Homogeneous Catalysis
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17.6, 2.1 Hz, 1H; minor), 2.18 (dq, J=17.6, 2.4 Hz, 1H; minor), 1.99 (dt,
J=3.8, 2.1 Hz, 3H; major), 1.97 ppm (dt, J=7.4, 0.9 Hz, 3H; minor);
13C NMR (100 MHz, CDCl3, 238C, DEPT): d=152.34 (major), 151.14
(minor), 140.75 (minor), 139.42 (major), 138.05 (minor), 136.35 (major),
135.14 (minor), 129.22 (CH, minor), 128.93 (CH, 2C, major), 128.90,
128.53 (CH, 2C, minor), 128.33 (CH, 2C, minor), 128.29 (CH, minor),
128.19 (CH, major), 127.89 (CH, 2C, major), 127.62 (CH, major), 127.17
(CH, major), 126.85 (CH, minor), 126.31 (CH, major), 123.40 (CH,
minor), 118.50, 117.44 (CH, minor), 116.40 (CH, major), 105.54 (CH,
minor), 104.62 (CH, major), 73.00 (CH2, minor), 71.57 (CH2, major),
66.14 (minor), 65.77 (major), 58.55 (CH, major), 57.72 (CH, minor),
44.75 (CH2, major), 39.20 (CH2, minor), 29.95 (CH3, minor), 29.72 (CH3,
major), 13.31 (CH3, minor), 13.22 ppm (CH3, major); HRMS-ESI: m/z
calcd for C21H21NONa: 326.1521; found: 326.1521 [M++Na].
[M++H]; the configuration at the exocylic double bond was determined
by a NOESY experiment.
A
and (2R,4R)-2,3,4,9-tetrahydro-4,9-dimethyl-1-methylene-1H-carbazol-2-
ol (27): Table 3, entry 3; white solid; m.p. 118–1208C; 1H NMR
(500 MHz, CDCl3, 238C): d=7.66 (d, J=7.9 Hz, 1H; minor), 7.61 (d, J=
8.0 Hz, 1H; major), 7.30 (d, J=8.3 Hz, 1H), 7.22 (t, J=8.6 Hz, 1H), 7.08
(t, J=7.5 Hz, 1H; major), 7.07 (t, J=7.6 Hz, 1H; minor), 5.47 (s, 1H;
minor), 5.42 (s, 1H; major), 5.36 (s, 1H; major), 5.34 (s, 1H; minor), 4.60
(brd, J=7.4 Hz, 1H; major), 4.44 (brd, J=10.0 Hz, 1H; minor), 3.82 (s,
3H; major), 3.81 (s, 3H; minor), 3.43–3.35 (m, 1H; major), 3.35–3.31 (m,
1H; minor), 2.35 (ddd, J=12.6, 6.2, 3.9 Hz, 1H; minor), 2.18 (ddd, J=
12.8, 8.8, 6.6, 1H; major), 1.90 (ddd, J=13.1, 5.3, 3.6, 1H; major), 1.77
(brs, 1H), 1.65 (ddd, J=12.0, 10.7, 5.4, 1H; minor), 1.49 (d, J=6.8 Hz,
3H; minor), 1.44 ppm (d, J=6.5 Hz, 3H; major); 13C NMR (125 MHz,
CDCl3, 238C, DEPT): d=141.35 (minor), 140.89 (major), 139.88 (minor),
139.81, (major), 132.52 (minor), 131.79 (major), 125.73 (minor), 125.67
(major), 122.64 (CH, major), 122.51 (CH, minor), 120.25 (CH, minor),
119.87 (CH, major), 119.26 (CH, major), 119.21 (CH, minor), 118.08
(major), 117.78 (minor), 109.46 (CH, minor), 109.39 (CH, major), 107.09
(CH2, major), 105.80 (CH2, minor), 71.43 (CH, minor), 70.39 (CH, major),
42.95 (CH2, minor), 41.34 (CH2, major), 31.92 (CH, major), 31.74 (CH,
minor), 27.52 (CH3, minor), 25.33 (CH3, major), 22.16 (CH3, minor),
21.66 ppm (CH3, major); HRMS-ESI m/z calcd for C15H18NO 228.1388;
found: 228.1384 [M++H].
Tetracycles 22g/22g’: Table 2, entry 10; 2.5:1 mixture of 22g/22g’ as a col-
orless oil; 1H NMR (400 MHz, CDCl3, 238C): d=7.35–7.28 (m, 4H),
7.25–7.23 (m, 3H), 7.19–7.16 (m, 1H), 7.00–6.98 (m, 2H), 6.75 (d, J=
2.6 Hz, 1H; minor), 6.71 (dd, J=8.4, 2.6 Hz, 1H; minor), 6.62 (dd, J=
8.5, 2.6 Hz, 1H; major), 6.33 (d, J=8.4 Hz, 1H; minor), 6.27 (d, J=
8.5 Hz, 1H; major), 5.44 (s, 1H), 5.43 (s, 1H), 5.23 (q, J=1.6 Hz, 1H;
minor), 4.19 (dd, J=8.6, 6.2 Hz, 1H; major), 4.09 (AB of doublet, J=9.1,
4.7 Hz, 1H; minor), 4.03 (AB of doublet, J=9.1, 5.8 Hz, 1H; minor),
3.90 (dd, J=11.7, 8.7 Hz, 1H; major), 3.77 (s, 3H; minor), 3.52 (dd, J=
11.7, 6.2 Hz, 1H; major), 3.50–3.48 (m, 1H), 3.39 (s, 3H; major), 3.01 (s,
3H; minor), 2.98 (s, 3H; major), 2.89 (d of quintet, J=16.9, 2.1 Hz, 1H;
major), 2.48 (dquint, J=16.9, 2.4 Hz, 1H; major), 2.23 (AB of quintet,
J=17.4, 2.3 Hz, 1H; minor), 2.17 (AB of quintet, J=17.4, 2.3 Hz, 1H;
minor), 1.96 (q, J=1.8 Hz, 3H; major), 1.94 ppm (q, J=1.7 Hz, 3H;
minor); 13C NMR (100 MHz, CDCl3, 238C, DEPT): d=153.0 (C, minor),
151.9 (C, major), 147.2 (C, major), 140.8 (C, minor), 139.9 (C, major),
138.5 (C, minor), 136.6 (C, minor), 136.5 (C. major), 130.0 (C, major),
129.1 (CH, major), 129.0 (CH, minor), 128.8 (CH, minor), 128.5 (CH,
minor), 128.2 (CH, major), 127.4 (CH, major), 127.3 (CH, major), 127.1
(CH, minor), 119.1 (C, minor), 114.6 (CH, major), 113.1 (CH, major),
112.8 (CH, minor), 111.4 (CH, minor), 106.2 (CH, minor), 105.6 (CH,
major), 73.3 (CH2, minor), 71.8 (CH2, major), 66.5 (C, minor), 66.2 (C,
major), 58.3 (CH, major), 57.8 (CH, minor), 56.4 (CH3, minor), 56.2
(CH3, major), 44.5 (CH2, major), 39.1 (CH2, minor), 30.9 (CH3, minor),
30.6 (CH3, major), 13.3 (CH3, minor), 13.2 ppm (CH3, major); HRMS-
ESI: m/z calcd for C22H23NO2Na: 356.1626; found: 356.1624 [M++Na];
elemental analysis calcd (%) for (C22H23NO2)2·H2O: C 77.16, H 7.06, N
4.09; found: C 77.25, H 6.74, N 4.46.
A
and
(4R,1R)-3,4-dihydro-1,4,9-trimethyl-1H-carbazol-2(9H)-one (28): Table 3,
1
entry 4; white solid; m.p. 109–1118C; H NMR (400 MHz, CDCl3, 238C):
d=7.85 (d, J=8.1 Hz, 1H; major), 7.56 (d, J=9.0 Hz, 1H; minor), 7.29
(d, J=8.1 Hz, 1H), 7.21 (t, J=8.0 Hz, 1H), 7.12 (td, J=7.9, 1.0 Hz, 1H),
3.66 (s, 3H; major), 3.63 (s, 3H; minor), 3.62–3.56 (m, 2H; major), 3.50–
3.45 (m, 2H; minor), 3.10 (dd, J=13.3, 6.8 Hz, 1H; minor), 2.80 (dd, J=
14.0, 6.3 Hz, 1H; major), 2.64 (dd, J=14.0, 4.6 Hz, 1H; major), 2.37 (dd,
J=13.3, 3.1 Hz, 1H; minor), 1.52 (d, J=7.2 Hz, 3H; major), 1.50 (d, J=
7.0, 3H; minor), 1.38 (d, J=6.9, 3H; major), 1.31 ppm (d, J=6.9, 3H;
minor); 13C NMR (100 MHz, CDCl3, 238C, DEPT): d=211.51 (minor),
211.24 (major), 138.28 (minor), 138.10, (major), 136.29 (major), 135.56
(minor), 125.54 (major), 125.46 (minor), 121.52 (CH), 119.37 (CH),
118.61 (CH), 113.82 (major), 113.61 (minor), 109.11 (CH, minor), 109.09
(CH, major), 46.64 (CH2, major), 44.16 (CH2, minor), 42.65 (CH3, minor),
41.61 (CH3, major), 29.81 (CH, major), 29.63 (CH, minor), 28.07 (CH,
minor), 27.54 (CH, major), 23.18 (CH3, major), 22.66 (CH3, minor), 19.80
(CH3, major), 18.52 ppm (CH3, major); HRMS-ESI: m/z calcd for
C15H18NO: 228.1388; found: 228.1381 [M++H].
1,2,3,4-Tetrahydro-1-methylenecarbazol-3-spiro-5’-(1,3-dioxane-4,6-dione)
(24): Table 3, entry 1; white solid; m.p. 152–1548C; 1H NMR (400 MHz,
CDCl3, 238C): d=8.12 (brs, 1H), 7.42 (d, J=7.9 Hz, 1H), 7.31 (d, J=
8.2 Hz, 1H), 7.19 (td, J=7.1, 1.1 Hz, 1H), 7.08 (td, J=7.6, 0.9 Hz, 1H),
5.29 (s, 1H), 5.01 (s, 1H), 3.49 (s, 2H), 3.15 (s, 2H), 1.82 (s, 3H),
1.79 ppm (s, 3H); 13C NMR (100 MHz, CDCl3, 238C, DEPT): d=168.66,
136.88, 131.64, 131.46, 126.86, 123.52 (CH), 119.90 (CH), 118.52 (CH),
111.10 (CH), 108.82, 107.03 (CH2), 105.09, 49.85, 39.06 (CH2), 29.99
(CH2), 29.28 (CH3), 28.09 ppm (CH3); HRMS-CI m/z calcd for
C18H18NO4: 312.1236; found: 312.1227 [M++H].
Dimer 25: Table 3, entry 2; brown solid; m.p. 285–2878C; 1H NMR
(400 MHz, CDCl3, 238C): d=9.42 (s, 1H), 8.12 (s, 1H), 7.42 (d, J=
7.8 Hz, 1H), 7.22 (d, J=8.0 Hz, 1H), 6.93 (td, J=6.5, 1.4 Hz, 1H), 6.88
(t, J=7.0 Hz, 1H), 6.81–6.76 (m, 2H), 6.74 (d, J=7.4 Hz, 1H), 6.56 (d,
J=8.1 Hz, 1H), 5.56 (s, 1H), 3.73 (d, J=16.2 Hz, 1H), 3.65 (d, J=
16.0 Hz, 1H), 3.61 (d, J=16.3 Hz, 1H), 3.49 (d, J=15.7 Hz, 1H), 3.13 (d,
J=13.0 Hz, 1H), 2.64 (d, J=14.1 Hz, 1H), 2.51 (d, J=14.4 Hz, 1H), 2.32
(d, J=13.2 Hz, 1H), 1.99 (s, 3H), 1.94 (s, 3H), 1.86 (s, 3H), 1.85 (s, 3H),
1.52 ppm (s, 3H); 13C NMR (100 MHz, CDCl3, 238C, DEPT): d=171.00,
170.41, 169.88, 136.85, 136.68, 134.20, 133.90, 132.25, 125.37, 124.82,
122.10 (CH), 121.78 (CH), 119.41 (CH), 118.89 (CH), 118.62 (CH),
117.35 (CH), 117.20 (CH), 111.35 (CH), 110.95 (CH), 106.16, 105.87,
102.40, 52.97, 49.44, 46.67 (CH2), 41.89 (CH2), 35.51, 32.44 (CH2), 29.98
(CH3), 29.96 (CH3), 29.52 (CH3), 28.63 (CH3), 28.56 (CH3), 28.19 ppm
(CH2); HRMS-CI: m/z calcd for C36H35N2O8: 623.2393; found: 623.2393
(R)-4,9-Dihydro-4,9-dimethyl-3H-carbazole (30): Table 3, entry 5; white
1
solid; m.p. 75–778C; [a]D23 =À9.6 (c=0.9 in CH2Cl2); H NMR (400 MHz,
CDCl3, 238C): d=7.65 (dt, J=8.0, 0.8 Hz, 1H), 7.24 (d, J=8.4 Hz, 1H),
7.13 (td, J=6.8 1.2 Hz, 1H), 7.06 (td, J=8.0, 0.8 Hz, 1H), 6.52 (ddd, J=
10.0, 2.4, 1.6 Hz, 1H), 5.95 (ddd, J=10.0, 5.2, 4.0 Hz, 1H), 3.67 (s, 3H),
3.30–3.21 (m, 1H), 2.63 (ddd, J=17.2, 4.0, 2.8 Hz, 1H), 2.25 (ddd, J=
17.2, 5.2, 1.6 Hz, 1H), 1.27 ppm (d, J=7.3 Hz, 3H); 13C NMR (100 MHz,
CDCl3, 238C, DEPT): d=137.24, 133.81, 126.94 (CH), 125.87, 120.81
(CH), 119.18 (CH), 118.54 (CH), 116.39 (CH), 113.78, 109.03 (CH), 32.91
(CH2), 29.04 (CH3), 26.48 (CH), 20.17 ppm (CH3); HRMS-CI m/z calcd
for C13H13N: 198.1283; found: 198.1287 [M++H].
2-(4,5-Dihydro-5-methyleneoxazol-2-yl)1H-indole (32): Scheme 3; white
solid; m.p. 175–1778C; 1H NMR (500 MHz, CDCl3, 238C): d=9.64 (brs,
1H), 7.70 (d, J=8.0 Hz, 1H), 7.40 (d, J=8.3 Hz, 1H), 7.31 (t, J=7.9 Hz,
1H), 7.16 (t, J=7.4 Hz, 1H), 7.15 (s, 1H), 4.88 (q, J=2.9 Hz, 1H), 4.69
(t, J=2.6 Hz, 2H), 4.43 ppm (q, J=2.7 Hz, 1H); 13C NMR (125 MHz,
CDCl3, 238C, DEPT): d=159.02, 158.26, 137.35, 127.63, 124.90 (CH),
124.20, 122.16 (CH), 120.68 (CH), 111.59 (CH), 107.26 (CH), 84.40
(CH2), 57.11 ppm (CH2); HRMS-CI: m/z calcd for C12H11N2O: 199.0871;
found: 199.0872 [M++H].
General procedure for the gold-catalyzed intermolecular reactions of in-
doles with alkynes (Table 4 and Schemes 4–8): The alkyne (0.51–
0.85 mol) was added to a mixture of indole derivative (0.84 mol) and
gold catalyst (0.05 mol) in toluene (4 mL). The reaction mixtures were
Chem. Eur. J. 2007, 13, 1358 –1373
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