The Journal of Organic Chemistry
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in dry Et3N (30 mL) under N2. PdCl2(PPh3)2 (98 mg, 0.14 mmol)
and CuI (53 mg, 0.28 mmol) were added, and the reaction mixture
was heated to 100 °C for 30 min. After cooling to room temperature,
saturated aqueous NH4Cl solution (100 mL) was added and the
product was extracted with CH2Cl2 (3 × 50 mL). The organic phases
were dried over Na2SO4 and evaporated. Chromatography on a silica
gel column with pentane gave a white solid (1.80 g, 7.11 mmol,
∼100%). 1H NMR (400 MHz, CDCl3): δ [ppm] 7.45−7.41 (m, 2 H),
7.33−7.30 (m, 2 H), 0.25 (s, 9 H).
22.4. HRMS (ESI TOF) m/z: [M]+ Calcd for C46H44NO2B 653.3467;
Found 653.3456. Anal. Calcd for C46H44NO2B·0.5H2O: C, 83.37; H,
6.84; N, 2.11. Found: 83.74; H, 6.83; N, 2.20. Water is also detected in
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the H NMR spectrum; see the Supporting Information.
N3-phCC-B. Compound 15 (217 mg, 0.30 mmol) and compound 3
(100 mg, 0.25 mmol) were dissolved in dry Et3N (10 mL) under a N2
atmosphere. PdCl2(PPh3)2 (3.5 mg, 0.005 mmol) and CuI (1.9 mg,
0.01 mmol) were added, and the reaction mixture was refluxed
overnight. After cooling to room temperature, saturated aqueous
NH4Cl solution was added, and the product was extracted with
CH2Cl2 (3 × 50 mL). The combined organic phases were dried over
Na2SO4 and evaporated. Chromatography on a silica gel column with a
1:2 (v:v) mixture of pentane and CH2Cl2 afforded the product as an
orange oil (110 mg, 0.11 mmol, 42%). When drops of a concentrated
solution of this oil in CH2Cl2 were added to water, an orange solid was
obtained. 1H NMR (400 MHz, acetone-d6): δ [ppm] 7.48 (ABq, 4 H,
ΔδAB = 0.02, JAB = 8.0 Hz), 7.37−7.33 (m, 2 H), 7.07−7.00 (m, 12 H),
6.91−6.84 (m, 18 H), 3.77 (s, 12 H), 2.28 (s, 6 H), 2.00 (s, 12 H). 13C
NMR (100 MHz, acetone-d6): δ [ppm] 157.2, 150.2, 146.7, 146.4,
142.5, 141.9, 140.4, 139.8, 139.1, 137.1, 129.3, 127.9, 127.5, 122.4,
119.8, 115.7, 114.1, 93.8, 89.3, 55.9, 23.9, 21.4. HRMS (ESI TOF) m/
z: [M]+ Calcd for C72H66N3O4B 1047.5152; Found 1047.5127. Anal.
Calcd for C72H66N3O4B: C, 82.51; H, 6.35; N, 4.01. Found: 82.45; H,
6.65; N, 3.80.
Compound 12.15 Compound 11 (1.00 g, 4.0 mmol),14 dianisyl-
amine (7) (725 mg, 3.2 mmol), NaOtBu (6.3 mg, 65.6 mmol),
Pd(dba)2 (190 mg, 0.3 mmol), and PtBu3 (0.98 mL, 0.3 mmol) were
dissolved in dry deoxygenated toluene (60 mL) under N2. The mixture
was refluxed for 30 h, and after cooling to room temperature, brine
(100 mL) was added. After phase separation, the aqueous layer was
extracted with CH2Cl2 (3 × 50 mL), and the combined organic phases
were dried over Na2SO4. Column chromatography on silica gel with a
1:3 (v:v) mixture of pentane and CH2Cl2 afforded the pure product as
a yellow solid (810 mg, 2.0 mmol, 64%). 1H NMR (250 MHz,
acetone-d6): δ [ppm] 7.27−7.19 (m, 2 H), 7.12−7.05 (m, 4 H), 6.97−
6.89 (m, 4 H), 6.76−6.68 (m, 2 H), 3.80 (s, 6 H), 0.2 (s, 9 H).
Compound 13. Compound 11 (150 mg, 0.59 mmol), oligotriaryl-
amine 8 (308 mg, 0.49 mmol),10c NaOtBu (942 mg, 9.80 mmol),
Pd(dba)2 (28 mg, 0.05 mmol), and (HPtBu3)BF4 (14 mg, 0.05 mmol)
were dissolved in dry and deoxygenated toluene (15 mL). The mixture
was refluxed under N2 for 20 h. Brine (100 mL) was added to the
cooled mixture, and the aqueous phase was extracted with CH2Cl2 (3
× 50 mL). After drying over Na2SO4 and evaporation of the solvents,
the crude product was purified by column chromatography on silica
gel using CH2Cl2 as the eluent. The pure product was obtained as a
N3-phCC-B2. Compound 15 (180 mg, 0.25 mmol) and compound
6 (195 mg, 0.29 mmol)13 were suspended in dry Et3N (10 mL) under
N2. PdCl2(PPh3)2 (3.5 mg, 0.005 mmol) and CuI (1.9 mg, 0.01 mmol)
were added, and the mixture was reacted at reflux overnight. After
cooling to room temperature, saturated aqueous NH4Cl solution (100
mL) was added and the product was extracted with CH2Cl2 (3 × 50
mL). The combined organic phases were dried over Na2SO4 and
evaporated. Column chromatography on silica gel with a 1:2 (v:v)
mixture of pentane and CH2Cl2 gave a yellow oil. When drops of a
concentrated solution of this oil in CH2Cl2 were added to methanol,
the product was obtained as an orange solid (110 mg, 0.09 mmol,
34%). 1H NMR (400 MHz, acetone-d6): δ [ppm] 7.66 (d, J = 1.3 Hz,
2 H), 7.54 (t, J = 1.3 Hz, 1 H), 7.25 (d, J = 8.7 Hz, 2 H), 7.07−7.01
(m, 8 H), 6.98 (d, J = 8.7 Hz, 4 H), 6.92−6.68 (m, 8 H), 6.86−6.81
(m, 6 H), 6.79 (s, 8 H), 3.77 (s, 12 H), 2.24 (s, 12 H), 1.97 (s, 24 H).
13C NMR (100 MHz, acetone-d6): δ [ppm] 157.2, 149.9, 148.0, 146.7,
142.5, 142.2, 141.9, 141.5, 140.5, 140.2, 133.4, 129.3, 127.7, 127.4,
124.8, 122.4, 119.8, 115.8, 115.2, 114.2, 91.6, 88.9, 55.9, 23.9, 21.5.
HRMS (ESI TOF) m/z: [M]+ Calcd for C90H87N3O4B2 1295.6902;
Found 1295.6878. Anal. Calcd for C90H87N3O4B2·0.5H2O: C, 82.81;
H, 6.80; N, 3.22. Found: 82.64; H, 6.74; N, 2.94. Water is also
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yellow oil which solidified over time (290 mg, 0.36 mmol, 74%). H
NMR (400 MHz, acetone-d6): δ [ppm] 7.25−7.23 (m, 2 H), 7.08−
7.06 (m, 8 H), 6.99−6.97 (m, 4 H), 6.90−6.82 (m, 14 H), 3.78 (s, 12
H), 0.19 (s, 9 H).
Compound 14.15 Compound 12 (0.80 g, 2.0 mmol) was dissolved
in THF (40 mL) under N2, and TBAF solution in methanol (18.0 mL,
5.4 mmol) was added dropwise. The reaction mixture was stirred at
room temperature for 1 h, and then, the solvents were evaporated. The
solid residue was taken up in EtOAc and washed with water (3 × 100
mL). After drying over Na2SO4 and evaporating the solvent, the pure
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product was obtained as a yellow solid (0.65 g, 2.0 mmol, 99%). H
NMR (250 MHz, CDCl3): δ [ppm] 7.30−7.23 (m, 2 H), 7.11−7.01
(m, 4 H), 6.89−6.76 (m, 6 H), 3.80 (s, 6 H).
Compound 15. Compound 13 (300 mg, 0.38 mmol) was dissolved
in dry THF (10 mL) under N2. TBAF solution in THF (1.40 mL, 0.38
mmol) was added dropwise, and the reaction mixture was stirred at
room temperature for 1.5 h. After removal of THF, the solid residue
was taken up in EtOAc (100 mL) and washed with water. The organic
phases were dried over Na2SO4 and evaporated to dryness. This
afforded the pure product as a yellow solid (250 mg, 0.35 mmol, 91%).
1H NMR (400 MHz, C6D6): δ [ppm] 7.38−7.36 (m, 2 H), 7.12−7.07
(m, 8 H), 7.05−6.97 (m, 10 H), 6.73−6.68 (m, 8 H), 3.29 (s, 12 H),
2.76 (s, 1 H).
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detected in the H NMR spectrum; see the Supporting Information.
NMR spectroscopy, ESI-HRMS, elemental analysis, cyclic voltam-
metry, optical absorption, and luminescence spectroscopy occurred
using the same equipment as described in detail in a recent
publication.10c Fluorescence lifetime measurements were performed
using a commercial fluorescence lifetime spectrometer. Absolute
photoluminescence quantum yields were measured on a commercial
absolute photoluminescence quantum yield measurement system.
N-phCC-B.9b Compound 3 (270 mg, 0.67 mmol) and compound
14 (200 mg, 0.61 mmol) were suspended in dry Et3N (15 mL) under
N2. CuI (4.5 mg, 0.02 mmol) and PdCl2(PPh3)2 (8.4 mg, 0.01 mmol)
were added, and the reaction mixture was refluxed for 30 h. After
cooling to room temperature, saturated aqueous NH4Cl solution (100
mL) was added, and the aqueous phase was extracted with CH2Cl2 (3
× 50 mL). After drying over Na2SO4 and evaporation of the solvents,
the crude product was purified by chromatography on silica gel using
an 18:1 (v:v) mixture of pentane and EtOAc as the eluent. Subsequent
recrystallization by dropping a concentrated CH2Cl2 solution into
methanol afforded the pure product as a yellow solid (172 mg, 0.26
mmol, 43%). 1H NMR (250 MHz, acetone-d6): δ [ppm] 7.49 (ABq, 4
H, ΔδAB = 0.04, JAB = 8.8 Hz), 7.38−7.32 (m, 2 H), 7.16−7.09 (m, 4
H), 6.99−6.91 (m, 4 H), 6.85 (s, 4 H), 6.81−6.75 (m, 2 H), 3.81 (s, 6
H), 2.29 (s, 6 H), 2.00 (s, 12 H). 13C NMR (100 MHz, acetone-d6): δ
[ppm] 158.9, 151.5, 147.3, 143.4, 142.5, 141.6, 140.8, 138.0, 134.5,
132.7, 130.2, 129.5, 129.4, 120.0, 116.9, 114.8, 94.7, 90.1, 56.9, 24.8,
ASSOCIATED CONTENT
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* Supporting Information
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1H and H/13C-HMBC NMR spectra, ESI-HRMS spectra, and
additional electrochemical and optical spectroscopic data. This
material is available free of charge via the Internet at http://
AUTHOR INFORMATION
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Corresponding Author
Notes
The authors declare no competing financial interest.
J
J. Org. Chem. XXXX, XXX, XXX−XXX