A. Fürstner et al.
FULL PAPER
2-(2-Prop-1-ynyl-phenyl)-1H-indole (34): 1H NMR (400 MHz, CD2Cl2):
d=9.60 (brs, 1H), 7.74 (dd, J=8, 0.9 Hz, 1H), 7.61 (dd, J=7.9, 0.9 Hz,
1H), 7.50 (dd, J=8, 0.8 Hz, 1H), 7.41 (dt, J=8.2, 0.8 Hz, 1H), 7.36 (dd,
J=8, 1.4 Hz, 1H), 7.24 (dt, J=8, 1.3 Hz, 1H), 7.18 (dt, J=8.1, 1.1 Hz,
1H), 7.08 (dt, J=7.9, 0.9 Hz, 1H), 6.94 (dd, J=2.2, 0.9 Hz, 1H), 2.17 (s,
3H); 13CNMR (100 MHz, CD 2Cl2): d=137.1, 136.4, 134.4, 133.1, 128.5,
128.4, 127.9, 127.3, 122.5, 120.6, 120.2, 111.1, 101.8, 91.0, 78.8, 4.5; IR
(KBr): n˜ =3407, 3054, 2910, 2845, 2227, 1616, 1595, 1532, 1471, 1446,
760 cmꢀ1; MS (EI): m/z (%): 231 (100) [M +], 204 (12); elemental analy-
sis calcd (%) for C17H13N (231.29): C88.28, H 5.67, N 6.06; found: C
88.20, H 5.75, N 6.12.
3H); 13CNMR (100 MHz, CDCl 3): d=159.4, 157.5, 133.2, 132.6, 130.0,
129.0, 127.0, 126.3, 124.0, 123.5, 120.7, 118.9, 98.1, 95.7, 56.1, 55.9; IR
(KBr): n˜ =3050, 3000, 2958, 2936, 2834, 1619, 1601, 1579, 1521, 1505,
1466, 1454, 1424, 1403, 1269, 1153, 815, 750 cmꢀ1; MS (EI): m/z (%): 238
(100) [M +], 223 (8), 195 (24), 180 (14), 163 (6), 152 (22).
Benzo[c]phenanthrene (13):[77] 1H NMR (400 MHz, CDCl3): d=9.04 (d,
J=8.4 Hz, 2H), 7.92 (dd, J=7.9, 1.4 Hz, 2H), 7.79 (d, J=8.5 Hz, 2H),
7.72 (d, J=8.5 Hz, 2H), 7.59 (dt, J=6.9, 1.5 Hz, 2H), 7.52 (dt, J=7,
1 Hz, 2H); 13CNMR (100 MHz, CDCl 3): d=135.0, 132.4, 131.8, 128.2,
127.6, 127.1, 126.5, 125.8, 125.5; IR (KBr): n˜ =3049, 3008, 1600, 1519,
1495, 833, 746 cmꢀ1; MS (EI): m/z (%): 228 (100) [M +], 113 (25).
1-Methyl-2-(2-prop-1-ynyl-phenyl)-1H-indole (28): A solution of com-
pound 34 (105 mg, 0.24 mmol) in THF (1 mL) was added to a suspension
of NaH (13.1 mg, 0.546 mmol) in THF (1 mL) at ambient temperature
and the resulting mixture was heated under reflux for 30 min. After cool-
ing to ambient temperature, freshly distilled methyl iodide (34 mL,
0.546 mmol) was added and the resulting mixture was stirred overnight.
A standard extractive work-up followed by flash chromatography (hex-
anes/EtOAc 9:1) gave product 28 as a colorless syrup (92 mg, 83%). 1H
NMR (400 MHz, CD2Cl2): d=7.61 (dd, J=7.8, 0.9 Hz, 1H), 7.55 (m,
1H), 7.38 (m, 3H), 7.23 (dt, J=8.2, 1.2 Hz, 1H), 7.12 (dt, J=7.9, 1 Hz,
1H), 6.53 (d, J=0.7 Hz, 1H), 3.64 (s, 3H), 1.88 (s, 3H); 13CNMR
(100 MHz, CD2Cl2): d=140.5, 138.0, 135.0, 132.9, 131.4, 128.3, 128.2,
128.1, 127.6, 124.9, 121.5, 120.5, 119.7, 109.7, 102.1, 89.4, 18.6, 31.0, 4.2;
IR (KBr): n˜ =3056, 3022, 2948, 2913, 2848, 2229, 1609, 1542, 1466, 1429,
739 cmꢀ1; MS (EI): m/z (%): 245 (100) [M +], 230 (50), 202 (15); elemen-
tal analysis calcd (%) for C18H15N (245.32): C88.13, H 6.16, N 5.71;
found: C88.11, H 6.12, N 5.76.
1
Dibenzo[c,g]phenanthrene (15): H NMR (400 MHz, CDCl3): d=8.50 (d,
J=8.4 Hz, 2H), 7.95–7.75 (m, 8H), 7.51 (dt, J=6.9, 1 Hz, 2H), 7.27 (m,
2H); 13C(100 MHz, CDCl 3): d=132.6, 132.3, 130.8, 129.1, 127.8, 127.5,
127.3, 127.0, 126.4, 126.3, 124.4; IR (KBr): n˜ =3044, 839, 746 cmꢀ1; MS
(EI): m/z (%): 277 (100) [M +ꢀH], 138 (37).
5,6-Dihydro-benzo[c]phenanthrene (17):[78] 1H NMR (300 MHz, CDCl3):
d=8.46 (d, J=8.4 Hz, 1H), 7.85 (d, J=7.8 Hz, 1H), 7.78 (d, J=7.8 Hz,
1H), 7.64 (d, J=8.2 Hz, 1H), 7.37 (m, 2H), 7.25 (m, 2H), 7.19 (t, J=
7.3 Hz, 1H), 2.82 (m, 2H), 2.74 (m, 2H); 13C NMR (75 MHz, CDCl3):
d=139.3, 136.8, 133.8, 133.5, 131.3, 129.7, 128.3, 128.25, 127.4, 127.2,
126.5, 126.1, 125.7, 125.6, 125.2, 124.5, 30.2, 29.1; IR (KAP): n˜ =3050,
2937, 2892, 2834, 1619, 1594, 1510, 1485, 1448, 1428, 1381, 813, 791, 757,
737 cmꢀ1; MS (EI): m/z (%): 230 (100) [M +], 215 (18), 202 (8).
1-Methoxyphenanthrene (19a):[80] 1H NMR (400 MHz, CDCl3): d=8.59
(d, J=8.2, 1H), 8.20 (d, J=8.5 Hz, 1H), 8.16 (d, J=9.2 Hz, 1H), 7.82
(dd, J=7.6, 1.4 Hz, 1H), 7.67 (d, J=9.1 Hz, 1H), 7.60–7.45 (m, 3H), 6.94
(d, J=7.8 Hz, 1H), 3.97 (s, 3H); 13CNMR (100 MHz, CDCl 3): d=156.3,
132.6, 131.9, 130.4, 128.9, 127.0, 126.9, 126.7, 126.4, 123.6, 123.5, 120.7,
115.4, 106.2, 56.1; IR (KBr): n˜ =3051, 3001, 2956, 2935, 2831, 1620, 1608,
1597, 1522, 1463, 1434, 1253, 803, 754 cmꢀ1; MS (EI): m/z (%): 208 (100)
[M +], 193 (39), 165 (64).
Phenanthrenes and polycyclic heterocycles—Representative procedure
for PtCl2-catalyzed cycloisomerization reactions
1,3,10-Trimethyl-6,7-methylenedioxy-phenanthrene (23):
A solution of
alkyne 22 (528 mg, 2.0 mmol) and PtCl2 (26.6 mg, 0.1 mmol) in toluene
(10 mL) was stirred for 24 h at 808Cunder Ar until GCshowed complete
conversion of the substrate. For work up, the solvent was evaporated and
the residue was purified by flash chromatography (hexanes) to give phen-
anthrene 23 as a colorless solid (495 mg, 94%). M.p. 126–1278C; 1H
NMR (400 MHz, CDCl3): d=8.08 (s, 1H), 7.87 (s, 1H), 7.24 (s, 1H), 7.09
(s, 1H), 6.98 (s, 1H), 5.98 (s, 2H), 2.83 (s, 3H), 2.82 (s, 3H), 2.44 (s, 3H);
13CNMR (100 MHz, CDCl 3): d=147.1, 147.0, 135.5, 134.4, 131.7, 131.6,
131.4, 129.0, 127.8, 125.4, 120.9, 104.0, 100.9, 100.7, 26.1, 25.7, 21.1; IR
(KBr): n˜ =2965, 2931, 2904, 1614, 1596, 1504, 1490, 1460, 1438, 1233,
1039, 942, 876 cmꢀ1; MS (EI): m/z (%): 264 (100) [M +], 249 (18), 189
(11); elemental analysis calcd (%) for C18H16O2 (264.33): C81.79, H 6.10;
found: C81.75, H 6.13.
3,5-Dimethylphenanthrene (8a):[75] 1H NMR (400 MHz, CDCl3): d=8.76
(d, J=8.3 Hz), 8.45 (s, 1H), 7.96 (m, 2H), 7.78 (d, J=9.1 Hz, 1H), 7.75–
7.60 (m, 2H), 7.36 (s, 1H), 2.79 (s, 3H), 2.66 (s, 3H); 13CNMR
(100 MHz, CDCl3): d=135.4, 135.1, 134.3, 131.6, 130.1, 129.3, 128.5,
128.1, 126.0, 125.9, 125.4, 122.6, 122.4, 120.3, 21.7, 19.5; IR (KBr): n˜ =
3047, 3007, 2962, 2918, 2853, 1616, 1604, 1504, 1462, 1425, 1377, 858, 817,
754 cmꢀ1; MS (EI): m/z (%): 206 (100) [M +], 223 (18), 191 (42).
3-Methoxyphenanthrene (19b):[76,79,80] 1H NMR (400 MHz, CDCl3): d=
8.53 (d, J=7.6, 1H), 7.99 (d, J=2.4 Hz, 1H), 7.80 (dd, J=9.2, 7.7 Hz,
1H), 7.73 (d, J=8.7 Hz, 1H), 7.61 (d, J=8.8 Hz, 1H), 7.60–7.45 (m, 3H),
7.18 (dd, J=8.6, 2.1 Hz, 1H), 3.95 (s, 3H); 13C NMR (100 MHz, CDCl3):
d=158.1, 133.2, 132.1, 131.3, 129.6, 128.2, 126.4, 126.25, 126.2, 125.7,
124.2, 122.3, 116.3, 103.7, 55.1; MS (EI): m/z (%): 208 (100) [M +], 193
(24), 165 (60); IR (KBr): n˜ =3070, 3008, 2964, 2929, 2831, 1619, 1602,
1507, 1455, 1438, 1425, 1224, 843, 745 cmꢀ1
.
4-Methoxyphenanthrene (21):[81] 1H NMR (400 MHz, CDCl3): d=9.59
(dd, J=8.6, 0.6 Hz), 7.80 (dd, J=7.7, 1.6 Hz), 7.70–7.40 (m, 6H), 7.09 (d,
J=9.1, 1H), 4.07 (s, 3H); 13CNMR (100 MHz, CDCl 3): d=158.5, 134.3,
132.4, 130.0, 128.2, 127.9, 127.6, 126.7, 126.1, 126.0, 125.5, 121.2, 120.5,
108.0, 55.4; IR (KBr):n˜ =3138, 3048, 2995, 2962, 2939, 2835, 1609, 1598,
1569, 1449, 1431, 1417, 1245, 823, 739, 713 cmꢀ1; MS (EI): m/z (%): 208
(100) [M +], 193 (27), 165 (55).
Naphtho[1,2-b]thiophene (25a):[82] 1H NMR (400 MHz, CDCl3): d=8.13
(dd, J=8.1, 7.6 Hz, 1H), 7.92 (dd, J=8.5, 1 Hz, 1H), 7.72 (d, J=8.6 Hz,
1H), 7.55 (dd, J=8, 1.2 Hz, 1H), 7.50 (dt, J=4.1, 1.3 Hz, 2H), 7.45 (d,
J=5.3 Hz, 1H); 13CNMR (75 MHz, CDCl 3): d=137.42, 137.39, 130.8,
129.1, 128.8, 126.6, 125.6, 125.3, 125.1, 125.0, 123.6, 122.0.
4-Phenyl-naphtho[1,2-b]thiophene (25b): 1H NMR (300 MHz, CD2Cl2):
d=8.21 (d, J=7.8 Hz, 1H), 8.02 (d, J=7.7 Hz, 1H), 7.77 (s, 1H), 7.70
(dd, J=8.1, 1.6 Hz, 1H), 7.64–7.45 (m, 8H); 13CNMR (100 MHz,
CDCl3): d=141.6, 138.9, 137.2, 137.0, 131.8, 129.9, 129.6, 129.3, 129.0,
128.3, 127.4, 126.8, 125.9, 125.8, 125.4, 124.2; IR (KBr): n˜ =3048, 1492,
1470, 1446, 1436, 882, 779, 733, 682 cmꢀ1; MS (EI): m/z (%): 260 (100)
[M +], 215 (20); elemental analysis calcd (%) for C18H12S (260.35): C
83.04, H 4.65; found: C83.12, H 4.52.
1H-Benzo[g]indole (27a):[83] 1H NMR (400 MHz, CD2Cl2): d=8.93 (brs,
1H), 7.95 (d, J=8.2 Hz, 1H), 7.83 (d, J=8.1 Hz, 1H), 7.61 (d, J=8.1 Hz,
1H), 7.44 (m, 2H), 7.35 (dt, J=7, 1.2 Hz, 1H), 7.22 (t, J=2.8 Hz, 1H),
6.60 (dd, J=3, 2 Hz, 1H); 13CNMR (100 MHz, CD 2Cl2): d=131.2, 131.1,
129.5, 126.4, 126.2, 124.6, 123.1, 122.5, 121.5, 121.3, 120.1, 104.9; IR
(KBr): n˜ =3428, 3414, 3065, 3045, 2960, 2925, 2852, 1623, 1594, 1568,
1528, 1494, 1469, 1450, 811, 721, 688 cmꢀ1; MS (EI): m/z (%): 167 (100)
[M +], 139 (22).
1
1,3,10-Trimethylphenanthrene (8b): H NMR (400 MHz, CDCl3): d=8.63
(dd, J=7.8, 1.5 Hz), 8.45 (s, 1H), 7.76 (dd, J=7.8, 1.5 Hz, 1H), 7.56 (m,
2H), 7.48 (s, 1H), 7.27 (s, 1H), 2.99 (s, 6H), 2.58 (s, 3H); 13CNMR
(100 MHz, CDCl3): d=135.4, 134.7, 133.3, 132.3, 131.4, 131.4, 129.5,
128.1, 126.9, 126.0, 125.2, 122.5, 121.2, 114.0, 26.3, 25.7, 21.1; IR (KBr):
n˜ =3042, 2970, 2911, 2855, 1613, 1600, 1571, 1494, 1462, 1450, 1439, 876,
751 cmꢀ1; MS (EI): m/z (%): 220 (100) [M +], 205 (40), 189 (11); elemen-
tal analysis calcd (%) for C17H16 (220.32): C92.68, H 7.32; found: C
92.47, H 7.28.
1
1,3-Dimethyl-10-phenyl-phenanthrene (8e): H NMR (400 MHz, CDCl3):
d=8.70 (dd, J=8.2, 1.3 Hz, 1H), 8.50 (d, J=0.5 Hz, 1H), 7.81 (dd, J=
7.8, 1.7 Hz, 1H), 7.62 (ddd, J=8.4, 6.9, 1.5 Hz, 1H), 7.56 (ddd, J=8.4,
6.9, 1.5 Hz, 1H), 7.53 (s, 1H), 7.41 (m, 3H), 7.20 (d, J=0.6 Hz, 1H), 2.58
(s, 3H), 2.03 (s, 3H); 13CNMR (100 MHz, CDCl 3): d=145.4, 138.7,
136.0, 135.6, 132.5, 132.0, 131.0, 130.2, 129.9, 129.3, 129.2, 128.3, 127.8,
126.7, 126.3, 122.9, 121.2, 25.2, 21.7.
1,3-Dimethoxy-phenanthrene (11):[76] 1H NMR (400 MHz, CDCl3): d=
8.50 (d, J=7.7 Hz, 1H), 8.06 (d, J=9 Hz, 1H), 7.80 (dd, J=9.2, 1.9 Hz,
1H), 7.60–7.45 (m, 4H), 6.60 (d, J=2.1 Hz, 1H), 3.96 (s, 3H), 3.94 (s,
4566
ꢀ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2004, 10, 4556 – 4575