Y. Wang, P. Lu and X. Chen
(t, 3J
G
G
Typical procedure for the synthesis of 7-cyclohexenyl-12-phenyl-
(s, 1H; CH), 5.41 (s, 1H; CH), 5.19 (s, 1H; CH), 2.60 (s, 3H; CH3),
2.25 ppm (s, 3H; CH3); 13C NMR (100 MHz, CDCl3, 258C, TMS; see Fig-
ure S2 in the Supporting Information): d=144.4, 141.9, 141.0, 140.2,
137.7, 135.3, 134.8, 132.8, 129.8, 128.5, 127.7, 127.6, 127.0, 126.7, 123.5,
122.7, 115.2, 95.7, 28.9, 23.8 ppm; EIMS: m/z (%): 382 (79.29) [M+], 240
(100); HRMS: m/z: cacld for C20H15I: 382.0219 [M+]; found: 382.0223.
8,9,10,11-tetrahydrobenzo[k]fluoranthene (9): [PdACTHUNGTERN(NUG PPh3)4] (58 mg,
0.05 mmol) was added to a solution of 2b (462 mg, 1 mmol), PhB(OH)2
(146 mg, 1.2 mmol), and K2CO3 (690 mg, 5 mmol) in toluene and ethanol
(toluene/ethanol 9:1, 30 mL) at ambient temperature. The reaction mix-
ture was purged with nitrogen for 10 min. Then the sealed flask was
heated at 1008C for about 5 h. After complete consumption of 2b, deter-
mined by TLC, toluene and ethanol were removed and the residue was
dissolved in diethyl ether. The solution was washed with water and dried
over anhydrous Na2SO4. After filtration, the filtrate was distilled under
reduced pressure and the residue was purified by flash chromatography
on silica gel (eluent solvent: hexane). Compound 9 (379 mg, 92%) was
obtained as a yellow solid. M.p. 227.9–229.58C; 1H NMR (400 MHz,
CDCl3, 258C, TMS; see Figure S83 in the Supporting Information): d=
Typical procedure for the synthesis of 7-iodo-12-phenylindenoACTHNUGTRNEUNG[2,1-a]phe-
nalene (4a): In a 10 mL round-bottomed flask, 3a (164 mg, 0.5 mmol)
and NaHCO3 (84 mg, 1.0 mmol) were dissolved in CH3CN (5 mL).
Iodine (380 mg, 1.5 mmol) was added to the solution in one portion after
the temperature was raised to 508C. The solution turned in color to a
brownish red. After complete consumption of the starting material 3a as
tracked by TLC, the solution was washed with aqueous Na2S2O3 (3ꢂ
15 mL) and dried over anhydrous Na2SO4. After filtration, the filtrate
was distilled under reduced pressure and the residue was purified by
flash chromatography on silica gel (eluent solvent: hexane). Compound
4a (209 mg, 92%) was obtained as a reddish brown solid. M.p. 180.6–
181.88C; 1H NMR (400 MHz, CDCl3, 258C, TMS; see Figure S24 in the
8.02 (d, 3J
7.65 (d, 3J
7.50 (dd, 3J
2H; CH), 7.29–7.22 (m, 1H; CH), 6.37 (d, 3J
5.83 (s, 1H; CH), 3.00 (dt, 3J(H,H)=17.0, 6.4 Hz, 1H; CH), 2.74 (dt, 3J-
(H,H)=12.3, 5.8 Hz, 1H; CH), 2.45 (dt, 3J
(H,H)=59.5, 14.8 Hz, 6H),
A
ACHTUNGTREN(NUNG H,H)=8.1 Hz, 1H; CH),
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
Supporting Information): d=9.08 (m, 1H; CH), 8.21 (d, 3J
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
2.05–1.68 ppm (m, 8H); 13C NMR (100 MHz, CDCl3, 258C, TMS; see
Figure S84 in the Supporting Information): d=140.5, 139.6, 137.2, 136.63,
136.56, 134.9, 134.8, 134.6, 133.6, 133.1, 129.7, 129.2, 129.1, 129.0, 127.7,
127.5, 127.2, 125.9, 125.71, 125.66, 122.1, 122.0, 28.6, 28.5, 27.1, 25.6, 23.4,
23.2, 22.3 ppm; EIMS: m/z (%): 438 (100) [M+]; HRMS: m/z: calcd for
C32H28: 412.2191 [M+]; found: 412.2192.
7.5 Hz, 1H; CH), 7.76 (d, 3J
G
E
3
7.8 Hz, 1H; CH), 7.66 (d, J
A
7.55–7.45 (m, 4H; CH), 7.34 (m, 2H; CH), 7.23 (t, JACTHUNRTGNEUNG(H,H)=8.0 Hz, 1H;
CH), 7.04 ppm (m, 1H; CH); 13C NMR (100 MHz, CDCl3, 258C, TMS;
see Figure S25 in the Supporting Information): d=146.0, 144.0, 136.8,
136.4, 135.2, 134.8, 132.9, 132.6, 131.2, 130.8, 129.9, 128.9, 128.5, 128.1,
127.5, 126.6, 126.5, 126.0, 125.7, 124.5, 123.9, 120.6, 105.1 ppm; HRMS:
m/z: calcd for C26H15I: 454.0219 [M+]; found: 454.0207.
Typical procedure for the synthesis of 7,12-diphenylbenzo[k]fluoranthene
(12): Route B1: DDQ (1362 mg, 6 mmol) was added to a solution of 9
(412 mg, 1 mmol) in benzene (80 mL) at ambient temperature. The reac-
tion mixture was purged with nitrogen for 10 min. Then the sealed flask
was heated at 808C for about 48 h. After complete consumption of 9, as
determined by TLC, benzene was removed and the residue was dissolved
in diethyl ether. The solution was washed with water and dried over an-
hydrous Na2SO4. After filtration, the filtrate was distilled under reduced
pressure and the residue was purified by flash chromatography on silica
gel (eluent solvent: hexane). Compound 12 (307 mg, 76%) was obtained
Typical procedure for the synthesis of 7-iodo-8,8-dimethyl-9-phenyl(8-
H)cyclopenta[a]acenaphthylene (6a): In a 10 mL round-bottomed flask,
5a (155 mg, 0.5 mmol) was dissolved in dichloroethane (5 mL). Iodine
(380 mg, 1.5 mmol) was added in one portion to the solution at room
temperature. The solution turned in color to a light green, and finally to
a deep brown. After complete consumption of the starting material (5a)
as tracked by TLC, the solution was washed with aqueous Na2S2O3 (3ꢂ
15 mL) and dried over anhydrous Na2SO4. After filtration, the filtrate
was distilled under reduced pressure and the residue was purified by
flash chromatography on silica gel (eluent solvent: hexane). Compound
6a (151 mg, 72%) was obtained as a yellow solid. M.p. 74.6–76.08C;
1H NMR (400 MHz, CDCl3, 258C, TMS; see Figure S36 in the Support-
1
as a yellow solid. M.p. >3508C; H NMR (400 MHz, CDCl3, 258C, TMS;
see Figure S89 in the Supporting Information): d=7.70–7.61 (m, 10H),
7.56 (d, 3J
(H,H)=7.6 Hz, 4H; CH), 7.39 (dd, 3J
ACHUTGTNRENNUG CAHTUNGTRENNUNG
CH), 7.32 (t, 3J
G
ACHTUNGTRENNUNG
2H; CH); 13C NMR (100 MHz, CDCl3, 258C, TMS; see Figure S90 in the
Supporting Information): d=138.9, 136.6, 135.6, 134.9, 134.8, 132.9, 130.1,
130.0, 129.2, 128.0, 127.8, 126.8, 125.9, 125.8, 122.2 ppm; EIMS: m/z: 4
404 (100) [M+]; HRMS: m/z: calcd for C32H20: 404.1565 [M+]; found:
404.1563.
ing Information): d=8.11 (d, 3J
(H,H)=8.0 Hz, 1H; CH), 7.69 (d, 3J
3H), 7.49 (t, 3J
(H,H)=7.6 Hz, 2H), 7.47–7.39 (m, 3H), 1.38 ppm (s, 6H;
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
CH3); 13C NMR (100 MHz, CDCl3, 258C, TMS; see Figure S37 in the
Supporting Information): d=148.8, 147.4, 144.3, 143.0, 136.7, 132.4, 132.3,
131.7, 128.6, 128.1, 127.82, 127.78, 127.6, 125.9, 125.2, 118.7, 118.4, 100.2,
65.5, 23.9 ppm; HRMS: m/z: calcd for C23H17I: 420.0375 [M+]; found:
420.0374.
Typical procedure for the synthesis of dibenzoACTHUNTGRENNG{U [f,f’]-4,7’-diphenyl4’,7- di-
cyclohexenyl-}diindeno[1,2,3cd:1’,2’,3’-lm]perylene (13)
Route A1 method A:[32b] FeCl3 (325 mg, 2 mmol) was added to a solution
of 9 (206 mg, 0.5 mmol) in dry CH2Cl2 (50 mL) at ambient temperature.
The reaction mixture was purged with nitrogen for 10 min. Then the
sealed flask was stirred at 0–58C for about 1 h. After complete consump-
tion of 9 as determined by TLC, the solution was washed with water and
dried over Na2SO4. After filtration, the filtrate was distilled under re-
duced pressure and the residue was purified by flash chromatography on
silica gel (eluent solvent: CH2Cl2/hexane 1:15). Compound 13 (86 mg,
42%) was obtained as a red solid.
Typical procedure for the synthesis of 7-phenyl-9-methyl-10-(prop-1-en-2-
yl)acenaphthoACHTUNGTRENNUNG[1,2-c]pyridine (8a): In a 10 mL round-bottomed flask, 5a
(155 mg, 0.5 mmol) was dissolved in CH3CN (5 mL). Iodine (380 mg,
1.5 mmol) was added in one portion to the solution at room temperature.
The solution turned in color to a light green, and finally to a deep brown.
After complete consumption of starting material (5a) as tracked by TLC,
the solution was washed with aqueous Na2S2O3 (3ꢂ15 mL) and dried
over anhydrous Na2SO4. After filtration, the filtrate was distilled under
reduced pressure and the residue was purified by flash chromatography
on silica gel (eluent solvent: CH2Cl2/hexane 1:5). Compound 8a (115 mg,
69%) was obtained as yellow solid. M.p. 102.8–103.98C; 1H NMR
(400 MHz, CDCl3, 258C, TMS; see Figure S54 in the Supporting Infor-
Route A1 method B:[32a] DDQ (136 mg, 0.6 mmol) was added to a solu-
tion of 9 (206 mg, 0.5 mmol) in CH2Cl2 (50 mL) containing CH3SO3H
(10% v/v) at 0–58C. The reaction mixture was purged with nitrogen for
10 min. Then the sealed flask was stirred at 0–58C for about 1 h. After
complete consumption of 9, as determined by TLC, the reaction was
quenched with a saturated aqueous solution of NaHCO3 (100 mL). After
filtration, the filtrate was distilled under reduced pressure and the residue
was purified by flash chromatography on silica gel (eluent solvent:
CH2Cl2/hexane 1:15). Compound 13 (119 mg, 56%) was obtained as a
red solid. M.p. >3508C; 1H NMR (500 MHz, CDCl3, 258C, TMS; see
mation): d=8.25 (d, 3J
1H; CH), 7.81 (m, 3H), 7.65 (t, 3J
AHCTUNGTRENNUNG
N
ACHTUNGTREN(NUNG H,H)=8.2 Hz,
3H), 7.45 (m, 2H), 5.60 (s, 1H; CH), 5.24 (s, 1H; CH), 2.72 (s, 3H;
CH3), 2.30 ppm (s, 3H; CH3); 13C NMR (100 MHz, CDCl3, 258C, TMS;
see Figure S55 in the Supporting Information): d=154.3, 152.8, 143.7,
142.3, 140.6, 134.7, 134.5, 132.9, 132.6, 130.0, 129.2, 129.0, 128.65, 128.60,
127.92, 127.87, 126.8, 124.7, 123.0, 116.6, 23.1, 22.1 ppm; HRMS: m/z:
calcd for C25H19N: 333.1517 [M+]; found: 333.1518.
Figure S91 in the Supporting Information): d=8.17 (d, 3J
1H; CH), 8.04 (d, 3J(H,H)=7.7 Hz, 1H; CH), 7.96 (d, 3J
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
G
8112
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 8105 – 8114