T. B. Marder, J. C. Collings et al.
was stirred at room temperature for 20 h and then acidified to pH 1–2
with saturated aqueous NH4Cl (8 mL) and 1m HCl (2 mL). The mixture
was extracted with EtOAc (3ꢅ10 mL), the organic fractions were dried
over MgSO4, and the solvent was removed under reduced pressure to
give 22 (0.42 g, 85%) as a light-brown solid. M.p. 131–1328C; 1H NMR
(500 MHz, [D6]DMSO): d=8.69 (s, 2H), 8.45 (br s, 2H), 8.28 (d, J=
8 Hz, 2H), 8.17 (s, 4H), 8.07 ppm (t, J=8 Hz, 1H); 13C{1H} NMR
(125 MHz, [D6]DMSO): d=131.1, 131.0, 129.7, 127.8, 127.0, 126.5, 124.9,
2-Phenylethynylpyrene (26): Under a nitrogen atmosphere in a Youngꢄs
tube, compound 25 (0.10 g, 0.29 mmol), phenylacetylene (0.045 g,
0.44 mmol), [PdCl2ACTHNUTRGNE(UNG PPh3)2] (0.007 g, 0.01 mmol), and CuI (0.002 g,
0.01 mmol) were dissolved in Et3N (2 mL) and DMF (5 mL). The tube
was sealed and heated at 908C for 16 h. The reaction was quenched with
1m HCl (10 mL) and extracted with CH2Cl2 (3ꢅ20 mL), then the CH2Cl2
fractions were dried over MgSO4. The solvent was removed under re-
duced pressure and the residue was purified by column chromatography
(silica gel, hexane/CH2Cl2 4:1) to give 26 (0.068 g, 78%) as a pale-yellow
solid. M.p. 135–1368C; 1H NMR (400 MHz, CDCl3): d=8.35 (s, 2H),
8.19 (d, J=8 Hz, 2H), 8.09 (d, J=9 Hz, 2H), 8.05 (d, J=9 Hz, 2H), 8.02
(t, J=8 Hz, 1H), 7.63–7.66 (m, 2H), 7.37–7.43 ppm (m, 3H);
13C{1H} NMR (125 MHz, CDCl3): d=131.9, 131.4, 131.2, 128.6, 128.5,
128.2, 127.9, 127.1, 126.5, 125.5, 124.5, 124.4, 123.5, 120.8. 90.2, 89.9 ppm;
MS (EI): m/z: 302 [M]+; HRMS (EI): m/z calcd for C24H14: 302.1090
[M]+; found: 302.1093; elemental analysis calcd (%) for C24H14: C 95.33,
H 4.67. Found: C 94.65, H 4.69.
À
124.8, 123.9 ppm (C B not observed); MS (MALDI-TOF, negative ion
mode): m/z: 246 [M]À (higher mass condensation products were also ob-
served); elemental analysis calcd (%) for C16H11BO2: C 78.10, H 4.51;
found: C 77.35, H 4.54.
2-[4-(Dimesitylboryl)phenyl]pyrene (23): Under a nitrogen atmosphere,
compound 19 (0.31 g, 1.0 mmol), 1-iodo-4-(dimesitylboryl)benzene
(0.45 g, 1.0 mmol), [PdCl2ACTHNUGTRNEU(GN dppf)] (0.007 g, 0.01 mmol), and K2CO3 (0.28 g,
2.0 mmol) were dissolved in EtOH (5 mL). The mixture was heated at
808C for 16 h. The reaction was quenched with 1m HCl (10 mL) and ex-
tracted with CH2Cl2 (3ꢅ20 mL). The combined organic fractions were
dried over MgSO4 and the solvent was removed under reduced pressure.
Recrystallization of the residue from hexane gave 23 (0.34 g, 65%) as
a white solid. M.p. 216–2188C; 1H NMR (400 MHz, CDCl3): d=8.46 (s,
2H), 8.20 (d, J=8 Hz, 2H), 8.14 (d, J=9 Hz, 2H), 8.11 (d, J=9 Hz, 2H),
8.02 (t, J=8 Hz, 1H), 7.90 (d, J=8 Hz, 2H), 7.73 (d, J=8 Hz, 2H), 6.90
(s, 4H), 2.37 (s, 6H), 2.12 ppm (s, 12H); 13C{1H} NMR (125 MHz,
CDCl3): d=144.9, 141.8, 141.0, 138.8, 138.5, 137.4, 131.7, 131.3, 128.4,
128.0, 127.7, 127.5, 126.1, 125.3, 124.7, 124.3, 123.9, 23.7, 21.4 ppm (one
2-(Trimethylsilylethynyl)pyrene (27):[16f] Under a nitrogen atmosphere in
a
Youngꢄs tube, compound 25 (0.10 g, 0.29 mmol), TMSA (0.10 g,
1.0 mmol), [PdCl2A(PPh3)2] (0.007 g, 0.01 mmol), and CuI (0.002 g,
CTHUNGTRENNUNG
0.01 mmol) were dissolved in Et3N (2 mL) and DMF (5 mL). The tube
was sealed and heated at 808C for 16 h. The reaction was quenched with
1m HCl (10 mL) and extracted with CH2Cl2 (3ꢅ20 mL). The organic
fractions were dried over MgSO4 and the solvent was removed under re-
duced pressure. Purification of the residue by column chromatography
(silica gel, hexane/CH2Cl2 4:1) gave 27 (0.065 g, 75%) as a pale-yellow
solid. M.p. 107–1088C; 1H NMR (400 MHz, CDCl3): d=8.28 (s, 2H),
8.16 (d, J=8 Hz, 2H), 8.06 (d, J=8 Hz, 2H), 7.99–8.03 (m, 3H),
0.36 ppm (s, 9H); 13C{1H} NMR (125 MHz, CDCl3): d=131.4, 131.1,
128.2, 128.1, 127.0, 126.5, 125.5, 124.5, 124.4, 120.6, 105.9, 94.8, 0.2 ppm;
MS (MALDI-TOF, positive ion mode): m/z: 298 [M]+; HRMS (EI): m/z
calcd for C21H18Si: 298.1172 [M]+; found: 298.1171; elemental analysis
calcd (%) for C21H18Si: C 84.51, H 6.08; found: C 84.21, H 6.11.
À
C B not observed); MS (MALDI-TOF, positive ion mode): m/z: 526
[M]+; HRMS (EI): m/z calcd for C40H3510B: 525.2863 [M]+; found:
525.2858; elemental analysis calcd (%) for C40H35B: C 91.25, H 6.70;
found: C 90.45, H 6.70.
2-(Dimesitylboryl)pyrene (24): Under a nitrogen atmosphere, compound
20 (0.28 g, 1.0 mmol) was dissolved in Et2O (5 mL). The solution was
cooled to À788C and a solution of nBuLi in hexanes (1.6m, 0.8 mL,
1.3 mmol) was added dropwise by using a syringe. The reaction was
warmed to room temperature and stirred for 1 h. Then, the system was
cooled to À788C and a solution of dimesitylboron fluoride (0.27 g,
1.0 mmol) in Et2O (5 mL) was added. The mixture was again warmed to
room temperature and stirred overnight. The reaction was quenched with
1m HCl (10 mL) and extracted with CH2Cl2 (3ꢅ20 mL). The organic
fractions were dried over MgSO4 and the solvent was removed under re-
duced pressure. Purification of the residue by column chromatography
(silica gel, hexane/CH2Cl2, 4:1) gave 24 (0.14 g, 31%) as a pale-yellow
solid. M.p. 174–1758C; 1H NMR (400 MHz, CDCl3): d=8.38 (s, 2H),
8.18 (d, J=8 Hz, 2H), 8.02–8.09 (m, 5H), 6.92 (s, 4H), 2.40 (s, 6H),
2.04 ppm (s, 12H); 13C{1H} NMR (125 MHz, CDCl3): d=143.5, 142.1,
141.2, 139.0, 133.0, 132.1, 130.8, 128.5 (2 overlapped signals), 127.3, 126.9,
126.8, 125.0, 124.8, 23.8, 21.4 ppm; MS (MALDI-TOF, positive ion
mode): m/z: 450 [M]+; HRMS (EI): m/z calcd for C34H3110B: 449.2550
[M]+; found: 449.2544; elemental analysis calcd (%) for C34H31B: C
90.66, H 6.94; found: C 90.90, H 6.96.
4-(Pyren-2-yl)benzoic acid methyl ester (28): Under a nitrogen atmos-
phere, compound 22 (0.10 g, 0.41 mmol), methyl 4-iodobenzoate (0.11 g,
0.42 mmol), [PdCl2ACTHNUTRGNE(UNG dppf)] (0.007 g, 0.01 mmol), and K3PO4 (0.26 g,
1.2 mmol) were dissolved in DMF (5 mL) and heated at 808C for 16 h.
The reaction was quenched with 1m HCl (10 mL) and extracted with
CH2Cl2 (3ꢅ20 mL). The combined organic layers were washed with brine
(2ꢅ80 mL) and H2O (80 mL), and dried over MgSO4, then the solvent
was removed under reduced pressure. Purification of the residue by
column chromatography (silica gel, hexane/CH2Cl2, 4:1) afforded 28
(0.083 g, 60%) as
a
pale-yellow solid. M.p. 169–1708C; 1H NMR
(500 MHz, CDCl3): d=8.37 (s, 2H), 8.20 (d, J=8 Hz, 2H), 8.18 (d, J=
8 Hz, 2H), 8.09 (s, 4H), 8.00 (t, J=8 Hz, 1H), 7.92 (d, J=8 Hz, 2H),
3.99 ppm (s, 3H); 13C{1H} NMR (125 MHz, CDCl3): d=167.2, 146.1,
137.6, 131.7, 131.3, 130.4, 129.1, 128.1, 128.0, 127.6, 126.3, 125.4, 124.6,
124.4, 123.7, 52.3 ppm; MS (MALDI-TOF): m/z: 336 [M]+; HRMS (EI):
m/z calcd for C24H16O2: 336.1145 [M]+; found: 336.1143; elemental analy-
sis calcd (%) for C24H16O2: C 85.69, H 4.79; found: C 84.73, H 4.92.
2-Ethynylpyrene (29):[11b,16f,42a,43] Compound 27 (0.11 g, 0.37 mmol) was
added to a suspension of Na2CO3 (0.14 g, 1.3 mmol) in MeOH (30 mL)
and H2O (3 mL). After stirring for 16 h at room temperature, the mixture
was diluted with H2O (10 mL) and concentrated under reduced pressure.
Then it was extracted with Et2O (3ꢅ50 mL) and the Et2O fractions were
dried over MgSO4. The solvent was removed under reduced pressure and
the residue was purified on a 5 cm silica plug eluting with hexane/Et2O
(4:1), yielding 29 (0.068 g, 81%) as a pale-yellow solid. M.p. 107–1098C
[lit. 103–1048C,[16f], 110–1128C (dec.,[42a]), 112–1148C (EtOH,[11b]), 125–
1278C (EtOH,[43])]; 1H NMR (500 MHz, CDCl3): d=8.30 (s, 2H), 8.20
(d, J=8 Hz, 2H), 8.09 (d, J=8 Hz, 2H), 7.99–8.04 (m, 3H), 3.25 ppm (s,
1H); 13C{1H} NMR (100 MHz, CD2Cl2): d=131.7, 131.5, 128.6, 128.5,
127.2, 127.0, 125.9, 124.8, 124.6, 119.9, 84.5, 77.8 ppm; MS (EI): m/z: 226
[M]+; HRMS (EI): m/z calcd for C18H10: 226.0777 [M]+; found: 226.0774.
Pyrene-2-trifluoromethanesulfonate (25): Under a nitrogen atmosphere,
compound 21 (0.66 g, 3.0 mmol) was dissolved in dry pyridine (30 mL).
After cooling to 08C, triflic anhydride (2.54 g, 9.0 mmol) was added. The
mixture was stirred at 08C for 1 h and then allowed to warm to room
temperature overnight. The reaction was quenched with H2O (20 mL)
and the mixture was extracted with CH2Cl2 (3ꢅ30 mL). The organic frac-
tions were dried over MgSO4 and the solvent was removed under re-
duced pressure. Purification of the residue by column chromatography
(silica gel, hexane/CH2Cl2, 4:1) gave 25 (0.72 g, 69%) as a pale-yellow
1
solid. M.p. 143–1458C; H NMR (700 MHz, CDCl3): d=8.26 (d, J=8 Hz,
2H), 8.17 (d, J=9 Hz, 2H), 8.08 (t, J=8 Hz, 1H), 8.05 (d, J=9 Hz, 2H),
8.04 ppm (s, 2H); 13C{1H} NMR (176 MHz, CDCl3): d=147.2, 132.9,
131.0, 129.6, 126.8, 126.7, 126.4, 124.1, 123.0, 119.1 (q, JACTHNUTRGENUGN(C,F)=320 Hz),
116.5 ppm; 19F{1H} NMR (376 MHz, CDCl3): d=À73.0 ppm; MS (ESI):
m/z: 350 [M]+; HRMS (ESI): m/z calcd for C17H9F3O3S: 349.0152
[MÀH]+; found: 349.0151; elemental analysis calcd (%) for C17H9F3O3S:
C 58.29, H 2.59; found: C 58.32, H 2.61.
4-(Pyren-2-yl)butyric acid methyl ester (30): Under a nitrogen atmos-
phere, Zn powder (0.27 g, 4.1 mmol) was added to a Youngꢄs tube. After
heating the tube at 708C under vacuum for 45 min, I2 (0.035 g,
0.14 mmol) in DMF (9 mL) was added and the mixture was stirred until
5032
ꢃ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2012, 18, 5022 – 5035