The Journal of Organic Chemistry
Note
Rh2(esp)2 and 2.0 mL of toluene. Purification by MPLC (3/97 to 20/
80 EtOAc/hexanes) afforded the product as a white solid (0.046 g,
80%): 1H NMR (500 MHz, CDCl3) δ 8.32 (s, 0.58H), 7.81 (s,
0.39H), 7.27 (s, 1H), 7.19 (d, J = 8.5 Hz, 1H), 6.98 (d, J = 8.0 Hz,
1H), 4.65 (s, 2H), 3.76 (br s, 2H), 2.78 (t, J = 5.0 Hz, 2H), 2.46 (s,
3H), 1.54 (s, 9H); 13C{1H} NMR (125 MHz, CDCl3) δ 155.2 (C),
134.5 (C), 130.9 (C), 128.6 (C), 127.3 (C), 123.1 (CH), 117.7 (CH),
110.5 (CH), 107.9 (C), 80.1 (C), 42.7 (CH2), 41.9 (CH2), 28.6
(CH3), 21.5 (CH3), 21.2 (CH2); ATR-FTIR (thin film) 3288, 3005,
2914, 1676, 1579, 1409, 1361, 1250, 1231, 1162, 1091, 913 cm−1;
HRMS (ESI) m/z calcd for C17H23N2O2 (M + H)+ 287.1756, found
287.1760.
2917, 2853, 1672, 1414, 1365, 1306, 1230, 1160, 1099, 899, 799 cm−1;
HRMS (ESI) m/z calcd for C17H23N2O2 (M + H)+ 287.1756, found
287.1760.
tert-Butyl 2,3,4,9-Tetrahydro-1H-pyrido[2,3-b]indole-1-car-
boxylate 12k. The general procedure was followed by using 0.023
g of aryl azide 11k (0.073 mmol), 0.0027 g of Rh2(esp)2, and 0.7 mL
of toluene. Purification by MPLC (3/97 to 20/80 EtOAc/hexanes)
1
afforded the product as a yellow solid (0.019 g, 91%): mp 87 °C; H
NMR (500 MHz, CDCl3) δ 10.02 (s, 0.75H), 7.39−7.38 (m, 1H),
7.27 (m, 1H), 7.07 (m, 2H), 3.81 (t, J = 5.5 Hz, 2H), 2.74 (t, J = 6.0
Hz, 2H), 2.05 (m, 2H), 1.57 (s, 9H); 13C{1H} NMR (125 MHz,
CDCl3) δ 152.7 (C), 133.8 (C), 132.0 (C), 129.4 (C), 126.6 (C),
119.9 (CH), 119.4 (CH), 116.7 (CH), 110.5 (CH), 81.7 (C), 45.1
(CH2), 28.4 (CH3), 22.7 (CH2), 19.2 (CH2); ATR-FTIR (thin film)
3396, 2972, 2953, 2924, 2843, 1682, 1582, 1494, 1387, 1351, 1260,
1159, 1130, 740 cm−1; HRMS (ESI) m/z calcd for C16H21N2O2 (M +
H)+ 273.1610, found 273.1603.
(9H-Fluoren-9-yl)methyl 3,4-Dihydro-1H-pyrido[3,4-b]-
indole-2(9H)-carboxylate 12g. The general procedure was followed
by using 0.0320 g of aryl azide 11g (0.100 mmol), 0.0038 g of
Rh2(esp)2, and 1.0 mL of toluene. Purification by MPLC (3/97 to 20/
80 EtOAc/hexanes) afforded the product as a white solid (0.019 g,
1
1,3,4,9-Tetrahydropyrano[3,4-b]indole 12l. The general pro-
cedure was followed by using 0.032 g of aryl azide 11l (0.089 mmol),
0.006 g of Rh2(esp)2 and 1.0 mL of toluene. Purification by MPLC (3/
97 to 20/80 EtOAc/hexanes) afforded the product as a brown solid
65%): mp 174 °C; H NMR (500 MHz, CDCl3) δ 8.71 (s, 0.63H),
7.95 (s, 0.32H), 7.26 (dd, J = 9.0 Hz, 4.0 Hz, 1H), 7.15 (d, J = 9.0 Hz,
1H), 6.92 (dt, J = 9.0 Hz, 2.0 Hz, 1H), 4.65 (m, 2H), 3.80 (s, 2H),
2.79 (t, J = 5.5 Hz, 2H), 1.58 (s, 9H); 13C{1H} NMR (125 MHz,
CDCl3) δ 157.9 (d, JCF = 231 Hz, C), 155.5 (C), 132.7 (C), 127.4
(C), 111.4 (CH), 109.6 (d, JCF = 22.9 Hz, CH), 108.6 (C), 102.9 (d,
JCF = 26.6 Hz, CH), 80.3 (C), 42.6 (CH2), 41.9 (CH2), 28.6 (CH3),
21.4 (CH2), only visible peaks; 19F NMR (282 MHz, CDCl3) δ
−125.26; ATR-FTIR (thin film) 2972, 2934, 2836, 2117, 1691, 1481,
1416, 1237, 1113, 958 cm−1; HRMS (ESI) m/z calcd for
C16H20FN2O2 (M + H)+ 291.1508, found 291.1509.
(9H-Fluoren-9-yl)methyl 3,4-Dihydro-1H-pyrido[3,4-b]-
indole-2(9H)-carboxylate 12h. The general procedure was followed
by using 0.0390 g of aryl azide 11h (0.101 mmol), 0.0038 g of
Rh2(esp)2, and 1.00 mL of toluene. Purification by MPLC (3/97 to
20/80 EtOAc/hexanes) afforded the product as a white solid (0.027 g,
75%): 1H NMR (500 MHz, CDCl3) δ 8.91 (s, 0.66H), 8.02 (s,
0.30H), 7.31 (s, 1H), 7.27 (d, J = 9.0 Hz, 1H), 7.01 (d, J = 9.0 Hz,
1H), 4.69 (br m, 2H), 3.77 (t, J = 5.5 Hz, 2H), 2.78 (t, J = 5.5 Hz,
2H), 1.55 (s, 9H); 13C{1H} NMR (125 MHz, CDCl3) δ 155.6 (C),
143.1 (C), 134.5 (C), 132.9 (C), 127.3 (C), 120.9 (q, JCF = 253.4 Hz,
C), 115.4 (CH), 111.3 (CH), 110.5 (CH), 108.9 (C), 80.4 (C), 42.5
(CH2), 41.9 (CH2), 28.5 (CH3), 21.3 (CH2); 19F NMR (282 MHz,
CDCl3) δ −58.5; ATR-FTIR (thin film) 3269, 2976, 2934, 2849, 1666,
1423, 1243, 1212, 1133, 1101, 896 cm−1; HRMS (ESI) m/z calcd for
C17H20F3N2O3 (M + H)+ 357.1424, found 357.1426.
(9H-Fluoren-9-yl)methyl 3,4-Dihydro-1H-pyrido[3,4-b]-
indole-2(9H)-carboxylate 12i. The general procedure was followed
by using 0.440 g of aryl azide 11i (0.110 mmol, 83% pure), 0.0042 g of
Rh2(esp)2, and 1.10 mL of toluene. Purification by MPLC (3/97 to
20/80 EtOAc/hexanes) afforded the product as a white solid (0.020 g,
60%): 1H NMR (500 MHz, CDCl3) δ 8.24 (s, 0.52 H), 7.75 (s,
0.37H), 7.35 (d, J = 8.5 Hz, 1H), 6.83 (s, 1H), 6.79 (d, J = 8.5 Hz,
1H), 4.62 (br s, 2H), 3.83 (s, 3H), 3.75 (s, 2H). 2.76 (br s, 2H), 1.52
(s, 9H); 13C{1H} NMR (125 MHz, CDCl3) δ 156.2 (C), 155.2 (C),
137.0 (C), 129.3 (C), 121.5 (C), 118.5 (C), 118.4 (CH), 108.9 (CH),
95.0 (CH2), 80.1 (C), 55.8 (CH3), 42.6 (CH2), 41.7 (CH2), 28.5
(CH3), 21.5 (CH2); ATR-FTIR (thin film) 3297, 3008, 2979, 2908,
2830, 1665, 1631, 1478, 1421, 1365, 1249, 1231, 1155, 1112, 1032,
909, 815 cm−1; HRMS (ESI) m/z calcd for C17H23N2O3 (M + H)+
303.1702, found 303.1709.
1
(0.023 g, 83%): mp 111 °C; H NMR (500 MHz, CDCl3) δ 7.72 (s,
1H), 7.52 (d, J = 7.5 Hz, 1H), 7.31 (d, J = 8.0 Hz, 1H), 7.18 (t, J = 7.5
Hz, 1H), 7.14 (t, J = 7.5 Hz, 1H), 4.80 (s, 2H), 4.05 (t, J = 5.5 Hz,
2H), 2.86 (t, J = 5.5 Hz, 2H); 13C{1H} NMR (125 MHz, CDCl3) δ
135.9 (C), 131.5 (C), 127.2 (C), 121.7 (CH), 119.6 (CH), 118.0
(CH), 110.9 (CH), 107.6 (CH), 65.8 (CH2), 63.7 (CH2), 22.2
(CH2); ATR-FTIR (thin film) 3382, 2957, 2843, 2810, 1452, 1238,
1088, 747 cm−1; HRMS (ESI) m/z calcd for C11H12NO (M)+
174.0916, found 174.0919.
tert-Butyl Indolo[3,2-b]indole-5(10H)-carboxylate 12m. The
general procedure was followed by using 0.030 g of aryl azide 11m
(0.089 mmol), 0.0034 g of Rh2(esp)2, and 0.9 mL of toluene.
Purification by MPLC (3/97 to 20/80 EtOAc/hexanes) afforded the
product as a brown solid (0.030 g, 96%): 1H NMR (500 MHz,
CDCl3) δ 8.49 (m, 1H), 8.28 (br s, 1H), 8.18 (s, 1H), 7.64 (d, J = 7.5
Hz, 1H), 7.43 (d, J = 8.0 Hz, 1H), 7.36 (t, J = 7.5 Hz, 1H), 7.32−7.27
(m, 2H), 7.25−7.22 (m, 1H), 1.82 (s, 9H); 13C{1H} NMR (125 MHz,
CDCl3) δ 150.8 (C), 140.3 (C), 139.4 (C), 127.1 (C), 124.2 (CH),
124.0 (C), 122.9 (CH), 122.7 (CH), 121.5 (CH), 119.9 (CH), 118.7
(C), 117.4 (CH), 117.1 (C), 116.9 (CH), 111.8 (CH), 84.0 (C), 28.6
(CH3); ATR-FTIR (thin film) 3425, 3402, 1725, 1449, 1364, 1348,
1302, 1243, 1141, 737 cm−1; HRMS (ESI) m/z calcd for C19H19N2O2
(M + H)+ 307.1440, found 307.1447.
4H-Thieno[3,2-b]indole 12n.10a The general procedure was
followed by using 0.025 g of aryl azide 11n (0.012 mmol), 0.0047 g of
Rh2(esp)2, and 1.4 mL of toluene. Purification by MPLC (3/97 to 20/
80 EtOAc/hexanes) afforded the product as a white solid (0.021 g,
98%); spectral data of the product matched those reported by Sapi and
co-workers:10a 1H NMR (500 MHz, CDCl3) δ 8.11 (s, 1H), 7.77 (d, J
= 7.5 Hz, 1H), 7.41 (d, J = 8.0 Hz, 1H), 7.38 (d, J = 5.0 Hz, 1H), 7.28
(t, J = 7.5 Hz, 1H), 7.21 (t, J = 7.5 Hz, 1H), 7.05 (d, J = 5.0 Hz, 1H);
13C{1H} NMR δ 143.2 (C), 141.3 (C), 127.1 (CH), 122.9 (CH),
122.3 (C), 119.9 (CH), 118.9 (CH), 118.1 (C), 112.0 (CH), 111.7
(CH); ATR-FTIR (thin film) 3396, 3076, 3047, 1528, 1452, 1049,
1302, 1238, 1091, 743 cm−1; HRMS (ESI) m/z calcd for C10H8NS (M
+ H)+ 174.0376, found 174.0377.
( 4 S , 6 a R , 8 a S ) - 6 a , 8 a - D i m e t h y l -
(9H-Fluoren-9-yl)methyl 3,4-Dihydro-1H-pyrido[3,4-b]-
indole-2(9H)-carboxylate 12j. The general procedure was followed
by using 0.450 g of aryl azide 11j (0.142 mmol), 0.0054 g of
Rh2(esp)2, and 1.40 mL of toluene. Purification by MPLC (3/97 to
20/80 EtOAc/hexanes) afforded the product as a white solid (0.033 g,
1,3,4,5,6,6a,6b,7,8,8a,13,14,14a,14b-tetradecahydronaphtho-
[2′,1′:4,5]indeno[2,1-b]indol-4-yl Acetate 12p. The general
procedure was followed by using 0.034 g of aryl azide 11p (0.078
mmol), 0.0030 g of Rh2(esp)2, and 0.8 mL of toluene. Purification by
MPLC (3/97 to 20/80 EtOAc/hexanes) afforded the product as a
brown solid (0.0080 g, 25%): 1H NMR (500 MHz, CDCl3) δ 7.89 (s,
1H), 7.48 (m, 1H), 7.30 (dd, J = 6.5, 2.5 Hz, 1H), 7.08−7.05 (m, 2H),
5.44 (br s, 1H), 4.62 (m, 1H), 2.69 (dd, J = 14.5, 6.5 Hz, 1H), 2.54−
2.49 (m, 1H), 2.40−2.36 (m, 3H), 2.11 (m, 2H), 2.05 (s, 3H), 1.91−
1.88 (m, 3H), 1.78−1.72 (m, 3H), 1.62−1.58 (m, 2H), 1.20−1.17 (m,
2H), 1.12 (s, 3H), 1.03 (s, 3H); 13C{1H} NMR (125 MHz, CDCl3) δ
170.6 (C), 141.7 (C), 140.3 (C), 139.5 (C), 129.7 (C), 123.6 (C),
1
81%): mp 176 °C; H NMR (500 MHz, CDCl3) δ 8.18 (s, 0.57H),
7.76 (s, 0.39H), 7.36 (d, J = 8.0 Hz, 1H), 7.09 (s, 1H), 6.94 (d, J = 8.0
Hz, 1H), 4.63 (br s, 2H), 3.76 (br s, 2H), 2.77 (t, J = 5.5 Hz, 2H), 2.45
(s, 3H), 1.53 (s, 9H); 13C{1H} NMR (125 MHz, CDCl3) δ 155.3 (C),
136.7 (C), 131.3 (C), 130.0 (C), 124.9 (C), 121.1 (CH), 117.5 (CH),
110.9 (CH), 108.2 (C), 80.1 (C), 42.6 (CH2), 41.8 (CH2), 28.5
(CH3), 21.8 (CH3), 21.5 (CH2); ATR-FTIR (thin film) 3308, 2979,
2789
dx.doi.org/10.1021/jo500252e | J. Org. Chem. 2014, 79, 2781−2791