, 6H); 13C NMR (CDCl3,
150 MHz): 193.8, 162.0, 158.8, 157.7, 154.7, 141.4, 141.4, 135.4,
132.3,131.5, 131.3, 127.8, 120.7, 114.1, 112.3, 99.8, 47.8, 34.6, 18.0,
15.4 ppm; HRMS: m/z calcd for C24H25NO3S: 408.1628 [M+H]+;
found: 408.1634.
Synthesis of probe 3h: [Pd(PPh3)4] (22.7 mg, 0.02 mmol), Na2CO3
(209 mg, 2 mmol), and 4-acetylphenylboronic acid (77.5 mg,
0.48 mmol) were added to a solution of 3b (151 mg, 0.4 mmol) in
THF (10 mL) and H2O (3 mL) under argon. The resulting solution
was heated at reflux overnight. The mixture was then cooled, dilut-
ed with water, and extracted with CH2Cl2. The organic fractions
were then combined and dried over anhydrous Na2SO4. Removal
of solvent in vacuo and purification of the residue by column chro-
matography on silica gel with dichloromethane/methanol (10:0.05)
1
as the eluent to give 3h as a red solid (104 mg, 57.5%). H NMR
(CDCl3, 600 MHz): d=8.43 (d, J=15.6 Hz, 1H), 8.14 (d, J=7.8 Hz,
2H), 8.02 (d, J=7.2 Hz, 2H), 7.55 (t, J=7.2 Hz, 1H), 7.46 (m, 2H),
7.42 (d, J=8.4 Hz, 2H), 7.36 (d, J=15.0 Hz, 1H), 6.81 (d, 9.0 Hz,
Synthesis of 3e: A mixture of 3b (60 mg, 0.16 mmol), phenol
(74 mg, 0.78 mmol), sodium hydride (3.8 mg, 0.16 mmol), and DMF
(10 mL) was stirred at room temperature for 2 h, and then evapo-
Chem. Eur. J. 2015, 21, 4747 – 4754
4752
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim