Organometallics
Article
126.18, 125.83, 33.23, 29.62, 29.60, 29.49 ppm. HR-MS (ESI): calcd
for C25H20NS ([M + H]+) 366.1311, found 366.1308. Anal. Calcd for
C25H19NS: C, 82.15; H, 5.24; N, 3.83. Found: C, 82.00; H, 5.38; N,
3.86.
was added and this mixture was extracted with CH2Cl2. The
combined organic layers were washed with water, dried over
MgSO4 and concentrated using a rotary evaporator to afford the
crude dibromoboron compound. Without further purification the
crude product was placed in a round-bottom flask that was dried using
high vacuum and then filled with argon and toluene was added. To
this stirred solution was added AlMe3 (2.0 M in toluene) at room
temperature. After the mixture was stirred for 1/2 h, the reaction was
quenched by adding water and extracted with CH2Cl2. The combined
organic layers were washed with water and brine. The organic layer
was dried over Na2SO4 and concentrated using a rotary evaporator.
The crude product was purified by silica gel column chromatography
using an n-hexane/dichloromethane mixture as the mobile phase.
Synthesis of Compound 1. The quantities involved are as follows:
compound 1L (0.60 g, 1.67 mmol), N,N-diisopropylethylamine (0.29
mL, 1.67 mmol), BBr3 (1.0 M in CH2Cl2, 5.01 mL, 5.01 mmol), and
AlMe3 (2.0 M in toluene, 1.67 mL, 3.34 mmol). Yield: 0.43 g, (65%).
Synthesis of Compound 4L. The quantities involved are as
follows: 1-naphthaldehyde (0.77 mL, 5.67 mmol), 2-tetralone (1.5
mL, 11.34 mmol), and ammonium acetate (1.75 g, 22.68 mmol).
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Yield: 1.44 g, (62%). H NMR (400 MHz, CDCl3): δ 7.88 (dd, J =
8.0, 4.4 Hz, 2H), 7.70 (d, J = 8.4 Hz, 1H), 7.58−7.56 (m, 1H), 7.47−
7.42 (m, 2H), 7.40−7.31 (m, 5H), 7.19 (d, J = 7.4 Hz, 1H), 6.99 (td,
J = 7.2, 1.8 Hz, 1H), 6.63−6.57 (m, 2H), 3.34−3.27 (m, 1H), 3.20−
3.11 (m, 3H), 3.02−2.96 (m, 2H), 2.83−2.74 (m, 2H) ppm. 13C
NMR (176 MHz, CDCl3): δ 158.00, 153.25, 145.49, 139.92, 139.84,
138.58, 134.20, 133.16, 132.91, 132.01, 130.49, 129.00, 128.40,
128.36, 128.06, 127.98, 127.92, 127.05, 126.90, 126.31, 126.23,
126.10, 125.88, 125.72, 33.22, 29.78, 29.55, 29.38 ppm. HR-MS
(ESI): Calcd for C31H24N ([M + H]+) 410.1903, found 410.1904.
Anal. Calcd for C31H23N: C, 90.92; H, 5.66; N, 3.42. Found: C, 90.85;
H, 5.82; N, 3.43.
Synthesis of Compound 5L. The quantities involved are as
follows: 4-(9H-carbazol-9-yl)benzaldehyde (1.53 g, 5.67 mmol), 2-
tetralone (1.5 mL, 11.34 mmol), and ammonium acetate (1.75 g,
22.68 mmol). Yield: 1.54 g, (52%). Mp: 267 °C. 1H NMR (400 MHz,
CDCl3): δ 8.16 (d, J = 7.7 Hz, 2H), 7.74 (d, J = 8.0 Hz, 2H), 7.60−
7.55 (m, 3H), 7.50−7.29 (m, 10H), 7.25−7.22 (m, 1H), 7.05 (d, J =
4.0 Hz, 2H), 3.31−3.22 (m, 4H), 3.04−3.01 (m, 2H), 2.83−2.76 (m,
2H) ppm. 13C NMR (100 MHz, CDCl3): δ 158.45, 153.02, 146.07,
141.23, 140.91, 139.81, 139.01, 137.34, 133.05, 132.98, 131.58,
129.80, 129.26, 128.87, 128.06, 127.99, 127.95, 127.44, 127.24,
127.01, 126.24, 126.09, 125.82, 123.56, 120.43, 120.08, 109.97, 33.36,
29.68, 29.59, 29.35 ppm. HR-MS (ESI): calcd for C39H29N2 ([M +
H]+) 525.2325, found 525.2320. Anal. Calcd for C39H28N2: C, 89.28;
H, 5.38; N, 5.34. Found: C, 89.12; H, 5.23; N, 5.34.
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Mp: 251 °C. H NMR (400 MHz, CDCl3): δ 7.97 (d, J = 7.7 Hz,
1H), 7.81 (d, J = 8.1 Hz, 1H), 7.58−7.54 (m, 2H), 7.41−7.24 (m,
7H), 6.95 (t, J = 8 Hz, 1H), 2.81−4.04 (m, 8H), 0.25 (s, 6H) ppm.
13C NMR (100 MHz, CDCl3): δ 170.22, 155.71, 151.05, 149.83,
139.46, 139.03, 135.70, 131.67, 131.61, 129.70, 129.61, 129.27,
128.94, 128.63, 128.57, 128.40, 127.89, 127.84, 127.26, 126.37,
126.03, 124.82, 123.98, 30.29, 29.35, 28.78, 28.32, 9.16 ppm. 11B
NMR (128 MHz, CDCl3): δ 2.12 ppm. ESI-MS: calcd for C29H27BN
([M + H]+) 400.2236, found m/z 400.2263. Anal. Calcd for
C29H26BN: C, 87.22; H, 6.56; N, 3.51. Found: C, 87.02; H, 6.67;
N, 3.71.
Synthesis of Compound 2. The quantities involved are as follows:
compound 2L (0.73 g, 1.67 mmol), N,N-diisopropylethylamine (0.29
mL, 1.67 mmol), BBr3 (1.0 M in CH2Cl2, 5.01 mL, 5.01 mmol), and
AlMe3 (2.0 M in toluene, 1.67 mL, 3.34 mmol). Yield: 0.49 g, (62%).
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Mp: 291 °C. H NMR (400 MHz, CDCl3): δ 7.89 (d, J = 7.7 Hz,
Synthesis of Compound 6L. The quantities involved are as
follows: 4-(diphenylamino)benzaldehyde (1.55 g, 5.67 mmol), 2-
tetralone (1.5 mL, 11.34 mmol), and ammonium acetate (1.75 g,
22.68 mmol). Yield: 1.49 g, (50%). Mp: 238 °C. 1H NMR (400 MHz,
CDCl3): δ 7.53−7.51 (m, 1H), 7.37−7.24 (m, 10H), 7.17−7.12 (m,
5H), 7.07−6.97 (m, 6H), 3.16−3.09 (m, 4H), 2.98−2.95 (m, 2H),
2.77 (t, J = 8.0 Hz, 2H) ppm. 13C NMR (100 MHz, CDCl3): δ
158.20, 153.71, 147.73, 147.55, 145.78, 139.72, 138.80, 136.15,
133.36, 133.21, 130.93, 129.68, 129.29, 128.85, 128.75, 127.95,
127.68, 127.33, 127.07, 126.97, 126.12, 125.56, 124.48, 123.67,
122.93, 33.36, 29.64, 29.60, 29.32 ppm. HR-MS (ESI): calcd for
C39H31N2 ([M + H]+) 527.2482, found 527.2463. Anal. Calcd for
C39H30N2: C, 88.94; H, 5.74; N, 5.32. Found: C, 88.81; H, 5.65; N,
5.26.
1H), 7.65 (d, J = 8.3 Hz, 2H), 7.56−7.53 (m, 1H), 7.41−7.30 (m,
5H), 7.28−7.24 (m, 1H), 7.06 (dd, J = 8.5, 2.0 Hz, 1H), 4.04−2.81
(m, 8H), 0.22 (s, 6H) ppm. 13C NMR (100 MHz, CDCl3): δ 172.87,
155.84, 150.11, 150.08, 139.47, 139.17, 134.42, 131.50, 131.40,
129.76, 129.19, 129.08, 128.67, 128.61, 128.31, 127.97, 127.45,
127.13, 126.47, 126.32, 126.19, 125.42, 30.30, 29.34, 28.75, 28.33,
8.79 pppm. 11B NMR (128 MHz, CDCl3): δ 2.66 ppm. ESI-MS: calcd
for C29H26BBrN ([M + H]+) 478.1341, found m/z 478.1361. Anal.
Calcd for C29H25BNBr: C, 72.83; H, 5.27; N, 2.93. Found: C, 72.67;
H, 5.21; N, 2.75.
Synthesis of Compound 3. The quantities involved are as follows:
compound 3L (0.61 g, 1.67 mmol), N,N-diisopropylethylamine (0.29
mL, 1.67 mmol), BBr3 (1.0 M in CH2Cl2, 5.01 mL, 5.01 mmol), and
AlMe3 (2.0 M in toluene, 1.67 mL, 3.34 mmol). Yield: 0.20 g, (30%).
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Synthesis of Compound 7L. The quantities involved are as
follows: 4-(dimethylamino)benzaldehyde (0.85 g, 5.67 mmol), 2-
tetralone (1.5 mL, 11.34 mmol), and ammonium acetate (1.75 g,
Mp: 239 °C. H NMR (400 MHz, CDCl3): δ 8.28−8.24 (m, 1H),
7.48−7.45 (m, 1H), 7.42−7.37 (m, 4H), 7.32−7.29 (m, 3H), 7.12 (d,
J = 4.7 Hz, 1H), 3.44 (br s, 2H), 3.12 (t, J = 8 Hz, 2H), 2.94 (t, J =
6.7 Hz, 2H), 2.73 (t, J = 8 Hz, 2H), 0.23 (s, 6H) ppm. 13C NMR (100
MHz, CDCl3): δ 156.09, 149.48, 148.49, 139.02, 138.82, 133.66,
131.78, 131.24, 130.25, 129.00, 128.68, 128.16, 127.86, 127.71,
127.24, 127.07, 126.60, 126.49, 126.42, 126.14, 30.31, 29.31, 28.68,
28.17, 7.92 ppm. 11B NMR (128 MHz, CDCl3): δ 1.67. ESI-MS:
Calcd for C27H25BNS ([M + H]+) 406.1800, found m/z 406.1820.
Anal. Calcd for C27H24BNS: C, 80.00; H, 5.97; N, 3.46. Found: C,
79.85; H, 5.72; N, 3.67.
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22.68 mmol). Yield: 1.27 g, (56%). H NMR (700 MHz, CDCl3): δ
7.51 (d, J = 8 Hz, 1H), 7.36 (t, J = 8 Hz, 3H), 7.31 (t, J = 8 Hz, 1H),
7.27 (dd, J = 12, 8 Hz, 2H), 7.17−7.07 (m, 2H), 6.96 (t, J = 8 Hz,
1H), 6.69 (d, J = 8.0 Hz, 2H), 3.14−3.09 (m, 4H), 2.98 (s, 6H),
2.97−2.93 (m, 2H), 2.79−2.72 (m, 2H) ppm. 13C NMR (176 MHz,
CDCl3): δ 158.13, 154.29, 150.41, 145.73, 139.71, 138.66, 133.86,
133.46, 130.86, 130.13, 129.59, 128.71, 128.37, 127.89, 127.45,
126.85, 126.73, 126.66, 126.06, 125.77, 112.37, 40.67, 33.35, 29.74,
29.69, 29.47 ppm. ESI-MS: calcd for C29H27N2 ([M + H]+) 403.2169,
found 403.2160. Anal. Calcd for C29H26N2: C, 86.53; H, 6.51; N,
6.96. Found: C, 86.44; H, 6.45; N, 6.93.
General Procedure for the Synthesis of Compounds 1−7.
An oven-dried three-neck round-bottom flask with an addition funnel
was degassed and purged using vacuum−nitrogen cycles and charged
with a dichloromethane solution of compound 1L−7L. To this
solution was added diisopropylethylamine (i-Pr2NEt) at 0 °C, and the
mixture was stirred. After 10 min BBr3 (1.0 M in dichloromethane)
was added slowly at the same temperature and the mixture was
warmed to room temperature. After the reaction mixture was stirred
at room temperature for 24 h, a saturated K2CO3 aqueous solution
Synthesis of Compound 4. The quantities involved are as follows:
compound 4L (0.68 g, 1.67 mmol), N,N-diisopropylethylamine (0.29
mL, 1.67 mmol), BBr3 (1.0 M in CH2Cl2, 5.01 mL, 5.01 mmol), and
AlMe3 (2.0 M in toluene, 1.67 mL, 3.34 mmol). Yield: 0.32 g, (42%).
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Mp: 269 °C. H NMR (400 MHz, CDCl3): δ 7.87 (d, J = 7.9 Hz,
1H), 7.76 (t, J = 8.1 Hz, 2H), 7.68 (d, J = 7.2 Hz, 1H), 7.40−7.31 (m,
4H), 7.19−7.11 (m, 2H), 7.06 (d, J = 8.5 Hz, 1H), 6.93 (d, J = 7.7
Hz, 1H), 6.83 (t, J = 7.6 Hz, 1H), 6.69 (t, J = 7.4 Hz, 1H), 3.76−3.69
(m, 2H), 3.30−3.22 (m, 1H), 3.08−3.05 (m, 2H), 2.95 (t, J = 8 Hz,
2H), 2.86−2.77 (m, 1H), 0.32 (s, 3H), 0.21 (s, 3H) ppm. 13C NMR
(100 MHz, CDCl3): δ 173.20, 155.68, 152.10, 148.91, 139.46, 137.22,
133.78, 133.13, 131.95, 131.27, 130.69, 128.65, 128.56, 128.52,
F
Organometallics XXXX, XXX, XXX−XXX