The Journal of Organic Chemistry
Article
143.2, 139.6, 137.7, 136.0, 132.1, 129.4, 128.7, 128.4, 128.2, 127.9,
127.8, 127.3, 127.0, 126.5, 59.7, 21.4; HRMS (ESI, m/z) [M + Na]+
calculated for C22H21NNaO2S, 386.1191; found, 386.1199.
5.12 (1H), 4.78 (1H), 4.25 (1H), 2.10−1.85 (3H), 1.75−1.50 (3H);
13C NMR (100 MHz, CDCl3) 155.6, 136.6, 130.8, 128.5, 128.4, 128.1,
128.0, 127.7, 66.5, 46.3, 29.7, 24.7, 19.5; HRMS (ESI, m/z) [M + Na]+
calculated for C14H18NO2, 232.1338; found, 232.1359.
(E)-N-(1,3-Diphenylallyl)-4-nitrobenzenesulfonamide (3g): 0.175
g, 93% yield; Rf = 0.24 (30:70 = EtOAc/n-hexane); colorless solid; mp
156 °C; IR (neat) 3279, 3028, 2914, 1606, 1528, 1347, 1311, 1160,
N-(Cyclohex-2-en-1-yl)-4-methylbenzenesulfonamide (4d):14
0.112 g, 89% yield; Rf = 0.23 (5:95 = EtOAc/n-hexane); colorless
solid; mp 98−100 °C; IR (neat) 3282, 2927, 1597, 1427, 1327, 1157,
1
1090, 1027, 971, 853, 736, 697 cm−1; H NMR (400 MHz, CDCl3)
1
1072 cm−1; H NMR (400 MHz, CDCl3) 7.79 (d, J = 7.6 Hz, 2H),
8.12 (d, J = 8.8 Hz, 2H), 7.87 (d, J = 8.80 Hz, 2H), 7.28−7.19 (m,
10H), 6.45 (d, J = 15.92 Hz, 1H), 6.14 (dd, J = 6.90 and 9.04 Hz, 1H),
5.39 (s, 1H), 5.27 (d, J = 6.67 Hz, 1H); 13C NMR (100 MHz, CDCl3)
149.6, 146.6, 138.6, 135.4, 133.0, 128.9, 128.6, 128.4, 128.3, 127.3,
127.1, 126.4, 123.9, 60.2; HRMS (ESI, m/z) [M − H]+ calculated for
C21H17N2O4S, 393.0908; found, 393.0918.
7.31 (d, J = 7.6 Hz, 2H), 5.76 (d, J = 10 Hz, 1H), 5.36 (d, J = 9.8 Hz,
1H), 4.66 (d, J = 8.4 Hz, 1H), 3.82 (s, 1H), 2.44 (s, 3H), 2.10−1.45
(6H); 13C NMR (100 MHz, CDCl3) 143.2, 138.3, 131.5, 129.6,
127.06, 127.00, 48.9, 30.2, 24.4, 21.5, 19.3; HRMS (ESI, m/z) [M +
Na]+ calculated for C13H17NNaO2S, 274.0878; found, 274.0881.
Benzyl Cyclohept-2-en-1-ylcarbamate (4e): 0.075 g, 61% yield; Rf
= 0.29 (5:95 = EtOAc/n-hexane); colorless solid; mp 83−85 °C; IR
(E)-1-(1,3-Diphenylallyl)indolin-2-one (3h): 0.161 g, 99% yield; Rf
= 0.15 (20:80 = EtOAc/n-hexane); light brown liquid; IR (neat) 3055,
1
3028, 1712, 1612, 1450, 1338, 1199, 968 cm−1; H NMR (400 MHz,
1
(neat) 3422, 3314, 2916, 1685, 1541, 1400, 1254, 1038 cm−1; H
CDCl3) 7.54−7.22 (12H), 7.19−6.93 (2H), 6.90−6.73 (2H), 6.66 (d,
J = 7.6 Hz, 1H), 6.52 (d, J = 6.4 Hz, 1H), 3.69 (s, 2H); 13C NMR (100
MHz, CDCl3) 174.9, 143.0, 137.8, 136.2, 135.0, 128.7, 128.6, 128.1,
127.6, 127.4, 127.1, 126.7, 124.6, 124.5, 124.3, 122.1, 111.2, 56.0, 35.8;
HRMS (ESI, m/z) [M + Na]+ calculated for C23H20NO, 326.1545;
found, 326.1544.
NMR (400 MHz, CDCl3) 7.46−7.30 (5H), 5.95−5.70 (1H), 5.65−
5.50 (1H), 5.12 (s, 2H), 4.90 (s, 1H), 4.28 (s, 1H), 2.30−1.80 (4H),
1.78−1.32 (4H); 13C NMR (100 MHz, CDCl3) 155.5, 136.6, 134.9,
132.1, 128.5, 128.2, 128.1, 66.6, 52.2, 34.2, 28.4, 27.5, 26.6; HRMS
(ESI, m/z) [M + H]+ calculated for C15H20NO2, 246.1494; found,
246.1486.
(E)-1-(1,3-Diphenylallyl)pyrrolidin-2-one (3i): 0.137 g, 99% yield;
Benzyl (2-Methylcyclopent-2-en-1-yl)carbamate (4f): 0.083 g,
72% yield; Rf = 0.29 (10:90 = EtOAc/n-hexane); colorless solid; mp
50−52 °C; IR (neat) 3325, 2935, 1693, 1519, 1234, 1060, 1026 cm−1;
1H NMR (400 MHz, CDCl3) 7.44−7.28 (5H), 5.60−5.00 (3H),
4.85−4.40 (2H), 2.50−2.05 (3H), 1.85−1.50 (4H); 13C NMR (100
MHz, CDCl3) 156.1, 144.9, 139.7, 136.7, 136.6, 128.52, 128.50, 128.1,
128.0, 125.0, 66.5, 59.8, 35.2, 32.3, 29.8, 16.6, 13.7; HRMS (ESI, m/z)
[M + Na]+ calculated for C14H17NNaO2, 254.1157; found, 254.1165.
Benzyl (1,3-Diphenylprop-2-yn-1-yl)carbamate (4g):16a 0.115 g,
68% yield; Rf = 0.34 (10:90 = EtOAc/n-hexane); colorless solid; mp
Rf = 0.15 (10:90 = EtOAc/n-hexane); colorless solid; mp 63−65 °C;
1
IR (neat) 3028, 1681, 1492, 1415, 1265, 972 cm−1; H NMR (400
MHz, CDCl3) 7.55−7.20 (10H), 6.65 (d, J = 16 Hz, 1H), 6.48 (dd, J =
6.4, 15.6 Hz, 1H), 6.12 (d, J = 6.8 Hz, 1H), 3.52−3.40 (1H), 3.23−
3.09 (1H), 2.70−2.40 (2H), 2.20−1.90 (2H); 13C NMR (100 MHz,
CDCl3) 174.7, 138.7, 136.4, 133.4, 128.7, 128.6, 127.9, 127.8, 127.7,
126.5, 125.4, 56.2, 43.4, 31.2, 18.1; HRMS (ESI, m/z) [M + H]+
calculated for C19H20NO, 278.1545; found, 278.1547.
(E)-3-(1,3-Diphenylallyl)oxazolidin-2-one (3j):12b 0.138 g, 99%
yield; Rf = 0.23 (20:85 = EtOAc/n-hexane); colorless liquid; IR (neat)
3029, 1732, 1494, 1417, 1250, 974 cm−1; 1H NMR (400 MHz,
CDCl3) 7.50−7.26 (10H), 6.71 (d, J = 16 Hz, 1H), 6.49 (dd, J = 6.4,
16 Hz, 1H), 5.84 (d, J = 6.4 Hz, 1H), 4.45−4.25 (2H), 3.68−3.57
(1H), 3.37−3.25 (1H); 13C NMR (100 MHz, CDCl3) 158.2, 138.0,
136.2, 133.8, 128.9, 128.7, 128.17, 128.17, 127.8, 126.6, 124.8, 62.1,
58.4, 41.0; HRMS (ESI, m/z) [M + Na]+ calculated for
C18H17NaNO2, 302.1157; found, 302.1149.
1
88−90 °C; IR (neat) 3305, 3032, 1689, 1531, 1253, 1041 cm−1; H
NMR (400 MHz, CDCl3) 7.75−7.25 (15H), 5.99 (d, J = 8 Hz, 1H),
5.59 (d, J = 7.2 Hz, 1H), 5.29−5.09 (2H); 13C NMR (100 MHz,
CDCl3) 155.4, 139.0, 136.2, 131.8, 128.7, 128.6, 128.5, 128.3, 128.2,
127.0, 122.4, 86.9, 85.1, 67.2, 47.4; HRMS (ESI, m/z) [M + Na]+
calculated for C23H19NNaO2, 364.1308; found, 364.1302.
3-(1,3-Diphenylprop-2-yn-1-yl)oxazolidin-2-one (4h): 0.115 g,
83% yield; Rf = 0.2 (10:90 = EtOAc/n-hexane); light brown liquid;
IR (neat) 3491, 3059, 2916, 1955, 1894, 1743, 1489, 1415, 1246, 1068,
1029, 759 cm−1; 1H NMR (400 MHz, CDCl3) 7.67−7.60 (2H), 7.58−
7.51 (2H), 7.47−7.30 (6H), 4.48−4.37 (1H), 4.35−4.24 (1H), 3.87−
3.75 (1H), 3.32−3.20 (1H); 13C NMR (100 MHz, CDCl3) 157.8,
136.0, 131.9, 128.5, 127.4, 122.0, 87.4, 83.4, 62.2, 49.8, 40.4; HRMS
(ESI, m/z) [M + H]+ calculated for C18H16NO2, 278.1181; found,
278.1186.
N-(1,3-Diphenylprop-2-yn-1-yl)-4-methylbenzenesulfonamide
(4i):12b 0.138 g, 77% yield; Rf = 0.2 (10:90 = EtOAc/n-hexane);
colorless solid; mp 182−184 °C; IR (neat) 3267, 1593, 1489, 1427,
1323, 1153, 1049, 813 cm−1; 1H NMR (400 MHz, CDCl3) 7.84 (d, J =
8 Hz, 2H), 7.58 (d, J = 8 Hz, 2H), 7.45−7.20 (8H), 7.14 (d, J = 7.6
Hz, 2H), 5.58 (d, J = 9.2 Hz, 1H), 4.96 (d, J = 9.2 Hz, 1H), 2.34 (s,
3H); 13C NMR (100 MHz, CDCl3) 143.5, 137.4, 131.5, 129.5, 128.7,
128.6, 128.5, 128.1, 127.5, 127.3, 121.9, 86.7, 85.4, 49.8, 21.4; HRMS
(ESI, m/z) [M + Na]+ calculated for C22H19NaNO2S, 384.1034;
found, 384.1078.
(E)-N-(1,3-Diphenylallyl)-4-nitroaniline (3k):18c 0.140 g, 98% yield;
Rf = 0.3 (15:85 = EtOAc/n-hexane); yellow solid; mp 135−137 °C; IR
(neat) 3390, 3375, 1600, 1500, 1275, 1111, 968 cm−1; 1H NMR (400
MHz, CDCl3) 8.15−8.03 (2H), 7.55−7.15 (10H), 6.70−6.55 (3H),
6.41 (dd, J = 6, 16 Hz, 1H), 5.23 (d, J = 6 Hz, 1H), 4.93 (b s, 1H); 13C
NMR (100 MHz, CDCl3) 152.1, 140.3, 138.5, 136.0, 132.3, 129.2,
128.7, 128.6, 128.2, 128.1, 127.1, 126.6, 126.2, 112.1, 60.0; HRMS
(ESI, m/z) [M + Na]+ calculated for C21H18NaN2O2, 353.1266; found,
353.1278.
(E)-Benzyl 4-Phenylbut-3-enoate (4a): 0.080 g, 61% yield; Rf =
0.25 (10:90 = EtOAc/n-hexane); colorless oil; IR (neat) 3414, 3332,
3028, 2924, 1725, 1516, 1246, 964 cm−1; 1H NMR (400 MHz,
CDCl3) 7.55−7.20 (10H), 6.54 (d, J = 15.6 Hz, 1H), 6.35−6.05 (1H),
5.17 (s, 2H), 4.92 (b s, 1H), 4.02 (2H); 13C NMR (100 MHz, CDCl3)
156.2, 136.5, 131.8, 129.2, 128.6, 128.5, 128.3, 128.1, 127.7, 127.0,
126.4, 126.0, 125.7, 66.8, 43.2; HRMS (ESI, m/z) [M + H]+ calculated
for C17H18NO2, 268.1332; found, 268.1320.
(E)-Benzyl (4-Phenylbut-3-en-2-yl)carbamate (4b): 0.139 g, 99%
yield; Rf = 0.2 (10:90 = EtOAc/n-hexane); colorless solid; mp 66−68
°C; IR (neat) 3321, 3028, 1697, 1527, 1450, 1234, 1049, 964 cm−1; 1H
NMR (400 MHz, CDCl3) 7.60−7.15 (10H), 6.54 (d, J = 16 Hz, 1H),
6.18 (dd, J = 6, 16 Hz, 1H), 5.15 (s, 2H), 4.83 (b s, 1H), 4.51 (b s,
1H), 1.36 (d, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) 155.6,
136.6, 136.5, 131.1, 129.6, 128.6, 128.5, 128.1, 127.6, 126.4, 66.7, 48.4,
21.1; HRMS (ESI, m/z) [M + 2H]+ calculated for C18H20NO2,
282.1494; found, 282.1493.
Benzyl (1-(Naphthalen-2-yl)-3-phenylprop-2-yn-1yl)carbamate
(4j): 0.145 g, 74% yield; Rf = 0.32 (10:90 = EtOAc/n-hexane);
colorless solid; mp 160−165 °C; IR (neat) 3309, 2918, 1684, 1653,
1
1506, 1322, 1226, 1045, 972, 814, 757 cm−1; H NMR (400 MHz,
CDCl3) 8.06 (s, 1H), 7.95−7.82 (3H), 7.67 (d, J = 8.4 Hz, 1H), 7.58−
7.47 (4H), 7.45−7.32 (7H), 6.14 (d, J = 8.0 Hz, 1H), 5.45 (d, J = 7.6
Hz, 1H), 5.29−5.11 (2H); 13C NMR (100 MHz, CDCl3) 155.4, 136.1,
133.2, 133.1, 131.8, 128.7, 128.6, 128.5, 128.3, 128.2, 128.1, 127.6,
126.4, 126.3, 125.8, 124.8, 122.4, 86.9, 85.4, 67.2, 47.6; HRMS (ESI,
m/z) [M + H]+ calculated for C27H22NO2, 392.1651; found, 392.1640.
Benzyl (1-Phenyl-3-(triisopropylsilyl)prop-2-yn-1-yl)carbamate
(4k): 0.189 g, 91% yield; Rf = 0.31 (10:90 = EtOAc/n-hexane);
colorless oil; IR (neat) 3318, 2943, 2866, 1715, 1699, 1496, 1456,
Benzyl Cyclohex-2-en-1-ylcarbamate (4c):14 0.088 g, 76% yield; Rf
= 0.26 (10:90 = EtOAc/n-hexane); colorless solid; mp 83−85 °C; IR
(neat) 3313, 2916, 181, 1539, 1315, 1257, 1037 cm−1; 1H NMR (400
MHz, CDCl3) 7.50−7.30 (5H), 5.92−5.80 (1H), 5.68−5.55 (1H),
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dx.doi.org/10.1021/jo300706b | J. Org. Chem. 2012, 77, 5577−5583