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mmol, 64.2 mg, 4 equiv), and aqueous K2CO3 (86.5 mg, 0.626 mmol,
5 equiv) in toluene (10 mL). Column chromatography on silica gel
eluting with petroleum ether/CH2Cl2 4:6 to 1:9 as eluant to give
compound 8 as a yellow powder (13.9 mg, 31%): mp 209−210 °C; IR
(ATR) ν in cm−1 3097 (w), 3058 (w), 2923 (m), 1613 (m), 1563 (s),
mL). Column chromatography on silica gel eluting with petroleum
ether/CH2Cl2 8:2 to 5:5 as eluant to give compound 12 as a pale
yellow powder (43.7 mg, 90%): mp 218−219 °C; IR (ATR) ν in cm−1
2924 (w), 2857 (w), 1612 (m), 1563 (s), 1511 (s), 1435 (m), 1390
1
(s), 1209 (m), 1055 (m), 810 (s); H NMR (200 MHz, CDCl3) δ =
1
8.41 (d, 1H, 3J = 2.2 Hz), 7.41 (d, 1H, 3J = 2.2 Hz), 7.28 (AB sys, 4H,
JAB = 7.9 Hz, υoδ = 56.1 Hz), 3.23 (s, 12H), 2.36 (s, 3H), 2.29 (s, 3H);
13C NMR (CDCl3, 50 MHz) δ = 169.4, 163.4, 160.6, 137.7, 136.8,
131.3, 130.4, 129.0, 126.6, 120.8, 117.8, 112.5, 89.4, 87.2, 36.4, 21.5,
15.9; EI-MS, m/z (%) 387.1 (100). Anal. Calcd for C23H25N5O: C,
71.29; H, 6.50; N, 18.07. Found: C, 70.92; H, 6.32; N, 17.80.
1510 (s), 1434 (m), 1384 (s), 1210 (m), 1054 (m), 807 (m); H
NMR (300 MHz, CDCl3) δ =15.0 (s, 1H), 8.51 (d, 1H, 3J = 2.4 Hz),
7.50 (d, 1H, 3J = 2.4 Hz), 7.24 (m, 2H), 6.79 (dd, 1H, 3J = 5.2 Hz, 4J =
3.4 Hz), 3.22 (s, 12H), 2.34 (s, 3H); 13C NMR (CDCl3, 75 MHz) δ =
169.3, 163.1, 159.9, 144.9, 132.1, 127.8, 126.9, 124.5, 123.4, 121.8,
117.6, 36.5, 16.1; EI-MS, m/z (%) 356.1 (100). Anal. Calcd for
C18H21N5OS: C, 60.82; H, 5.95; N, 19.70. Found: C, 60.66; H, 5.77;
N, 19.52.
Compound 13. Prepared according to general procedure 6:
compound 7 (60.0 mg, 0.150 mmol), p-(dibutylamino)-
phenylacetylene (41.4 mg, 0.180 mmol, 1.2 equiv) in a mixture of
benzene/triethylamine (5 mL/1 mL). Column chromatography on
silica gel eluting with petroleum ether/CH2Cl2 7:3 to 3:7 as eluant to
give compound 13 as a greenish amorphous powder (78.4 mg, 40%):
IR (ATR) ν in cm−1 2955 (m), 2923 (m), 2854 (m), 1736 (w), 1610
Compound 9. Prepared according to general procedure 4:
compound 7 (100.0 mg, 0.250 mmol), 4,4′,5,5′-tetramethyl-1,3,2-
dioxaboronic ester of 3,4-ethylenedioxythiophene (0.376 mmol, 100.7
mg, 1.5 equiv), and aqueous K2CO3 (69.2 mg, 0.500 mmol, 2 equiv) in
toluene (10 mL). Column chromatography on silica gel eluting with
petroleum ether/CH2Cl2 4:6 to CH2Cl2 as eluant to give compound 9
as a yellow powder (28.1 mg, 27%): mp 227−229 °C; IR (ATR) ν in
cm−1 3097 (w), 3058 (w), 2923 (m), 2857 (w), 1613 (m), 1564 (s),
1
(m), 1562 (s), 1509 (s), 1466 (w), 1435 (m), 1398 (s), 810 (s); H
NMR (200 MHz, CDCl3) δ = 8.39 (d, 1H, 3J = 2.4 Hz), 7.38 (d, 1H,
3J = 2.4 Hz), 6.96 (AB sys, 4H, JAB = 5.6 Hz, υoδ = 157.8 Hz), 3.30−
3.12 (m, 4H), 3.16 (s, 12H), 2.28 (s, 3H), 1.56 (m, 4H), 1.39−1.31
1
1511 (s), 1433 (m), 1393 (s), 1054 (m), 807 (m); H NMR (200
MHz, CDCl3) δ = 8.57 (d, 1H, 3J = 1.4 Hz), 7.64 (d, 1H, 3J = 1.4 Hz),
6.22 (s, 1H), 4.30 (m, 2H), 4.25 (m, 2H), 3.24 (s, 12H), 2.36 (s, 3H);
13C NMR (CDCl3, 50 MHz) δ = 162.6, 159.1, 142.4, 137.3, 132.9,
127.3, 125.0, 123.9, 117.9, 117.5, 96.4, 64.9, 64.7, 36.8, 16.6; EI-MS,
m/z (%) 413.1 (100). Anal. Calcd for C20H23N5O3S: C, 58.09; H,
5.61; N, 16.94. Found: C, 57.74; H, 5.47; N, 16.79.
3
(m, 4H), 0.95 (t, 6H, J = 4.8 Hz); 13C NMR (CDCl3, 75 MHz) δ =
169.8, 163.9, 160.7, 148.3, 136.9, 132.9, 130.2, 127.1, 118.2, 113.6,
111.7, 109.5, 88.6, 87.6, 51.1, 36.7, 36.5, 29.8, 20.7, 16.1, 14.2; EI-MS,
m/z (%) 500.2 (100). Anal. Calcd for C30H40N6O: C, 71.97; H, 8.05;
N, 16.79. Found: C, 72.35; H, 8.41; N, 16.94.
Compound 14. A Schlenk tube was charged with a solution of 4,4-
difluoro-1,3,5,7,8-pentamethyl-2-iodo-4-bora-3a,4a-diaza-s-indacene
(190.0 mg, 0.490 mmol), trimethylsilylacetylene (50.6 mg, 0.515
mmol, 1.05 equiv) in a mixture of benzene/diisopropylamine (10 mL/
2 mL). The solution was degassed with argon for 30 min, then
[Pd(PPh2)2Cl2] (5 mol %, 18.1 mg) and CuI (6 mol %, 5.9 mg) were
added. The mixture was stirred at rt for one night (monitored by
TLC). Compound 7 (195.4, 0.490 mmol), DBU (895.6 mg, 5.88
mmol, 12 equiv), and 40 mol % of H2O were then added, and the
solution was stirred for an additional 3 days. The solution was then
extracted with CH2Cl2, washed with water, dried over MgSO4, and
evaporated under vacuum. The residue was purified by column
chromatography on silica gel eluting with petroleum ether/CH2Cl2 8:2
to 0:10 as eluant to give compound 14 as a purple powder (181.1 mg,
66%): mp dec >270 °C; IR (ATR) ν in cm−1 2923 (w), 2866 (w),
1556 (s), 1510 (s), 1467 (m), 1395 (s), 1199 (s), 1063 (s), 980 (s);
Compound 10. Prepared according to general procedure 4:
compound 7 (50.0 mg, 0.125 mmol), 5′-hexyl-2,2′-bithiophene-5-
boronic acid pinacol ester (0.250 mmol, 94.3 mg, 2 equiv), and
aqueous K2CO3 (86.5 mg, 0.626 mmol, 5 equiv) in toluene (10 mL).
Column chromatography on silica gel eluting with petroleum ether/
CH2Cl2 8:2 to 5:5 as eluant to give compound 10 as a yellow
amorphous powder (26.6 mg, 41%): IR (ATR) ν in cm−1 2923 (m),
2855 (w), 1611 (m), 1562 (s), 1508 (s), 1434 (m), 1394 (s), 1383 (s),
1209 (m), 1053 (m), 790 (s); 1H NMR (200 MHz, CDCl3) δ = 8.45
3
3
3
(d, 1H, J = 2.2 Hz), 7.47 (d, 1H, J = 2.2 Hz), 7.13 (d, 1H, J = 3.9
Hz), 7.02 (d, 1H, 3J = 3.6 Hz), 6.97 (d, 1H, 3J = 3.6 Hz), 6.66 (d, 1H,
3
3J = 3.9 Hz), 3.23 (s, 12H), 2.77 (t, 2H, J = 7.4 Hz), 2.33 (s, 3H),
3
1.65 (m, 2H), 1.28 (m, 6H), 0.87 (t, 3H, J = 6.6 Hz); 13C NMR
(CDCl3, 50 MHz) δ = 170.0, 163.9, 160.7, 145.7, 143.5, 136.1, 135.4,
131.5, 127.4, 126.5, 125.2, 124.3, 124.2, 123.3, 122.6, 118.3, 36.7, 36.5,
32.1, 32.0, 30.6, 29.2, 23.0, 16.3, 14.3; EI-MS, m/z (%) 521.1 (100).
Anal. Calcd for C28H35N5OS2: C, 64.46; H, 6.76; N, 13.42. Found: C,
64.22; H, 6.44; N, 13.18.
3
1H NMR (200 MHz, CDCl3) δ = 14.8 (s, 1H), 8.40 (d, 1H, J = 2.0
3
Hz), 7.40 (d, 1H, J = 2.0 Hz), 6.09 (s, 1H), 3.22 (s, 12 H), 2.67 (s,
3H), 2.62 (s, 3H), 2.56 (s, 3H), 2.54 (s, 3H), 2.43 (s, 3H), 2.29 (s,
3H); 13C NMR (CDCl3, 75 MHz) δ = 169.4, 163.5, 155.3, 155.1,
142.1, 141.6, 104.4, 136.8, 133.5, 133.2, 130.2, 126.8, 126.7, 124.8,
121.9, 117.8, 112.7, 96.4, 79.5, 36.5, 36.3, 17.5, 16.7, 16.0, 15.9, 15.3,
14.6; EI-MS, m/z (%) 557.2 (100). Anal. Calcd for C30H34BF2N7O: C,
64.64; H, 6.15; N, 17.59. Found: C, 64.52; H, 5.82; N, 17.38.
Compound 11. A Schlenk flask was charged with compound 7
(50.0 mg, 0.125 mmol), styrene (0.250 mmol, 0.029 mL, 2 equiv), and
K2CO3 (26.0 mg, 0.188 mmol, 1.5 equiv) in a mixture of benzene (2
mL) and DMF (6 mL). The solution was degassed with argon for 30
min, then [Pd(PPh3)2Cl2] (10 + 10 mol %) was added. The mixture
was stirred at 80 °C for 11 h (monitored by TLC). The solution was
extracted with CH2Cl2, washed with water, dried over MgSO4, and
evaporated under vacuum. The residue was purified by column
chromatography on silica gel eluting with petroleum ether/CH2Cl2 8:2
to 6:4 as eluant to give compound 11 as a white powder (13.0 mg,
28%): mp 180−182 °C; IR (ATR) ν in cm−1 3097 (w), 3058 (w),
2922 (m), 2850 (w), 1611 (m), 1563 (s), 1557 (s), 1509 (s), 1434
Compound 15. Prepared according to general procedure 5:
compound 7 (50.0 mg, 0.125 mmol), 1-ethynylpyrene (31.2 mg, 0.138
mmol, 1.1 equiv) in a mixture of benzene/triethylamine (5 mL/1 mL).
The solution was degassed with argon for 30 min, then [Pd(PPh3)4]
(10 mol %, 15.0 mg) and CuI (12 mol %, 3.0 mg) were added.
Column chromatography on silica gel eluting with petroleum ether/
CH2Cl2 7:3 to 5:5 as eluant to give an orange powder (79.0 mg, 41%):
mp dec >250 °C; IR (ATR) ν in cm−1 2920 (w), 1610 (m), 1569 (m),
1
(m), 1384 (s), 1210 (m), 1056 (m), 810 (s); H NMR (300 MHz,
3
3
(CD3)2CO) δ = 8.43 (d, 1H, J = 2.2 Hz), 7.61 (d, 1H, J = 2.2 Hz),
1
3
3
3
1513 (s), 1389 (s), 845 (s); H NMR (200 MHz, CDCl3) δ = 14.85
7.57 (d, 2H, J = 7.8 Hz), 7.35 (t, 2H, J = 7.7 Hz), 7.22 (t, 1H, J =
7.9 Hz), 7.22 (d, 1H, 3J = 16.0 Hz), 7.1 (d, 1H, 3J = 16.0 Hz), 3.24 (s,
12H), 2.27 (s, 3H); 13C NMR (CDCl3, 75 MHz) δ = 160.2, 138.1,
132.1, 131.7, 131.6, 129.1, 129.0, 128.8, 128.7, 128.5, 128.2, 127.1,
126.3, 126.0, 125.8, 36.6, 16.4; EI-MS, m/z (%) 375.2 (100). Anal.
Calcd for C22H25N5O: C, 70.38; H, 6.71; N, 18.65. Found: C, 70.11;
H, 6.54; N, 18.47.
(s, 1H), 8.70 (d, 1H, 3J = 9.3 Hz), 8.59 (d, 1H, 3J = 2.2 Hz), 8.26−8.00
(m, 8H), 7.61 (d, 1H, 3J = 2.2 Hz), 3.25−3.19 (m, 12H), 2.33 (s, 3H);
13C NMR (CD2Cl2, 75 MHz) δ = 168.8, 162.9, 160.7, 136.3, 131.1,
130.9, 130.7, 130.4, 130.0, 128.9, 127.7, 127.6, 127.4 126.8, 126.5,
125.8, 125.2, 125.0, 124.1, 123.8, 118.1, 117.5, 111.8, 95.6, 85.7, 35.9,
35.6, 15.3; EI-MS, m/z (%) 497.2 (100). Anal. Calcd for C32H27N5O:
C, 77.24; H, 5.47; N, 14.07. Found: C, 77.04; H, 5.25; N, 13.69.
Compound 16. Prepared according to general procedure 5:
compound 7 (50.0 mg, 0.125 mmol), 1-ethynylperylene (36.3 mg,
Compound 12. Prepared according to general procedure 5:
compound 7 (50.0 mg, 0.125 mmol), 4-ethynyltoluene (17.5 mg,
0.150 mmol, 2 equiv) in a mixture of benzene/triethylamine (5 mL/1
K
dx.doi.org/10.1021/jo301059u | J. Org. Chem. XXXX, XXX, XXX−XXX