LETTER
(b) Chanda, N.; Sharp, P. R. Organometallics 2007, 26,
1,2-Disubstituted Acenaphthylenes
1589
1-(4-Ethylphenyl)-2-phenylacenaphthylene (3g)
Orange oil; yield: 114 mg (69%). 1H NMR (400 MHz,
CDCl3): δ = 7.83 (dd, J = 8.1, 2.3 Hz, 2 H), 7.73 (dd,
1635.
(12) Brown, J. S.; Sharp, P. Organometallics 2003, 22, 3604.
(13) (a) Grigg, R.; Kennewell, P.; Teasdale, A.; Sridharan, V.
Tetrahedron Lett. 1993, 34, 153. (b) Jafarpour, F.; Hazrati,
H.; Nouraldinmousa, S. Org. Lett. 2013, 15, 3816.
(14) (a) Seyferth, D.; Vick, S. C. J. Organomet. Chem. 1977, 141,
173. (b) Kuroda, M.; Nakayama, J.; Hoshino, M.; Furusho,
N.; Kawata, T.; Ohba, S. Tetrahedron 1993, 49, 3735.
(15) 1,2-Disubstituted Acenaphthylenes 3a–p; General
Procedure
J = 14.9, 6.8 Hz, 2 H), 7.55–7.59 (m, 2 H), 7.44–7.46 (m, 2
H), 7.34–7.38 (m, 4 H), 7.29–7.31 (m, 1 H), 7.18 (d, J = 8.2
Hz, 2 H), 2.68 (q, J = 7.6 Hz, 2 H), 1.27 (t, J = 7.6 Hz, 3 H).
13C NMR (101 MHz, CDCl3): δ = 143.2, 140.2, 140.1, 138.2,
137.7, 135.5, 132.5, 130.1, 130.0, 128.4, 128.4, 128.3,
127.9, 127.8, 127.2, 127.1, 127.0, 124.1, 123.8, 28.7, 15.3.
HRMS (EI): m/z calcd for C26H20: 332.1565; found:
332.1567.
A Schlenk flask was charged with dibromoarene 1 (0.5
mmol), alkyne 2 (0.6 mmol), Pd(OAc)2 (5 mol%), Xantphos
(5.5 mol%) and K2CO3 (1.5 mmol) under N2. Anhyd DMF
(5 mL) was added from a syringe, and the mixture was
stirred at 120 °C until the reaction was complete (TLC). The
mixture was cooled to r.t., and H2O (10 mL) was added. The
resulting mixture was extracted with EtOAc (3 × 15 mL).
The organic layers were combined, dried (Na2SO4), and
concentrated to give a residue that was purified by column
chromatography (silica gel, PE–EtOAc).
Methyl 4-(2-phenylacenaphthylen-1-yl)benzoate (3b)
Orange solid; yield: 125 mg (69%); mp 166–167 °C. 1H
NMR (300 MHz, CDCl3): δ = 8.03 (d, J = 8.3 Hz, 2 H), 7.88
(dd, J = 8.0, 2.2 Hz, 2 H), 7.73–7.78 (m, 2 H), 7.59–7.64 (m,
2 H), 7.51 (d, J = 8.3 Hz, 2 H), 7.35–7.43 (m, 5 H), 3.93 (s,
3 H). 13C NMR (75 MHz, CDCl3): δ = 167.1, 140.3, 139.7,
139.6, 139.4, 136.9, 134.8, 130.0, 129.7, 128.6, 128.6,
128.3, 127.9, 127.9, 127.8, 127.6, 127.5, 124.5, 124.0, 52.1.
HRMS (EI): m/z calcd for C26H18O2: 362.1307; found:
362.1305.
1-Butyl-2-phenylacenaphthylene (3h)
Yellow oil; yield: 109 mg (77%). 1H NMR (400 MHz,
CDCl3): δ = 7.69–7.79 (m, 3 H), 7.51–7.58 (m, 7 H), 7.36–
7.49 (m, 1 H), 2.87 (t, J = 7.6 Hz, 2 H), 1.75 (t, J = 7.6 Hz, 2
H), 1.42 (dd, J = 14.8, 7.4 Hz, 2 H), 0.91 (t, J = 7.3 Hz, 3 H).
13C NMR (101 MHz, CDCl3): δ = 140.7, 139.9, 137.9, 135.8,
129.6, 128.5, 128.5, 128.2, 127.7, 127.7, 127.1, 126.9,
126.4, 122.6, 122.4, 33.6, 26.1, 23.1, 14.0. HRMS (EI): m/z
calcd for C22H20: 284.1565; found: 284.1566.
1-Phenyl-2-propylacenaphthylene (3i)
Yellow oil; yield: 112 mg (83%). 1H NMR (400 MHz,
CDCl3): δ = 7.69–7.79 (m, 3 H), 7.47–7.58 (m, 7 H), 7.38 (t,
J = 7.2 Hz, 1 H), 2.84 (t, J = 7.2 Hz, 2 H), 1.76–1.82 (m, 2
H), 1.00 (t, J = 7.3 Hz, 3 H). 13C NMR (101 MHz, CDCl3):
δ = 140.6, 140.6, 139.6, 138.0, 135.7, 129.5, 128.4, 128.3,
128.1, 127.7, 127.6, 127.0, 126.9, 126.4, 122.6, 122.3, 28.4,
24.6, 14.5. HRMS (EI): m/z calcd for C21H18: 270.1409;
found: 270.1410.
5,6-Bis(4-tert-butylphenyl)-1,2-dihydrocyclopenta-
[f,g]acenaphthylene (3l)
1-(4-Chlorophenyl)-2-phenylacenaphthylene (3c)
Orange solid; yield: 125 mg (74%); mp 122–123 °C. 1H
NMR (300 MHz, CDCl3): δ = 7.87 (d, J = 8.1 Hz, 2 H), 7.72
(dd, J = 10.9, 6.9 Hz, 2 H), 7.58–7.63 (m, 2 H), 7.31–7.44
(m, 9 H). 13C NMR (75 MHz, CDCl3): δ = 157.2, 139.8,
139.6, 138.7, 136.8, 135.0, 133.8, 133.1, 131.4, 130.1,
128.7, 128.6, 128.2, 127.9, 127.9, 127.6, 127.5, 127.4,
124.3, 123.8. HRMS (EI): m/z calcd for C24H15Cl: 338.0862;
found: 338.0862.
Orange solid; yield: 170 mg (77%); mp 170–171 °C. 1H
NMR (400 MHz, CDCl3): δ = 7.81 (d, J = 7.0 Hz, 2 H),
7.46–7.48 (m, 4 H), 7.42 (d, J = 7.0 Hz, 2 H), 7.36–7.38 (m,
4 H), 3.52 (s, 4 H), 1.36 (s, 18 H). 13C NMR (101 MHz,
CDCl3): δ = 149.6, 146.5, 137.1, 136.2, 135.3, 133.5, 129.6,
127.0, 126.0, 125.2, 120.7, 34.6, 32.6, 31.4. HRMS (EI): m/z
calcd for C34H34: 442.2661; found: 442.2658.
5,6-Diphenyl-1,2-dihydrocyclopenta[f,g]acenaphthylene
(3m)
1,2-Bis(2-chlorophenyl)acenaphthylene (3d)
Orange solid; yield: 66 mg (40%); mp 219–221 °C. 1H NMR
(400 MHz, CDCl3): δ = 7.82 (d, J = 6.9 Hz, 2 H), 7.51–7.53
(m, 4 H), 7.46 (d, J = 7.0 Hz, 2 H), 7.34–7.38 (m, 4 H), 7.30
(m, 2 H), 3.55 (s, 4 H). 13C NMR (101 MHz, CDCl3): δ =
146.9, 137.6, 136.3, 135.7, 135.4, 130.0, 128.4, 126.8,
126.0, 120.8, 32.6. HRMS (EI): m/z calcd for C26H18:
330.1409; found: 330.1399.
Yellow solid; yield: 121 mg (65%); mp 152–154 °C. 1H
NMR (400 MHz, CDCl3): δ = 7.85–7.88 (m, 2 H), 7.54–7.62
(m, 4 H), 7.41–7.45 (m, 2 H), 7.28 (ddd, J = 10.1, 4.8, 2.7
Hz, 3 H), 7.25–7.15 (m, 3 H). 13C NMR (101 MHz, CDCl3):
δ = 139.3, 138.7, 138.1, 134.5, 134.1, 134.1, 133.8, 132.1,
132.1, 130.2, 129.5, 129.0, 128.8, 128.5, 128.0, 127.7,
127.7, 127.6, 127.6, 126.7, 126.3, 124.7, 124.5. HRMS (EI):
m/z calcd for C24H14Cl2: 372.0473; found: 362.0477.
1,2-Bis(4-tert-butylphenyl)acenaphthylene (3e)
Orange solid; yield: 172 mg (83%); mp 164–165 °C. 1H
NMR (300 MHz, CDCl3): δ = 7.83 (d, J = 8.1 Hz, 2 H), 7.75
(d, J = 6.8 Hz, 2 H), 7.54–7.59 (m, 2 H), 7.35–7.42 (m, 8 H),
1.36 (s, 18 H). 13C NMR (75 MHz, CDCl3): δ = 149.9, 140.4,
137.6, 132.4, 129.7, 128.3, 128.3, 127.7, 127.0, 125.2,
123.9, 34.6, 31.4. HRMS (EI): m/z calcd for C32H32:
416.2504; found: 416.2507.
5,6-Bis(2-chlorophenyl)-1,2-dihydrocyclopenta-
[f,g]acenaphthylene (3n)
Yellow solid; yield: 46 mg (23%); mp 207–210 °C. 1H NMR
(400 MHz, CDCl3): δ = 7.69 (dd, J = 15.4, 6.9 Hz, 2 H),
7.41–7.45 (m, 4 H), 7.30 (d, J = 6.0 Hz, 1 H), 7.11–7.29 (m,
5 H), 3.52 (s, 4 H). 13C NMR (101 MHz, CDCl3): δ = 147.3,
147.3, 138.2, 137.6, 135.4, 135.1, 134.0, 133.9, 132.3,
132.2, 130.2, 129.5, 128.7, 128.5, 126.8, 126.6, 126.6,
126.2, 120.7, 120.6, 32.7. HRMS (EI): m/z calcd for
C26H16Cl2: 398.0629; found: 398.0616.
1-Mesityl-2-phenylacenaphthylene (3f)
5-Butyl-6-phenyl-1,2-dihydrocyclopenta-
Yellow oil; yield: 52 mg (30%). 1H NMR (400 MHz,
CDCl3): δ = 7.80–7.85 (m, 3 H), 7.60 (dd, J = 8.0, 7.1 Hz, 1
H), 7.50 (dd, J = 8.1, 6.9 Hz, 1 H), 7.37–7.39 (m, 2 H), 7.27–
7.32 (m, 3 H), 7.24 (d, J = 2.6 Hz, 1 H), 6.91 (s, 2 H), 2.33
(s, 3 H), 2.03 (s, 6 H). 13C NMR (101 MHz, CDCl3): δ =
140.4, 139.9, 138.4, 138.2, 137.1, 136.8, 135.8, 131.5,
128.7, 128.4, 128.3, 128.2, 127.9, 127.6, 127.0, 127.0,
123.7, 123.2, 21.2, 20.6. HRMS (EI): m/z calcd for C27H22:
346.1722; found: 346.1720.
[f,g]acenaphthylene (3o)
Yellow solid; yield: 103 mg (66%); mp 87–88 °C. 1H NMR
(400 MHz, CDCl3): δ = 7.76 (d, J = 6.9 Hz, 1 H), 7.58–7.62
(m, 3 H), 7.47–7.50 (m, 2 H), 7.34–7.41 (m, 3 H), 3.48 (s, 4
H), 2.94 (t, J = 6.5 Hz, 2 H), 1.80 (t, J = 6.4 Hz, 2 H), 1.41–
1.50 (m, 2 H), 0.92 (t, J = 7.3 Hz, 3 H). 13C NMR (101 MHz,
CDCl3): δ = 146.3, 145.7, 139.7, 137.4, 136.7, 136.5, 136.3,
135.1, 129.5, 128.4, 127.0, 126.7, 124.6, 124.6, 120.5,
120.5, 33.6, 32.6, 32.4, 27.0, 23.0, 14.0. HRMS (EI): m/z
© Georg Thieme Verlag Stuttgart · New York
Synlett 2014, 25, 1585–1590