N. Zhao et al. / Tetrahedron xxx (xxxx) xxx
7
185.1079 [M þ H]þ; found: 185.1085.
202.1235.
4.18. (Z)-1-(1,2-Diphenylvinyl)-1H-imidazole (3n)
4.24. 1-Styrylpyrrolidin-2-one (3t)
Z-isomer: yellow oil (60.2 mg, 64% yield). 1H NMR (400 MHz,
Yellow solid (112.4 mg, 91% yield). 1H NMR (400 MHz, CDCl3):
d
¼ 7.45 (s, 1H), 7.39e7.37 (m, 3H), 7.28e7.23 (m, 6H), 6.98 (s, 1H),
CDCl3): ¼ 7.33e7.29 (m, 2H), 7.25e7.22 (m, 1H), 7.20e7.18 (m, 2H),
6.79 (d, J ¼ 9.6 Hz, 1H), 6.00 (d, J ¼ 9.6 Hz, 1H), 3.20 (t, 2H), 2.41 (t,
2H), 1.94 (m, 2H); 13C NMR (100 MHz, CDCl3):
129.13, 127.77, 126.83, 123.82, 113.77, 48.04, 30.34, 18.82; HRMS:
calcd for C12H13NO: 188.1075 [M þ H]þ; found: 188.1078.
E-isomer: white solid (8.5 mg, 9% yield). 1H NMR (400 MHz,
d
6.90 (t, 1H), 6.88e6.86 (m, 2H); 13C NMR (100 MHz, CDCl3):
d
¼ 137.60, 137.50, 134.47, 133.86, 130.18, 129.25, 128.82, 128.72,
d
¼ 175.54, 136.25,
128.61, 128.38, 125.91, 124.69, 119.64; HRMS: calcd for C17H14N2:
247.1235 [M þ H]þ; found: 247.1230.
4.19. (Z)-1-Styryl-1H-indole (3o)
CDCl3):
(m, 2H), 7.19e7.15 (m, 1H), 5.87 (d, J ¼ 14.8 Hz, 1H), 3.63 (t, 2H), 2.53
(t, 2H), 2.14 (m, 2H); 13C NMR (100 MHz, CDCl3):
d
¼ 7.62 (d, J ¼ 14.8 Hz, 1H), 7.36e7.34 (m, 2H), 7.30e7.27
Brown oil (79.3 mg, 72% yield). 1H NMR (400 MHz, CDCl3):
d
¼ 173.30, 136.28,
d
¼ 7.53 (d, 1H, J ¼ 8.0 Hz), 7.29 (d, 1H, J ¼ 8.0 Hz), 7.19e7.00 (m, 7H),
128.57, 126.46, 125.53, 123.48, 111.66, 45.13, 31.15, 17.33; HRMS:
6.94 (d, 1H, J ¼ 3.2 Hz), 6.88 (d, 1H, J ¼ 9.2 Hz), 6.42 (d, 1H,
calcd for C12H13NO: 188.1075 [M þ H]þ; found: 188.1074.
J ¼ 3.2 Hz), 6.21 (d, 1H, J ¼ 9.2 Hz); 13C NMR (100 MHz, CDCl3):
d
¼ 135.87, 134.96, 128.69, 128.56, 128.42, 127.52, 127.09, 123.30,
4.25. (Z)-3-Styryloxazolidin-2-one (3u)
122.43, 120.87, 120.69, 119.60, 110.11, 103.94; HRMS: calcd for
C
16H13N: 220.1126 [M þ H]þ; found: 220.1121.
Yellow oil (85.5 mg, 90% yield). 1H NMR (400 MHz, CDCl3):
d
¼ 7.34e7.30 (m, 2H), 7.27e7.25 (m,1H), 7.23e7.20 (m, 2H), 6.67 (d,
4.20. (Z)-1-Styryl-1H-benzo[d]imidazole (3p)
1H, J ¼ 9.6 Hz), 5.99 (d, 1H, J ¼ 9.6 Hz), 4.26 (t, 2H), 3.37 (t, 2H); 13
C
NMR (100 MHz, CDCl3):
d
¼ 135.56, 129.29, 127.94, 127.11, 124.24,
Yellow solid (38.8 mg, 35% yield): mp 115e117 ꢀC. 1H NMR
112.78, 62.63, 44.97; HRMS: calcd for C11H11NO2: 190.0868 [M þ
(400 MHz, CDCl3):
d
¼ 7.84e7.80 (m, 2H), 7.37e7.30 (m, 3H),
H]þ; found: 190.0867.
7.25e7.22 (m, 3H), 7.11e7.08 (m, 2H), 6.87 (d,1H, J ¼ 8.8 Hz), 6.58 (d,
1H, J ¼ 8.8 Hz); 13C NMR (100 MHz, CDCl3):
d
¼ 143.29, 141.99,
4.26. (Z)-5-Methoxy-1-styryl-1H-indole (3v)
133.63, 133.00, 128.86, 128.46, 128.44, 125.36, 123.63, 122.86,
120.40, 120.31, 110.27; HRMS: calcd for C15H12N2: 221.1079 [M þ
H]þ; found: 221.1083.
White solid (97.4 mg, 78% yield). 1H NMR (400 MHz, CDCl3):
d
¼ 7.25e7.17 (m, 6H), 7.07 (d, J ¼ 2.4 Hz, 1H), 6.99 (d, J ¼ 2.8 Hz, 1H),
6.92e6.86 (m, 2H), 6.42 (d, J ¼ 3.2 Hz, 1H), 6.24 (d, J ¼ 9.2 Hz, 1H),
3.85 (s, 3H); 13C NMR (100 MHz, CDCl3):
4.21. (Z)-1-Styryl-1H-1,2,3-triazole (3q)
d
¼ 154.89, 135.01, 130.97,
129.02, 128.65, 128.40, 127.61, 127.45, 123.41, 119.18, 112.24, 110.82,
103.63, 102.87, 55.83; HRMS: calcd for C17H15NO: 250.1232 [M þ
H]þ; found: 250.1234.
Yellow solid (35.4 mg, 41% yield). 1H NMR (400 MHz, CDCl3):
d
¼ 7.59 (d, 1H, J ¼ 1.2 Hz), 7.40 (d, 1H, J ¼ 1.2 Hz), 7.34e7.32 (m, 3H),
7.28 (d, 1H, J ¼ 9.6 Hz), 7.14e7.12 (m, 2H), 6.58 (d, 1H, J ¼ 9.6 Hz); 13
C
NMR (100 MHz, CDCl3):
d
¼ 133.47, 133.11, 128.96, 128.76, 128.49,
4.27. (E)-5-Fluoro-1-styryl-1H-indole (3w)
123.98, 123.36; HRMS: calcd for C10H9N3: 172.0875 [M þ H]þ;
found: 172.0879.
Yellow solid (97.7 mg, 82% yield). 1H NMR (400 MHz, CDCl3):
d
¼ 7.58 (d, J ¼ 14.8 Hz, 1H), 7.51 (d, J ¼ 3.6 Hz, 1H), 7.45e7.42 (m,
4.22. (Z)-9-Styryl-9H-carbazole (3r)
3H), 7.36 (t, 2H), 7.28e7.22 (m, 2H), 7.04e6.99 (m, 1H), 6.66 (d,
J ¼ 14.4 Hz, 1H), 6.61 (d, J ¼ 3.6 Hz, 1H); 13C NMR (100 MHz, CDCl3):
Yellow solid (87.9 mg, 65% yield): mp 90e92 ꢀC. 1H NMR
d
¼ 159.65, 157.30, 135.80, 132.20, 129.60, 129.50, 128.83, 127.01,
(400 MHz, CDCl3):
d
¼ 8.09 (d, 1H, J ¼ 8.0 Hz), 7.36e7.32 (m, 2H),
125.71, 125.34, 123.43, 114.69, 111.07, 110.82, 110.32, 110.22, 106.37,
7.27e7.23 (m, 2H), 7.19 (d, 1H, J ¼ 8.0 Hz), 7.11e7.07 (m, 5H), 6.92 (d,
106.14, 105.06, 105.02; 19F NMR (376 MHz, CDCl3):
d
¼ ꢁ123.34;
1H, J ¼ 8.8 Hz), 6.67 (d, 1H, J ¼ 8.8 Hz); 13C NMR (100 MHz, CDCl3):
HRMS: calcd for C16H12FN: 238.1032 [M þ H]þ; found: 238.1035.
4.28. (Z)-Butyl(styryl)sulfane (4a)
d
¼ 139.23, 134.80, 128.75, 128.31, 127.83, 126.41, 125.89, 123.98,
122.01, 120.24, 120.11, 111.09; HRMS: calcd for C20H15N: 270.1283
[M þ H]þ; found: 270.1287.
Yellow oil (87.7 mg, 91% yield). 1H NMR (400 MHz, CDCl3):
4.23. 1-Styrylpiperidin-2-one (3s)
d
¼ 7.50 (d, 2H, J ¼ 7.6 Hz), 7.36 (t, 2H), 7.23e7.19 (m, 1H), 6.44 (d,
1H, J ¼ 10.8 Hz), 6.26 (d, 1H, J ¼ 10.8 Hz), 2.80 (t, 2H), 1.73e1.65 (m,
Z-isomer: yellow oil (26.5 mg, 26% yield). 1H NMR (400 MHz,
2H), 1.51e1.41 (m, 2H), 0.94 (t, 3H); 13C NMR (100 MHz, CDCl3):
CDCl3):
1H), 6.10 (d, J ¼ 9.2 Hz, 1H), 3.20 (t, 2H), 2.51 (t, 2H), 1.84e1.78 (m,
2H), 1.72e1.66 (m, 2H); 13C NMR (100 MHz, CDCl3):
d
¼ 7.34e7.29 (m, 2H), 7.27e7.21 (m, 3H), 6.79 (d, J ¼ 9.2 Hz,
d
¼ 137.05,128.58,128.18,127.68, 126.53,125.24, 35.58, 32.28, 21.68,
13.62; HRMS: calcd for C12H16S: 193.1051 [M þ H]þ; found:
d
¼ 170.83,
193.1054.
135.77, 128.96, 128.56, 128.20, 127.25, 119.70, 48.79, 32.28, 23.09,
20.94; HRMS: calcd for C13H15NO: 202.1232 [M þ H]þ; found:
202.1234.
4.29. (Z)-(4-Methoxyphenyl)(styryl)sulfane (4b)
E-isomer: white solid (32.4 mg, 32% yield). 1H NMR (400 MHz,
Yellow oil (109.4 mg, 90% yield). 1H NMR (400 MHz, CDCl3):
CDCl3):
7.17 (t, 1H), 5.96 (d, J ¼ 15.2 Hz, 1H), 3.55e3.51 (m, 2H), 2.56e2.52
(m, 2H), 1.94e1.82 (m, 4H); 13C NMR (100 MHz, CDCl3):
d
¼ 8.17 (d, J ¼ 15.2 Hz, 1H), 7.38e7.36 (m, 2H), 7.29 (t, 2H),
d
¼ 7.60 (d, 2H, J ¼ 7.2 Hz), 7.44e7.37 (m, 3H), 7.29e7.26 (m, 2H),
7.00e6.97 (m, 1H), 6.91 (dd, 1H, J1 ¼8.0 Hz, J2 ¼ 1.2 Hz), 6.64 (d, 1H,
d
¼ 168.57,
J ¼ 10.8 Hz), 6.48 (d, 1H, J ¼ 10.8 Hz), 3.91 (s, 3H); 13C NMR
136.71, 128.51, 126.92, 126.32, 125.66, 110.68, 45.18, 32.92, 22.49,
(100 MHz, CDCl3):
d
¼ 157.24, 130.93, 128.84, 128.46, 128.20, 127.65,
20.36; HRMS: calcd for C13H15NO: 202.1232 [M þ H]þ; found:
126.97, 125.29, 121.29, 110.91, 55.87; HRMS: calcd for C15H14OS:
Please cite this article as: N. Zhao et al., Anti-Markovnikov stereoselective hydroamination and hydrothiolation of (hetero)aromatic alkynes