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K.L. Toups et al. / Journal of Organometallic Chemistry 694 (2009) 571–575
4.2. Hydroarylation products
J = 1.2, 7.4, 15.2 Hz, 1H), 4.95 (d, J = 7.2 Hz, 1H), 3.67 (s, 3H), 2.34
(s, 3H), 1.74–1.72 (m, 3H). 1H NMR (11b): d 7.65–6.94 (m, 9H),
6.62 (dd, J = 5.6, 16.0 Hz, 1H), 6.45 (dd, J = 1.6, 16.0 Hz, 1H), 3.99–
3.91 (m, 1H), 3.67 (s, 3H), 2.40 (s, 3H), 1.59 (d, J = 7.2 Hz, 3H).
13C{1H} NMR (126 MHz; 11a + 11b): d 144.4, 138.0, 136.8, 135.4,
133.0, 132.2, 128.5, 128.1, 127.7, 126.9, 126.8, 126.5, 126.1,
126.0, 125.8, 120.4, 119.5, 119.3, 119.3, 118.7, 118.6, 114.1,
112.9, 108.7, 60.4, 45.2, 45.1, 22.9, 29.4, 21.1, 20.5, 18.0, 14.2,
10.6. IR (neat, cmꢁ1): 3024, 2927, 1612, 1470, 1367, 966, 736,
696. HRMS calcd. (found) for C20H21N (M+): 275.1674 (275.1673).
4.2.1. (E)-Dimethyl 2-(4-(1,2-dimethyl-1H-indol-3-yl)but-2-
enyl)malonate (3)
A mixture of (1)AuCl (9.3 mg, 0.015 mmol) and AgOTf (3.9 mg,
0.015 mmol) was treated with a solution of 1,2-dimethylindole
(24 mg, 0.31 mmol), 2 (58 mg, 0.31 mmol), and n-hexadecane
(25 lL, 0.08 mmol) in 1,4-dioxane (0.6 mL) and the resulting sus-
pension was stirred at room temperature for 48 h. Column chro-
matography of the reaction mixture (hexanes–EtOAc = 4:1) gave
3 (79 mg, 82%) as a pale yellow oil. TLC (hexanes–EtOAc = 5:1):
Rf = 0.21. 1H NMR: d 7.49 (d, J = 7.6 Hz, 1H), 7.27 (d, J = 8.4 Hz,
1H), 7.18 (t, J = 7.1 Hz, 1H), 7.09 (t, J = 7.1 Hz, 1H), 5.72 (td,
J = 6.9, 15.0 Hz, 1H), 5.46 (td, J = 7.4, 15.0 Hz, 1H), 3.70 (s, 6H),
3.68 (s, 3H), 3.44 (d, J = 7.6 Hz, 2H), 3.43 (t, J = 7.6 Hz, 1H), 2.61
(t, J = 7.6 Hz, 2H), 2.36 (s, 3H). 13C{1H} NMR: d 169.6, 136.7,
133.2, 133.0, 127.8, 125.1, 120.7, 118.8, 118.3, 108.8, 108.6, 52.6,
52.1, 32.0, 29.6, 27.8, 10.3. IR (neat, cmꢁ1): 2952, 1749, 1733,
1615, 1435, 1231, 740. HRMS calcd. (found) for C19H23O4N (M+):
329.1627 (329.1626).
4.2.6. 3-(2,4-Dimethylpent-3-en-2-yl)-1,2-dimethyl-1H-indole (13)
TLC (hexanes–EtOAc = 5:1): Rf = 0.48. 1H NMR:
d 7.81 (d,
J = 8.0 Hz, 1H), 7.21 (d, J = 8.0 Hz, 1H), 7.09 (t, J = 7.6 Hz, 1H), 6.97
(t, J = 7.6 Hz, 1H), 5.62–5.60 (m, 1H), 3.61 (s, 3H), 2.40 (s, 3H),
1.66 (d, J = 1.6 Hz, 3H), 1.58 (s, 6H), 1.17 (d, J = 1.2 Hz, 3H).
13C{1H} NMR: d 136.6, 136.3, 131.9, 131.0, 121.1, 119.6, 118.0,
108.4, 36.9, 31.9, 29.7, 29.3, 26.7, 18.2, 12.4. IR (neat, cmꢁ1):
2924, 1465, 1367, 1071, 735, 669, 650. HRMS calcd. (found) for
C17H23N (M+): 241.1831 (241.1831).
The E-configuration of the C@C bond of 3 and of hydroarylation
products 8–11 was established by the large (JHH ꢂ 15 Hz) coupling
constant of the olefinic hydrogen atoms.
4.2.7. (E)-dimethyl 2-(4-(1-methyl-1H-indol-3-yl)but-2-
enyl)malonate (14)
TLC (hexanes–EtOAc = 4:1): Rf = 0.28. 1H NMR:
d 7.53 (d,
4.2.2. (E)-1,2-Dimethyl-3-(7-tridecen-6-yl)-1H-indole (8)
J = 8.0 Hz, 1H), 7.29–7.16 (m, 2H), 7.08 (t, J = 7.2 Hz, 1H), 6.79 (s,
1H), 5.78 (td, J = 7.0, 15.2 Hz, 1H), 5.53 (td, J = 7.4, 15.2 Hz, 1H),
3.72 (s, 3H), 3.69 (s, 6H), 3.44 (t, J = 7.4 Hz, 1H), 3.43 (d,
J = 7.2 Hz, 2H), 2.63 (t, J = 7.4 Hz, 2H). 13C{1H} NMR: d 169.7,
137.4, 132.8, 127.9, 126.6, 126.1, 121.7, 119.3, 118.9, 113.3,
109.3, 52.7, 52.1, 32.8, 32.0, 28.7. IR (neat, cmꢁ1): 2953, 1733,
1435, 1231, 1152, 971, 740. HRMS calcd. (found) for C18H21NO4
(M+): 315.1471 (315.4173).
TLC (hexanes–EtOAc = 20:1): Rf = 0.62. 1H NMR: d 7.60 (d,
J = 8.0 Hz, 1H), 7.23 (dd, J = 0.8, 8.0 Hz, 1H), 7.12 (t, J = 7.6 Hz,
1H), 7.01 (d, J = 7.4 Hz, 1H), 5.79 (dd, J = 6.8, 15.2 Hz, 1H), 5.44
(td, J = 5.6, 15.2 Hz, 1H), 3.64 (s, 3H), 3.46 (q, J = 7.2 Hz, 1H), 2.35
(s, 3H), 1.97 (q, J = 6.8 Hz, 2H), 1.83 (q, J = 8.0 Hz, 2H), 1.36–1.16
(m, 12H), 0.89–0.81 (m, 6H). 13C{1H} NMR: d 133.8, 132.5, 129.4,
126.8, 120.3, 119.8, 118.4, 114.0, 108.7, 40.4, 35.4, 32.8, 32.1,
31.7, 29.7, 29.5, 28.0, 22.9, 22.8, 14.3, 10.8. IR (neat, cmꢁ1): 2924,
2854, 1469, 1407, 965, 735. HRMS calcd. (found) for C23H35
N
4.2.8. (E)-dimethyl 2-(4-(2-methyl-1H-indol-3-yl)but-2-
enyl)malonate (15)
(M+): 325.2770 (325.2765).
TLC (hexanes–EtOAc = 7:3): Rf = 0.30. 1H NMR: d 7.85 (s, 1H),
7.46 (d, J = 7.8 Hz, 1H), 7.25 (dd, J = 1.0, 7.8 Hz, 1H), 7.12 (dt,
J = 1.2, 7.0 Hz, 1H), 7.07 (dt, J = 1.0, 6.7 Hz, 1H), 5.71 (dtd, J = 1.2,
6.2, 15.2 Hz, 1H), 5.45 (td, J = 7.3, 15.2 Hz, 1H), 3.67 (s, 6H), 3.42
(t, J = 7.6 Hz, 1H), 3.40 (d, J = 7.2 Hz, 2H), 2.61 (t, J = 7.1 Hz, 2H),
2.33 (s, 3H). 13C{1H} NMR: d 169.7, 135.4, 132.9, 131.4, 128.8,
125.3, 121.1, 119.3, 118.4, 110.4, 109.6, 52.6, 52.2, 32.0, 27.6,
11.7. IR (neat, cmꢁ1): 3399, 2953, 2360, 1731, 1435, 1232, 1154,
970, 742. HRMS calcd. (found) for C18H21NO4 (M+): 315.1471
(315.1473).
4.2.3. (E)-Ethyl 5-cyclohexyl-5-(1,2-dimethyl-1H-idol-3-yl)pent-3-
enoate (9)
TLC (hexanes–EtOAc = 5:1): Rf = 0.38. 1H NMR:
d 7.58 (d,
J = 8.0 Hz, 1H), 7.22 (d, J = 8.4 Hz, 1H), 7.11 (t, J = 7.6 Hz, 1H), 7.01
(t, J = 7.4 Hz, 1H), 6.01 (dd, J = 8.4, 15.2 Hz, 1H), 5.53 (td, J = 7.3,
14.8 Hz, 1H), 4.09 (q, J = 7.1 Hz, 2H), 3.62 (s, 3H), 3.18 (t,
J = 9.4 Hz, 1H), 3.04–2.93 (m, 2H), 2.33 (s, 3H), 2.04–0.67 (m,
11H), 1.21 (t, J = 7.2 Hz, 3H). 13C{1H} NMR: d 172.2, 136.8, 136.2,
132.7, 126.4, 121.5, 120.2, 119.4, 118.3, 112.5, 108.6, 60.4, 47.7,
41.0, 38.1, 32.4, 21.5, 29.7, 29.5, 26.6, 26.4, 14.2, 10.7. IR (neat,
cmꢁ1): 2918, 2848, 1730, 1471, 1445, 1368, 1300, 1161, 1126,
1098, 964, 739. HRMS calcd. (found) for C23H31O2N (M+):
353.2355 (353.2362).
4.2.9. (E)-dimethyl 2-(4-(5-methyl-1H-indol-3-yl)but-2-
enyl)malonate (16)
TLC (hexanes–EtOAc = 4:1): Rf = 0.19. 1H NMR: d 7.95 (s, 1H),
7.38 (s, 1H), 7.28 (t, J = 8.2 Hz, 1H), 7.06 (d, J = 7.8 Hz, 1H), 6.94
(d, J = 2.0 Hz, 1H), 5.84 (td, J = 7.1, 15.2 Hz, 1H), 5.58 (td, J = 7.4,
15.2 Hz, 1H), 3.74 (s, 6H), 3.50 (t, J = 7.8 Hz, 1H), 3.47 (d,
J = 6.4 Hz, 2H), 2.69 (t, J = 7.2 Hz, 2H), 2.51 (s, 3H). 13C{1H} NMR:
d 169.7, 135.0, 132.8, 128.6, 127.8, 126.1, 123.8, 122.0, 118.9,
114.4, 111.0, 52.7, 52.2, 32.1, 28.8, 21.7. IR (neat, cmꢁ1): 3409,
2953, 2358, 1731, 1434, 1228, 1153, 971, 794. HRMS calcd. (found)
for C18H21NO4 (M+): 315.1471 (315.1473).
4.2.4. (E)-1,2-Dimethyl-3-(4-methyl-1-phenylpent-2-enyl)-1H-indole
(10)
TLC (hexanes–CH2Cl2 = 9:1): Rf = 0.36. 1H NMR: d 7.34 (d,
J = 8.0 Hz, 1H), 7.28–7.08 (m, 7H), 6.94 (t, J = 7.2 Hz, 1H), 5.98
(dd, J = 6.8, 15.2 Hz, 1H), 5.45 (dd, J = 6.8, 15.2 Hz, 1H), 4.92 (d,
J = 7.6 Hz, 1H), 3.61 (s, 3H), 2.37–2.27 (m, 1H), 2.30 (s, 3H), 1.00
(d, J = 6.8 Hz, 3H), 0.97 (d, J = 6.8 Hz, 3H). 13C{1H} NMR
(125.7 MHz): d 144.6, 138.6, 136.8, 133.2, 128.9, 128.2, 128.1,
127.1, 125.8, 120.4, 119.6, 118.7, 113.0, 108.6, 45.0, 31.1, 29.8,
29.6, 22.7, 10.8. IR (neat, cmꢁ1): 2955, 1600, 1492, 1470, 1367,
971, 736, 699. HRMS calcd. (found) for C22H25N (M+): 303.1987
(303.1987).
4.2.10. (E)-dimethyl 2-(4-(5-chloro-1,2-dimethyl-1H-indol-3-yl)but-
2-enyl)malonate (17)
TLC (hexanes–EtOAc = 7:3): Rf = 0.29. 1H NMR:
d 7.39 (d,
J = 1.8 Hz, 1H), 7.13 (dd, J = 0.8, 8.8 Hz, 1H), 7.07 (dd, J = 1.6,
9.0 Hz, 1H), 5.64 (ttd, J = 1.2, 6.0, 15.2 Hz, 1H), 5.39 (ttd, J = 1.6,
7.2, 15.2 Hz, 1H), 3.66 (s, 6H), 3.62 (s, 3H), 3.39 (t, J = 7.6 Hz, 1H),
3.35 (d, J = 5.6 Hz, 2H), 2.58 (t, J = 7.2 Hz, 2H), 2.30 (s, 3H).
13C{1H} NMR: d 169.6, 135.2, 134.8, 132.6, 128.9, 125.5, 124.6,
4.2.5. Compounds 11a and 11b (1:1.2 mixture of regioisomers)
TLC (hexanes–CH2Cl2 = 9:1): Rf = 0.36. 1H NMR (11a): d 7.65–
6.94 (m, 9H), 6.09 (qdd, J = 1.2, 7.4, 15.2 Hz, 1H), 5.51 (dqd,