C.-M. Che et al.
FULL PAPERS
(2 mL) was stirred at room temperature for 15 min. Allene (0.3 mmol)
and indole (1.5 mmol) were added successively and the mixture was
stirred for 12 h to 20 h until completion of the reaction. The reaction mix-
ture was concentrated and loaded directly onto a silica column; elution
with ethyl acetate/hexane afforded the product.
1-Methyl-3-((E)-1,3-di-o-tolylallyl)-1H-indole (3 f): Yellow solid, analyti-
cal TLC (silica gel 60, 5% EtOAc in hexane), Rf =0.51; 1H NMR
(300 MHz, CDCl3): d=2.30 (s, 3H), 2.41 (s, 3H), 3.72 (s, 3H), 5.29 (d,
J=7.2 Hz, 1H), 6.47–6.61 (m, 2H), 6.65 (s, 1H), 7.00 (t, J=7.2 Hz, 1H),
7.11–7.21 (m, 6H), 7.23–7.32 (m, 3H), 7.41 (d, J=8.2 Hz, 1H), 7.48–
7.60 ppm (m, 1H); 13C NMR (100 MHz, CDCl3): d=20.09, 20.25, 42.87,
109.62, 117.32, 119.28, 120.36, 122.07, 126.23, 126.46, 126.50, 126.76,
127.50, 127.89, 128.12, 128.66, 129.06, 130.61, 130.87, 134.06, 135.76,
136.60, 137.35, 137.91, 142.10 ppm; IR (KBr, neat): n˜ =3058, 3025, 2930,
1602, 1459, 1360, 1266, 1186, 967, 741, 701 cmÀ1; EIMS m/z 351 (M+);
HRMS (EI) for C26H25N, calcd 351.1987, found 351.1989; 7% ee deter-
mined by HPLC (Chiral OD column, 2-propanol/hexane=0.6:99.4,
0.45 mLminÀ1, major isomer 22.17 min, minor isomer 15.07 min).
1-Methyl-3-((E)-1,3-diphenylallyl)-1H-indole (3a): Yellow solid, analyti-
cal TLC (silica gel 60, 2% EtOAc in hexane), Rf =0.25; 1H NMR
(300 MHz, CDCl3): d=3.69 (s, 3H), 5.09 (d, J=7.3 Hz, 1H), 6.41 (d, J=
15.8 Hz, 1H), 6.68–6.75 (m, 2H), 6.99 (t, J=7.1 Hz, 1H), 7.17–7.42 ppm
(m, 13H); 13C NMR (75 MHz, CDCl3): d=32.69, 46.16, 109.16, 118.15,
118.86, 119.94, 121.62, 126.30, 126.33, 127.12, 127.36, 128.39, 128.47,
130.42, 132.71, 137.53, 143.54 ppm; IR (KBr, neat): n˜ =3058, 3024, 2932,
1599, 1489, 1472, 1372, 1329, 1156, 968, 741, 700 cmÀ1; EIMS m/z 323
(M+); HRMS (EI) for C24H2N, calcd 323.1674, found 323.1675; 41% ee
determined by HPLC (Chiral OD column, 2-propanol/hexane=1:99,
0.7 mLminÀ1, major isomer 12.47 min, minor isomer 13.86 min).
5-Chloro-1-methyl-3-((E)-1,3-di-p-tolylallyl)-1H-indole (3g): Yellow
solid, analytical TLC (silica gel 60, 5% EtOAc in hexane), Rf =0.51;
1H NMR (300 MHz, CDCl3): d=2.31 (s, 3H), 2.34 (s, 3H), 3.71 (s, 3H),
4.98 (d, J=7.2 Hz, 1H), 6.34 (d, J=15.8 Hz, 1H), 6.56 (dd, J1 =7.2 Hz,
J2 =15.8 Hz, 1H), 6.76 (s, 1H), 7.07–7.12 (m, 5H), 7.17–7.20 (m, 3H),
7.24–7.25 (m, 2H), 7.49 ppm (s, 1H); 13C NMR (75 MHz, CDCl3): d=
21.03, 21.13, 32.86, 45.46, 110.18, 117.18, 119.27, 121.89, 124.68, 126.19,
128.23, 128.59, 129.16, 130.29, 131.44, 134.63, 135.80, 135.94, 136.93,
140.19 ppm; IR (KBr, neat): n˜ =3057, 3025, 2932, 1697, 1597, 1504, 1227,
1158, 972, 833, 741 cmÀ1; EIMS m/z 312 (M+); HRMS (EI) for C22H20N2,
calcd 312.1626, found 312.1621; 40% ee determined by HPLC (Chiral
OD column, 2-propanol/hexane=0.6:99.4, 0.45 mLminÀ1, major isomer
21.41 min, minor isomer 20.47 min).
1-Methyl-3-((E)-1,3-di-p-tolylallyl)-1H-indole (3b): Yellow solid, analyti-
cal TLC (silica gel 60, 2% EtOAc in hexane), Rf =0.25; 1H NMR
(300 MHz, CDCl3): d=2.32 (s, 3H), 2.33 (s, 3H), 3.67 (s, 3H), 5.05 (d,
J=7.2 Hz, 1H), 6.41 (d, J=15.8 Hz, 1H), 6.61 (dd, J1 =7.3 Hz, J2 =
15.8 Hz, 1H), 6.74 (s, 1H), 6.98 (t, J=7.4 Hz, 1H), 7.07–7.12 (m, 4H),
7.16–7.30 (m, 6H), 7.42 ppm (d, J=7.9 Hz, 1H); 13C NMR (75 MHz,
CDCl3): d=21.03, 21.11, 32.65, 45.73, 109.10, 117.38, 118.78, 119.99,
121.53, 126.18, 127.29, 128.32, 129.05, 129.11, 130.03, 131.91, 134.78,
135.72, 136.76, 137.15, 140.65 ppm; IR (KBr, neat): n˜ =3057, 3025, 2930,
1600, 1459, 1360, 1266, 1185, 969, 741, 701 cmÀ1; EIMS m/z 351 (M+);
HRMS (EI) for C26H25N, calcd 351.1987, found 351.1988; 60% ee deter-
mined by HPLC (Chiral OD column, 2-propanol/hexane=1:99,
0.7 mLminÀ1, major isomer 14.76 min, minor isomer 17.56 min).
Methyl 1-methyl-3-((E)-1,3-di-p-tolylallyl)-1H-indole-6-carboxylate (3h):
Yellow solid, analytical TLC (silica gel 60, 5% EtOAc in hexane), Rf =
0.51; 1H NMR (300 MHz, CDCl3): d=2.31 (s, 3H), 2.33 (s, 3H), 3.79 (s,
3H), 3.94 (s, 3H), 5.04 (d, J=6.1 Hz, 1H), 6.35 (d, J=15.8 Hz, 1H), 6.58
(dd, J1 =7.2 Hz, J2 =15.8 Hz, 1H), 6.89 (s, 1H), 7.07–7.13 (m, 4H), 7.18–
7.26 (m, 4H), 7.40 (d, J=8.4 Hz, 1H), 7.67 (dd, J1 =1.1 Hz, J2 =8.4 Hz,
1H), 8.10 ppm (s, 1H); 13C NMR (75 MHz, CDCl3): d=21.04, 21.13,
32.88, 45.56, 51.90, 111.69, 117.95, 119.57, 119.89, 123.19, 126.19, 127.84,
128.26, 128.65, 129.17, 130.38, 130.66, 130.70, 131.39, 134.59, 135.97,
136.79, 136.98, 140.24, 168.25 ppm; IR (KBr, neat): n˜ =3057, 3026, 2926,
1742, 1600, 1458, 1362, 1265, 1152, 968, 741, 701 cmÀ1; EIMS m/z 409
(M+); HRMS (EI) for C28H27NO2, calcd 409.2042, found 409.2040;
37% ee determined by HPLC (Chiral OD column, 2-propanol/hexane=
5:95, 0.7 mLminÀ1, major isomer 33.35 min, minor isomer 25.20 min).
3-((E)-1,3-Bis(4-tert-butylphenyl)allyl)-1-methyl-1H-indole (3c): Yellow
solid, analytical TLC (silica gel 60, 2% EtOAc in hexane), Rf =0.30;
1H NMR (300 MHz, CDCl3): d=1.30 (s, 9H), 1.34 (s, 9H), 3.68 (s, 3H),
5.06 (d, J=7.2 Hz, 1H), 6.40 (d, J=15.8 Hz, 1H), 6.63–6.72 (m, 2H), 6.99
(t, J=7.3 Hz, 1H), 7.17–7.33 (m, 10H), 7.46 ppm (d, J=7.9 Hz, 1H);
13C NMR (75 MHz, CDCl3): d=26.69, 31.29, 31.41, 32.67, 45.63, 109.09,
117.25, 118.75, 120.06, 121.51, 124.85, 125.22, 125.34, 125.98, 127.32,
128.00, 129.85, 132.16, 134.84, 137.35, 140.58, 158.12, 159.23 ppm; IR
(KBr, neat): n˜ =3058, 3026, 2935, 1602, 1458, 1362, 1265, 1183, 965, 741,
702 cmÀ1; EIMS m/z 435 (M+); HRMS (EI) for C32H37N, calcd 435.2926,
found 435.2928; 56% ee determined by HPLC (Chiral OD column, 2-
propanol/hexane=0.6:99.4, 0.4 mLminÀ1, major isomer 26.12 min, minor
isomer 24.84 min).
1,2-Dimethyl-3-((E)-1,3-di-p-tolylallyl)-1H-indole (3i): Yellow solid, ana-
lytical TLC (silica gel 60, 5% EtOAc in hexane), Rf =0.51; 1H NMR
(300 MHz, CDCl3): d=2.30 (s, 6H), 2.62 (s, 3H), 3.66 (s, 3H), 5.09 (d,
J=7.1 Hz, 1H), 6.33 (d, J=15.8 Hz, 1H), 6.75 (dd, J1 =7.2 Hz, J2 =
15.8 Hz, 1H), 6.93 (t, J=7.3 Hz, 1H), 7.07–7.19 (m, 5H), 7.22–7.30 (m,
6H), 7.49 ppm (d, J=7.6 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
11.28, 24.49, 21.63, 30.04, 45.45, 109.07, 112.93, 119.23, 119.99, 120.86,
126.64, 127.48, 128.61, 129.12, 129.37, 129.63, 129.75, 130.62, 132.10,
133.83, 135.35, 135.90, 137.28, 141.21 ppm; IR (KBr, neat): n˜ =3058, 3021,
2928, 1599, 1457, 1361, 1265, 1182, 972, 741, 702 cmÀ1; EIMS m/z 365
(M+); HRMS (EI) for C27H27N, calcd 365.2143, found 365.2142; 41% ee
determined by HPLC (Chiral OD column, 2-propanol/hexane=1:99,
0.7 mLminÀ1, major isomer 10.76 min, minor isomer 16.21 min).
3-((E)-1,3-Bis(4-methoxyphenyl)allyl)-1-methyl-1H-indole (3d): Yellow
solid, analytical TLC (silica gel 60, 5% EtOAc in hexane), Rf =0.45;
1H NMR (300 MHz, CDCl3): d=3.72 (s, 3H), 3.78 (s, 3H), 5.02 (d, J=
7.2 Hz, 1H), 6.32 (d, J=15.8 Hz, 1H), 6.47 (dd, J1 =7.2 Hz, J2 =15.8 Hz,
1H), 6.73 (s, 1H), 6.80–6.86 (m, 4H), 7.00 (t, J=7.1 Hz, 1H), 7.16–7.31
(m, 6H), 7.39 ppm (d, J=7.9 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=
32.67, 45.29, 55.25, 55.29, 109.13, 113.75, 113.88, 117.62, 118.16, 118.80,
120.03, 121.56, 127.29, 127.39, 129.39, 129.52, 130.42, 130.92, 135.92,
158.08, 158.85 ppm; IR (KBr, neat): n˜ =3058, 3022, 2932, 1598, 1456,
1360, 1262, 1180, 962, 741, 701 cmÀ1; EIMS m/z 383 (M+); HRMS (EI)
for C26H25NO2, calcd 383.1885, found 383.1882; 53% ee determined by
HPLC (Chiral OD column, 2-propanol/hexane=3:97, 1 mLminÀ1, major
isomer 10.90 min, minor isomer 12.05 min).
1-Benzyl-3-((E)-1,3-di-p-tolylallyl)-1H-indole (3j): Yellow solid, analyti-
cal TLC (silica gel 60, 5% EtOAc in hexane), Rf =0.51; 1H NMR
(400 MHz, CDCl3): d=2.31 (s, 3H), 2.32 (s, 3H), 5.06 (d, J=7.4 Hz, 1H),
5.28 (s, 2H), 6.38 (d, J=15.8 Hz, 1H), 6.70 (dd, J1 =7.4 Hz, J2 =15.8 Hz,
1H), 6.86 (s, 1H), 6.98 (t, J=7.4 Hz, 1H), 7.07–7.14 (m, 7H), 7.21–7.30
(m, 8H), 7.42 ppm (d, J=7.9 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
21.03, 21.11, 45.83, 50.00, 109.68, 119.07, 120.14, 121.77, 126.21, 126.58,
126.77, 127.46, 127.58, 128.34, 128.71, 129.08, 129.13, 130.15, 131.88,
134.79, 135.74, 136.82, 137.09, 137.78, 140.57 ppm; IR (KBr, neat): n˜ =
3-((E)-1,3-Bis(4-fluorophenyl)allyl)-1-methyl-1H-indole (3e): Yellow
solid, analytical TLC (silica gel 60, 5% EtOAc in hexane), Rf =0.51;
1H NMR (400 MHz, CDCl3): d=3.74 (s, 3H), 5.06 (d, J=7.3 Hz, 1H),
6.32 (d, J=15.8 Hz, 1H), 6.55 (dd, J1 =7.3 Hz, J2 =15.8 Hz, 1H), 6.73 (s,
1H), 6.93–7.02 (m, 5H), 7.17 (t, J=7.2 Hz, 1H), 7.24–7.32 (m, 5H),
7.35 ppm (d, J=7.9 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=32.71,
45.31, 109.27, 115.03, 115.21, 115.31, 115.50, 116.79, 118.98, 119.79, 121.76,
126.99, 127.27, 127.69, 127.79, 129.78, 129.88, 130.20, 133.47, 137.44,
139.09, 163.15, 163.75 ppm; IR (KBr, neat): n˜ =3056, 3025, 2931, 1595,
1452, 1365, 1265, 1182, 961, 741, 700 cmÀ1; EIMS m/z 359 (M+); HRMS
(EI) for C24H19F2N, calcd 359.1486, found 359.1485; 63% ee determined
3058, 3020, 2931, 1697, 1612, 1450, 1358, 1265, 1180, 972, 741, 702 cmÀ1
;
EIMS m/z 427 (M+); HRMS (EI) for C33H29N, calcd 427.2300, found
427.2301; 35% ee determined by HPLC (Chiral OD column, 2-propanol/
hexane=1:99, 0.7 mLminÀ1
,
major isomer 26.13 min, minor isomer
20.37 min).
by HPLC (Chiral OD-H column, 2-propanol/hexane=1:99, 0.5 mLminÀ1
,
major isomer 31.62 min, minor isomer 29.41 min).
822
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Chem. Asian J. 2011, 6, 812 – 824