The Journal of Organic Chemistry
Note
the volatiles and subsequent column chromatography on silica gel,
eluting with hexane: CHCl3 = 1:1, resulted in two colorless
compounds, 1 and S-1 in 52 and 45% yields, respectively. The
product was recrystallized from hexane to give colorless prismatic
crystals: mp 173−174 °C; 1H NMR (CDCl3, 400 MHz), δ = 9.18 (d, J
= 2 Hz, 1 H), 8.66 (s, 1 H), 8.23 (d, J = 2 Hz, 1 H), 8.19 (d, J = 2 Hz,
1 H), 8.16 (d, J = 2 Hz, 1 H), 8.00 (AB quartet), 1.59 (s, 9H), 1.56 (s,
9H), 1.51 (12 H); 13C{1H} NMR (CDCl3, 125 MHz), δ = 148.5,
148.4, 138.5, 133.1, 130.8, 130.7, 130.0, 127.9, 126.7, 124.0, 123.5,
122.9, 122.81, 122.75, 121.9, 83.8, 35.4, 35.2, 31.97, 31.95, 25.1. Anal.
Calcd: for C30H37BO2; C 81.81, H 8.47; found C, 81.68; H, 8.43.
HRMS (MALDI/DHB) Calcd for C30H3710BO2 440.2881; found
440.2887. HRMS (ESI) Calcd for C30H3810BO2 441.2965; found
441.2975.
4-Tolyl-2,7-di-tert-butylpyrene (2). Compound 1 (0.40 g, 1.0
mmol) and 4-bromo-toluene (0.34 g, 2.0 mmol) were placed in a 100
mL Schlenk tube, which was evacuated and purged with nitrogen gas
three times. Pd(PPh3)4 (12 mg, 0.01 mmol), toluene (∼10 mL) and a
saturated aqueous solution of Na2CO3 (∼0.5 mL) were added under
nitrogen. The tube was sealed with a Teflon cap and stirred at 80 °C
for 16 h before it was quenched. The mixture was extracted with
CH2Cl2, dried over MgSO4, and concentrated in vacuo. Purification by
column chromatography (silica gel using chloroform-petroleum ether
(1: 6)) gave a colorless oil in 64% yield. The product was recrystallized
from hexane with addition of hexafluorobenzene to give colorless
needle-like crystals: mp 121−123 °C; 1H NMR (CDCl3, 400 MHz), δ
= 8.29 (d, J = 2 Hz, 1 H), 8.20 (d, J = 1 Hz, 1H), 8.18 (s, 2 H), 8.05
(d, J = 2 Hz, 2 H), 7.974 (s, 1 H), 7.60 (d, J = 8 Hz, 2 H), 7.38 (d, J =
8 Hz, 2 H), 2.52 (s, 3 H), 1.58 (s, 9 H), 1.48 (s, 9 H); 13C{1H} NMR
(CDCl3, 100 MHz), δ = 148.8, 148.3, 139.5, 138.2, 137.0, 131.0, 130.8,
130.6, 130.1, 129.9, 129.1, 128.4, 127.9, 127.7, 127.2, 123.2, 122.4,
122.1, 121.8, 121.2, 35.3, 35.2, 32.0, 31.9, 21.3. Anal. Calcd: for
C31H32: C 92.03, H 7.97; found C 91.97; H, 8.01. HRMS (MALDI/
DHB) Calcd for C31H32 404.2499; found 404.2496. HRMS (ESI)
Calcd for C31H33 405.2582; found 405.2547.
H), 7.38 (m, 4 H), 7.31 (d, J = 8 Hz, 2 H), 2.51 (s, 3 H), 2.47 (s, 3 H),
2.43 (s, 3 H); 13C {H} NMR (CDCl3, 100 MHz), δ =140.1, 139.0,
138.9, 138.7, 137.9, 137.28, 137.25, 137.14, 131.7, 131.5, 131.3, 130.9,
130.0, 129.8, 129.7, 129.3, 128.3, 128.1, 127.93, 127.85, 127.75, 124.1,
123.9, 123.74, 123.69, 123.5, 123.2, 122.8, 21.4, 21.2, 21.2. Anal. Calcd:
for C37H28: C 94.03, H 5.97; found C 94.07; H, 5.93. HRMS
(MALDI/DHB) Calcd for C37H28 472.2182; found 472.2185. HRMS
(ESI) Calcd for C37H29 473.2269; found 473.2261.
ASSOCIATED CONTENT
* Supporting Information
■
S
Details of NMR, HRMS, and crystallographic data in CIF
format for 1−4, absorption and excitation spectra of 1, 3, 5, 6,
and absorption and emission spectra of 2 and 4. This material is
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support from the National Natural Science
Foundation of China (20802026, 50803033) is gratefully
acknowledged. Z.L. thanks the Royal Society and BP for a
China Incoming Fellowship to support collaboration with Prof.
T. B. Marder at Durham University (U.K.). T.B.M. thanks
AllyChem Co., Ltd. for a generous gift of B2pin2, the Royal
Society for a Wolfson Research Merit Award, the Alexander von
Humboldt Foundation for a Research Award, EPSRC for an
Overseas Research Travel Grant, and the Royal Society of
Chemistry for a Journals Grant for International Authors.
2,4,7-Tri-Bpin-pyrene (3). In a dry, nitrogen-filled Schlenk tube,
in a glovebox, the precatalyst [Ir(COD)Cl]2 (33.5 mg, 0.1 mmol Ir),
ligand dtbpy (27 mg, 0.1 mmol) and a small amount of B2pin2 (ca. 50
mg) were mixed in 2 mL of hexane and stirred vigorously until the
solution turned brown. Then 2,7-di-Bpin-pyrene (S-2) (2.27 g, 5
mmol), B2pin2 (2.54 g, 10 mmol) and 20 mL of hexane were added
under N2 into this tube, and the system was sealed with a Teflon cap
and stirred at 80 °C for 48 h to give a dark red solution. The mixture
was filtered through a short silica pad to remove the Ir-containing
catalyst and then concentrated. Removal of the volatiles and
subsequent column chromatography on silica gel, eluting with
hexane:CHCl3 = 1:1, resulted in two colorless compounds, 3 and S-
2 in 62 and 30% yields, respectively. The product was recrystallized
REFERENCES
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1
from hexane to give colorless prismatic crystals: mp 260−262 °C; H
NMR (CDCl3, 400 MHz), δ = 9.43 (s, 1 H), 8.69 (s, 1 H), 8.66 (s, 1
H), 8.62 (s, 1 H), 8.58 (s, 1 H), 8.05 (AB quartet, 2 H), 1.51 (s, 12 H),
1.45 (s, 12 H), 1.44 (12 H); 13C{1H} NMR (CDCl3, 100 MHz), δ =
138.3, 133.2, 132.5, 132.1, 132.0, 131.03, 130.96, 130.8, 130.0, 128.1,
127.4, 127.0, 126.3, 84.1, 84.0, 25.11, 25.08, 25.05. Anal. Calcd: for
C34H43B3O6; C 70.39, H 7.47; found C, 70.42; H, 7.45. HRMS (ESI)
Calcd for C34H44B3O6 581.3417; found 581.3414.
2,4,7-Tri-4-tolyl-pyrene (4). Compound 3 (0.58 g, 1.0 mmol)
and 4-bromo-toluene (1.00 g, 6.0 mmol) were placed in a 100 mL
Schlenk tube, which was evacuated and purged with nitrogen gas three
times. Pd(PPh3)4 (12 mg, 0.01 mmol), toluene (∼10 mL) and a
saturated aqueous solution of Na2CO3 (∼0.5 mL) were added under
nitrogen. The tube was sealed with a Teflon cap and stirred at 80 °C
for 16 h before it was quenched. This mixture was extracted with
dichloromethane, dried over MgSO4, and concentrated in vacuo.
Purification by column chromatography (silica gel using chloroform/
petroleum ether (1:6)) gave a colorless oil in 75% yield. The product
was recrystallized from toluene to give colorless single crystals: mp
1
202−204 °C; H NMR (CDCl3, 400 MHz), δ = 8.43 (d, J = 1 Hz, 1
H), 8.39 (d, J = 1 Hz, 1H), 8.38 (s, 2 H), 8.15 (s, 2 H), 8.06 (d, 1 H),
7.80 (d, J = 8 Hz, 2 H), 7.66 (d, J = 8 Hz, 2 H), 7.62 (d, J = 8 Hz, 2
(16) Ishiyama, T.; Nobuta, Y.; Hartwig, J. F.; Miyaura, N. Chem.
Commun. 2003, 2924.
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dx.doi.org/10.1021/jo301293w | J. Org. Chem. 2012, 77, 7124−7128