The Journal of Organic Chemistry
Article
1.46 (3H, s, CH3), 3.37−3.49 (1H, m, CH2), 3.59−3.84 (3H, m,
CH2), 6.45 (1H, d, J = 15.9, CH), 6.82 (1H, d, J = 7.8, CH), 6.90 (1H,
d, J = 15.9, CH), 6.97 (1H, td, J = 7.4, 0.7, CH), 7.10 (1H, dd, J = 7.3,
0.7 CH), 7.19 (1H, td, J = 7.7, 1.2, CH), 7.53 (2H, d, J = 8.3, CH),
7.64 (2H, d, J = 8.3, CH); 13C NMR (75 MHz) δ 20.5 (CH3), 28.5
(CH3), 48.2 (C), 50.3 (CH2), 63.8 (CH2), 109.7 (C), 111.2 (C),
112.2 (CH), 119.0 (C), 122.0 (CH), 122.5 (CH), 127.3 (2 × CH),
127.9 (CH), 130.6 (CH), 130.7 (CH), 132.6 (2 × CH), 139.6 (C),
H]+, 370 (100) [M(Br79) + H]+; HRMS (FAB+): m/z calcd. for
C20H21BrNO: 370.0807 [M(Br79) + H]+; found: 370.0802.
10-[2-(2-Bromophenyl)ethylene]-9,9-trimethyl-indolino[2,1-b]-
oxazolidine (2l). Product was isolated as a pale yellow solid (307 mg,
1
83%). m.p.: 96−98 °C; H NMR (300 MHz) δ 1.21 (3H, s, CH3),
1.49 (3H, s, CH3), 3.49−3.60 (1H, m, CH2), 3.63−3.76 (2H, m,
CH2), 3.82−3.90 (1H, m, CH2), 6.21 (1H, d, J = 15.8, CH), 6.83 (1H,
d, J = 8.0, CH), 6.97 (1H, t, J = 7.0, CH), 7.11 (1H, d, J = 6.6, CH),
7.13 (1H, d, J = 7.4, CH), 7.18 (1H, d, J = 7.8, CH), 7.25 (1H, d, J =
16.1, CH), 7.31 (1H, t, J = 7.2, CH), 7.58 (2H, m, CH); 13C NMR (75
MHz) δ 20.5 (CH3), 28.5 (CH3), 47.9 (C), 50.3 (CH2), 63.7 (CH2),
109.8 (C), 112.2 (CH), 121.8 (CH), 122.5 (CH), 124.0 (C), 127.5
(CH), 127.7 (2 × CH), 129.2 (CH), 129.3 (CH), 131.8 (CH), 133.1
141.0 (C), 150.4 (C); IR U = 2964, 2926, 2867, 2226 cm−1; MS (FAB
̅
+): m/z (%): 317 (100) [M + H]+; HRMS (FAB+): m/z calcd. for
C21H21N2O: 317.1654 [M + H]+; found: 317.1650.
10-[2-(4-Nitrophenyl)ethylene]-9,9-trimethyl-indolino[2,1-b]-
oxazolidine (2h). Product was isolated as a brown-red solid (274 mg,
1
(CH), 137.0 (C), 139.7 (C), 150.8 (C); IR U = 2963, 2924, 2877
̅
82%). m.p.: 145−147 °C; H NMR (300 MHz) δ 1.18 (3H, s, CH3),
cm−1; MS (FAB+): m/z (%): 372 (80) [M(Br81) + H]+, 370 (90)
[M(Br79) + H]+; HRMS (FAB+): m/z calcd. for C20H21BrNO:
370.0807 [M(Br79) + H]+; found: 370.0792.
1.47 (3H, s, CH3), 3.40−3.51 (1H, m, CH2), 3.60−3.82 (3H, m,
CH2), 6.50 (1H, d, J = 15.9, CH), 6.83 (1H, d, J = 7.8, CH), 6.96 (1H,
d, J = 15.9, CH), 6.97 (1H, td, J = 7.4, 0.7, CH), 7.10 (1H, dd, J = 7.3,
0.7, CH), 7.20 (1H, td, J = 7.7, 1.2, CH), 7.58 (2H, d, J = 8.8, CH),
8.21 (2H, d, J = 8.8, CH); 13C NMR (75 MHz) δ 20.6 (CH3), 28.5
(CH3), 48.3 (C), 50.3 (CH2), 63.9 (CH2), 109.7 (C), 112.2 (CH),
122.1 (CH), 122.5 (CH), 124.2 (2 × CH), 127.4 (2 × CH), 127.9
(CH), 130.3 (CH), 131.6 (CH), 139.5 (C), 143.0 (C), 147.2 (C),
10-[2-(Bithiophenyl)ethylene]-9,9-trimethyl-indolino[2,1-b]-
oxazolidine (3c). Product was isolated as a pink solid (260 mg, 69%).
1
m.p.: 122−124 °C; H NMR (300 MHz) δ 1.18 (3H, s, CH3), 1.45
(3H, s, CH3), 3.41−3.53 (1H, m, CH2), 3.58−3.86 (3H, m, CH2),
6.11 (1H, d, J = 15.6, CH), 6.81 (1H, d, J = 7.8, CH), 6.90−7.12 (6H,
m, CH), 7.14−7.21 (2H, m, CH), 7.22 (1H, dd, J = 5.1, 1.0, CH); 13C
NMR (75 MHz) δ 20.4 (CH3), 28.5 (CH3), 48.2 (C), 50.2 (CH2),
63.7 (CH2), 109.7 (C), 112.1 (CH), 121.9 (CH), 122.5 (CH), 123.9
(CH), 124.0 (CH), 124.7 (CH), 125.6 (CH), 125.9 (CH), 127.5
(CH), 127.7 (CH), 128.0 (CH), 136.7 (C), 137.4 (C), 139.8 (C),
150.3 (C); IR U = 2967, 2931, 2890 cm−1; MS (FAB+): m/z (%): 337
̅
(100) [M + H]+; HRMS (FAB+): m/z calcd. for C20H21N2O3:
337.1552 [M + H]+; found: 337.1551.
10-[2-(3-Methoxyphenyl)ethylene]-9,9-trimethyl-indolino[2,1-b]-
140.7 (C), 150.5 (C); IR U = 2998, 2952, 2886 cm−1; MS (FAB+):
oxazolidine (2i). Product was isolated as a light-brown solid (220 mg,
̅
1
m/z (%): 380 (100) [M + H]+; HRMS (FAB+): m/z calcd. for
C22H22NOS2: 380.1143 [M + H]+; found: 380.1144.
69%). m.p.: 98−100 °C; H NMR (300 MHz) δ 1.20 (3H, s, CH3),
1.48 (3H, s, CH3), 3.44−3.54 (1H, m, CH2), 3.61−3.75 (2H, m,
CH2), 3.78−3.87 (1H, m, CH2), 3.84 (3H, s, CH3), 6.32 (1H, d, J =
15.9, CH), 6.84 (1H, d, J = 7.6, CH), 6.85 (1H, d, J = 7.9, CH), 6.88
(1H, d, J = 15.9, CH), 6.98 (1H, t, J = 7.3, CH), 7.03 (1H, s, CH),
7.09 (1H, d, J = 8.3, CH), 7.11 (1H, d, J = 8.0, CH), 7.20 (1H, td, J =
7.8, 1.0, CH), 7.29 (1H, t, J = 7.9, CH); 13C NMR (75 MHz) δ 20.5
(CH3), 28.5 (CH3), 48.1 (C), 50.2 (CH2), 55.4 (CH3), 63.7 (CH2),
109.9 (C), 112.0 (CH), 112.1 (CH), 113.7 (CH), 119.5 (CH), 121.8
(CH), 122.5 (CH), 126.3 (CH), 127.7 (CH), 129.8 (CH), 132.3
10-[2-(Ferrocenyl)ethylene]-9,9-trimethyl-indolino[2,1-b]-
oxazolidine (3d). Product was isolated as a green solid (228 mg, 57%).
1
m.p.: 129−131 °C; H NMR (300 MHz) δ 1.20 (3H, s, CH3), 1.47
(3H, s, CH3), 3.45−3.55 (1H, m, CH2), 3.62−3.84 (3H, m, CH2),
4.13 (5H, s, Fc-H), 4.26 (2H, t, J = 1.8, Fc-H), 4.43 (2H, m, Fc-H),
5.87 (1H, d, J = 15.6, CH), 6.66 (1H, d, J = 15.8, CH), 6.81 (1H, d, J =
7.8, CH), 6.96 (1H, td, J = 7.4, 0.6, CH), 7.11 (1H, dd, J = 7.3, 0.8,
CH), 7.19 (1H, td, J = 7.7, 1.2, CH); 13C NMR (75 MHz) δ 20.4
(CH3), 28.6 (CH3), 47.6 (C), 50.3 (CH2), 63.5 (CH2), 67.2 (2 × Fc-
H), 69.1 (2 × Fc-H), 69.2 (5 × Fc-H), 82.3 (C), 110.1 (C), 112.1
(CH), 121.8 (CH), 122.3 (CH), 122.5 (CH), 127.7 (CH), 130.5
(CH), 138.0 (C), 139.8 (C), 150.6 (C), 160.0 (C); IR U = 2992,
̅
2964, 2937, cm−1; MS (FAB+): m/z (%): 322 (100) [M + H]+;
HRMS (FAB+): m/z calcd. for C21H24NO2: 322.1807 [M + H]+;
found: 322.1800.
(CH), 139.8 (C), 150.7 (C); IR U = 3104, 2990, 2956, 2887 cm−1;
̅
MS (FAB+): m/z (%): 400 (100) [M + H]+; HRMS (FAB+): m/z
calcd. for C24H26FeNO: 400.1364 [M + H]+; found: 400.1362.
2-(3′,3′-Dimethyl-6-nitro-3′H-spiro[chromene-2,2′-indol]-1′-yl)-
ethanol (5). Product was isolated as a purple solid (317 mg, 90%).
10-[2-(2-Methoxyphenyl)ethylene]-9,9-trimethyl-indolino[2,1-b]-
oxazolidine (2j). Product was isolated as a light-yellow solid (246 mg,
1
77%). m.p.: 74−76 °C; H NMR (300 MHz) δ 1.19 (3H, s, CH3),
1.46 (3H, s, CH3), 3.45−3.55 (1H, m, CH2), 3.60−3.74 (2H, m,
CH2), 3.78−3.86 (1H, m, CH2), 3.86 (3H, s, CH3), 6.33 (1H, d, J =
16.1, CH), 6.82 (1H, d, J = 7.8, CH), 6.91 (1H, d, J = 8.5, CH), 6.95
(2H, t, J = 7.4, CH), 7.10 (1H, d, J = 6.8, CH), 7.18 (1H, td, J = 7.6,
1.4, CH), 7.19 (1H, d, J = 16.1, CH), 7.26 (1H, td, J = 7.4, 1.5 CH),
7.52 (1H, dd, J = 7.6, 1.3, CH); 13C NMR (75 MHz) δ 20.5 (CH3),
28.5 (CH3), 47.9 (C), 50.2 (CH2), 55.5 (CH3), 63.6 (CH2), 110.2
(C), 111.1 (CH), 112.1 (CH), 120.7 (CH), 121.7 (CH), 122.5 (CH),
125.6 (C), 126.3 (CH), 127.3 (2 × CH), 127.6 (CH), 129.0 (CH),
1
m.p.: 152−154 °C; H NMR (300 MHz) δ 1.19 (3H, s, CH3), 1.29
(3H, s, CH3), 3.27−3.52 (2H, m, CH2), 3.67−3.89 (2H, m, CH2),
5.88 (1H, d, J = 10.4, CH), 6.67 (1H, d, J = 7.78, CH), 6.76 (1H, d, J =
8.7, CH), 6.91 (1H, td, J = 7.3, 0.7, CH), 6.91 (1H, d, J = 10.8, CH),
7.10 (1H, dd, J = 7.3, 0.8, CH), 7.20 (1H, td, J = 7.7, 1.2, CH), 8.00
(1H, d, J = 2.5, CH), 8.02 (1H, dd, J = 8.7, 2.7, CH); 13C NMR (75
MHz) δ 20.1 (CH3), 26.0 (CH3), 46.2 (C), 52.9 (CH2), 60.9 (CH2),
106.8 (C), 107.0 (CH), 115.6 (CH), 118.6 (C), 120.0 (CH), 122.0 (2
× CH), 122.9 (CH), 126.1 (CH), 127.9 (CH), 128.3 (CH), 135.9
139.9 (C), 150.9 (C), 157.1 (C); IR U = 3024, 2992, 2887, cm−1; MS
̅
(C), 141.2 (C), 147.1 (C), 159.4 (C); IR U = 3364 (bs), 2961, 2926,
̅
(FAB+): m/z (%): 322 (100) [M + H]+; HRMS (FAB+): m/z calcd.
for C21H24NO2: 322.1807 [M + H]+; found: 322.1811.
2867 cm−1; MS (FAB+): m/z (%): 353 (100) [M + H]+; HRMS
(FAB+): m/z calcd. for C20H21N2O4: 353.1501 [M + H]+; found:
10-[2-(3-Bromophenyl)ethylene]-9,9-trimethyl-indolino[2,1-b]-
36
1
353.1498. H and 13C NMR were consistent with literature data.
oxazolidine (2k). Product was isolated as a pale yellow solid (325 mg,
1
88%). m.p.: 112−114 °C; H NMR (300 MHz) δ 1.17 (3H, s, CH3),
ASSOCIATED CONTENT
1.45 (3H, s, CH3), 3.39−3.50 (1H, m, CH2), 3.59−3.82 (3H, m,
CH2), 6.30 (1H, d, J = 15.9, CH), 6.81 (1H, d, J = 7.8, CH), 6.82 (1H,
d, J = 15.6, CH), 6.95 (1H, t, J = 7.4, CH), 7.09 (1H, d, J = 7.4, CH),
7.18 (1H, td, J = 7.6, 1.1, CH), 7.21 (1H, t, J = 7.8, CH), 7.36 (1H, d, J
= 8.8, CH), 7.40 (1H, d, J = 8.2, CH), 7.60 (1H, t, J = 1.7, CH); 13C
NMR (75 MHz) δ 20.5 (CH3), 28.5 (CH3), 48.1 (C), 50.3 (CH2),
63.7 (CH2), 109.8 (C), 112.2 (CH), 121.9 (CH), 122.5 (CH), 123.0
(C), 125.5 (CH), 127.8 (CH), 127.9 (CH), 129.7 (CH), 130.3 (CH),
■
S
* Supporting Information
Additional data and the copies of H and 13C NMR. This
material is available free of charge via the Internet at http://
1
AUTHOR INFORMATION
Corresponding Authors
■
130.8 (CH), 131.0 (CH), 138.8 (C), 139.7 (C), 150.6 (C); IR U =
̅
2959, 2925, 2886 cm−1; MS (FAB+): m/z (%): 372 (70) [M(Br81) +
G
J. Org. Chem. XXXX, XXX, XXX−XXX