FEATURE ARTICLE
HI-Catalysis
151
HRMS: m/z (%) calcd for [C15H17NO+]: 227.1310; found: 227.1309
(69).
HRMS: m/z (%) calcd for [C15H1337ClF3N+]: 301.0659; found:
301.0677 (24); calcd for [C15H1335ClF3N+]: 299.0689; found:
299.0683 (65).
Anal. Calcd for C15H17NO (227.3): C, 79.26; H, 7.54; N, 6.16.
Found: C, 79.05; H, 7.55; N, 6.14.
Anal. Calcd for C15H13ClF3N (299.7): C, 60.11; H, 4.37; N, 4.67.
Found: C, 60.05; H, 4.41; N, 4.63.
Amine 15b
The general procedure B was used to synthesize amine 15b from 1-
methoxy-4-vinylbenzene (5) and 4-chlorobenzenamine (8). After
purification by flash chromatography (PE–EtOAc, 5:1), amine 15b
(1.018 g, 83%) was obtained as a brown oil.
17b
IR (neat): 3447, 3372, 3040, 2976, 2933, 2876, 1620, 1491, 1421,
1414, 1327, 1283, 1161, 1115, 1070, 1018, 885, 875, 843, 816, 614
cm–1.
IR (neat): 3448, 3369, 2966, 2933, 2853, 1732, 1614, 1511, 1489,
1460, 1413, 1245, 1178, 1033, 877, 833, 815 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.57 (d, J = 7.3 Hz, 3 H), 3.43 (br
s, 2 H), 3.77 (s, 3 H), 3.96 (q, J = 6.8 Hz, 1 H), 6.54 (d, J = 8.3 Hz,
1 H), 6.82 (d, J = 8.8 Hz, 2 H), 7.02 (dd, J = 8.3, 2.0 Hz, 1 H), 7.09
(d, J = 8.3 Hz, 2 H), 7.22 (d, J = 2.0 Hz, 1 H).
13C NMR (125 MHz, DEPT, CDCl3): d = 21.8 (CH3), 39.5 (CH),
55.2 (CH3), 114.2 (CH), 117.2 (CH), 123.4 (C), 126.9 (CH), 127.1
(CH), 128.3 (CH), 131.7 (C), 136.7 (C), 142.9 (C), 158.3 (C).
HRMS: m/z (%) calcd for [C15H1637ClNO+]: 263.0891; found:
263.0908 (17); calcd for [C15H1635ClNO+]: 261.0920; found:
261.0916 (55).
1H NMR (300 MHz, CDCl3): d = 1.60 (d, J = 7.2 Hz, 3 H), 3.38 (br
s, 2 H), 4.07 (q, J = 7.2 Hz, 1 H), 6.56 (d, J = 8.3 Hz, 1 H), 7.05 (dd,
J = 8.3, 2.5 Hz, 1 H), 7.22 (d, J = 2.3 Hz, 1 H), 7.29 (d, J = 8.1 Hz,
2 H), 7.54 (d, J = 8.3 Hz, 2 H).
13C NMR (75 MHz, DEPT, CDCl3): d = 21.6 (CH3), 40.0 (CH),
117.5 (CH), 123.7 (C), 124.2 (C, q, J = 272.2 Hz), 125.9 (CH, q,
J = 3.8 Hz), 127.2 (CH), 127.5 (CH), 127.8 (CH), 129.0 (C, q,
J = 32.4 Hz), 130.4 (C), 142.8 (C), 149.0 (C).
HRMS: m/z (%) calcd for [C15H1337ClF3N+]: 301.0659; found:
301.0675 (30); calcd for [C15H1335ClF3N+]: 299.0689; found:
299.0707 (100).
Anal. Calcd for C15H13ClF3N (299.7): C, 60.11; H, 4.37; N, 4.67.
Found: C, 60.14; H, 4.48; N, 4.73.
Anal. Calcd for C15H16ClNO (261.8): C, 68.83; H, 6.16; N, 5.35.
Found: C, 68.68; H, 6.26; N, 5.40.
Amines 18a/18b
The general procedure B was used to synthesize amines 18a and
18b from 1-fluoro-4-vinylbenzene (7) and aniline (2). After purifi-
cation by flash chromatography (PE–EtOAc, 5:1), amine 18a (576
mg, 57%) and amine 18b (254 mg, 25%) were obtained as colorless
oils.
Amine 16a
The general procedure B was used to synthesize amine 16a from 1-
(trifluoromethyl)-4-vinylbenzene (6) and aniline (2). After purifica-
tion by flash chromatography (PE–EtOAc, 10:1), amine 16a (125
mg, 10%) was obtained as a colorless oil.
IR (neat): 3410, 3053, 2971, 2929, 2871, 1619, 1603, 1506, 1419,
1327, 1258, 1209, 1164, 1123, 1016, 841, 751, 693 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.52 (d, J = 6.9 Hz, 3 H), 4.05 (br
s, 1 H), 4.53 (q, J = 6.9 Hz, 1 H), 6.47 (d, J = 7.8 Hz, 2 H), 6.67 (t,
J = 7.3 Hz, 1 H), 7.09 (dd, J = 8.3, 7.3 Hz, 2 H), 7.48 (d, J = 7.8 Hz,
2 H), 7.57 (d, J = 7.8 Hz, 2 H).
13C NMR (125 MHz, DEPT, CDCl3): d = 25.1 (CH3), 53.3 (CH),
113.3 (CH), 117.7 (CH), 124.2 (C, q, J = 272.2 Hz), 125.7 (CH, q,
J = 3.8 Hz), 126.2 (CH), 129.2 (CH), 129.2 (C, q, J = 32.0 Hz),
146.8 (C), 149.5 (C).
18a
IR (neat): 3407, 3053, 2967, 2931, 2870, 1604, 1508, 1451, 1429,
1340, 1257, 1180, 1093, 835, 751, 693 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.45 (d, J = 6.8 Hz, 3 H), 3.98 (br
s, 1 H), 4.43 (q, J = 6.8 Hz, 1 H), 6.47 (d, J = 7.7 Hz, 2 H), 6.64 (t,
J = 7.4 Hz, 1 H), 6.97 (t, J = 8.7 Hz, 2 H), 7.08 (dd, J = 8.7, 7.4 Hz,
2 H), 7.29 (dd, J = 7.4, 5.5 Hz, 2 H).
13C NMR (75 MHz, DEPT, CDCl3): d = 25.1 (CH3), 52.8 (CH),
113.3 (CH), 115.4 (CH, d, J = 21.4 Hz), 117.4 (CH), 127.3 (CH, d,
J = 8.2 Hz), 129.1 (CH), 140.9 (C, d, J = 3.3 Hz), 147.1 (C), 161.7
(C, d, J = 244.3 Hz).
HRMS: m/z (%) calcd for [C15H14F3N+]: 265.1078; found: 265.1084
(45).
HRMS: m/z (%) calcd for [C14H14FN+]: 215.1110; found: 215.1099
(55).
Anal. Calcd for C15H14F3N (265.3): C, 67.91; H, 5.32; N, 5.28;
Found: C, 67.63; H, 5.34; N, 4.95.
Anal. Calcd for C14H14FN (215.3): C, 78.11; H, 6.56; N, 6.51.
Found: C, 78.08; H, 6.55; N, 6.47.
Amines 17a/17b
The general procedure B was used to synthesize amines 17a and
17b from 1-(trifluoromethyl)-4-vinylbenzene (6) and 4-chloroben-
zenamine (8). After purification by flash chromatography (PE–
EtOAc, 5:1), amine 17a (213 mg, 15%) and amine 17b (245 mg,
17%) were obtained as brown oils.
18b
IR (neat): 3453, 3373, 3064, 3035, 2968, 2932, 2874, 1622, 1602,
1508, 1496, 1453, 1295, 1221, 1158, 1097, 1015, 751, 553 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.59 (d, J = 7.2 Hz, 3 H), 3.40 (br
s, 2 H), 4.05 (q, J = 7.2 Hz, 1 H), 6.64 (d, J = 7.9 Hz, 1 H), 6.84 (dd,
J = 7.5, 7.4 Hz, 1 H), 6.95 (t, J = 8.7 Hz, 2 H), 7.07 (dd, J = 7.5, 1.3
Hz, 1 H), 7.14 (dd, J = 8.7, 5.5 Hz, 2 H), 7.25 (d, J = 7.7 Hz, 1 H).
13C NMR (75 MHz, DEPT, CDCl3): d = 21.9 (CH3), 39.4 (CH),
115.5 (CH, d, J = 20.9 Hz), 116.3 (CH), 118.8 (CH), 127.1 (CH),
127.4 (CH), 128.8 (CH, d, J = 7.7 Hz), 129.5 (C), 141.3 (C, d,
J = 3.3 Hz), 144.1 (C), 161.4 (C, d, J = 244.3 Hz).
17a
IR (neat): 3422, 2971, 2928, 2871, 1619, 1601, 1500, 1418, 1325,
1164, 1127, 1067, 1017, 841, 816 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.50 (d, J = 6.8 Hz, 3 H), 4.10 (br
s, 1 H), 4.46 (q, J = 6.6 Hz, 1 H), 6.37 (d, J = 9.0 Hz, 2 H) 7.02 (d,
J = 8.9 Hz, 2 H), 7.44 (d, J = 8.1 Hz, 2 H), 7.56 (d, J = 8.1 Hz, 2 H).
13C NMR (75 MHz, DEPT, CDCl3): d = 24.9 (CH3), 53.4 (CH),
114.4 (CH), 122.3 (C), 124.3 (C, q, J = 247.0 Hz), 125.8 (CH, q,
J = 3.8 Hz), 126.1 (CH), 129.0 (CH), 129.4 (C, q, J = 32.4 Hz),
145.3 (C), 149.0 (C).
HRMS: m/z (%) calcd for [C14H14FN+]: 215.1110; found: 215.1094
(44).
Anal. Calcd for C14H14FN (215.3): C, 78.11; H, 6.56; N, 6.51.
Found: C, 77.99; H, 6.58; N, 6.54.
Synthesis 2007, No. 1, 145–154 © Thieme Stuttgart · New York