Nickel-Catalyzed Coupling of Fluoroarenes and Amines
J=9 Hz, 2H, C6H4), 7.43–7.57 (m, 3H, C6H5), 7.73 (d, J=
8.1 Hz, 2H, C6H5), 7.80 (d, J=9 Hz, 2H, C6H4); 13C NMR:
d=47.66, 66.67, 113.28, 127.89, 128.20, 129.66, 131.63,
132.53, 138.82, 154.14, 195.30.
1.32–1.53 (m, 3H, CH+CH2), 1.73 (d, J=12.8, 2H, CH2),
2.60 (dt, J=2.4, 11.6 Hz, 2H, CH2), 3.47 (d, J=12.4 Hz, 2H,
CH2), 3.76 (s, 3H, CH3), 6.82 (d, J=9.2 Hz, 2H, C6H4), 6.91
(d, J=9.2 Hz, 2H, C6H4); 13C NMR: d=22.01, 30.70, 34.53,
51.80, 55.69, 111.48, 118.86, 146.67, 153.71; HR-MS (EI):
m/z=205.1457, calcd. for C13H19NO: 205.1467.
(E)-4-(4-Styrylphenyl)piperidine (4d): White solid; mp
140–1428C; 1H NMR: d=0.98 (d, J=6.3 Hz, 3H, CH3),
1.26–1.43 (m, 2H, CH2), 1.45–1.62 (m, 1H, CH), 1.74 (d, J=
11.1 Hz, 2H, CH2), 2.73 (t, J=11.3 Hz, 2H, CH2), 3.71 (d,
J=11.4 Hz, 2H, CH2), 6.84–7.09 (m, 4H, Ar+CH), 7.14–
7.23 (m, 1H, C6H5), 7.32( t, J=7.4 Hz, 2H, Ar), 7.40 (d, J=
8.4 Hz, 2H, Ar), 7.47 (d, J=6.9 Hz, 2H, Ar); 13C NMR: d=
21.96 30.78, 33.98, 49.66, 116.19, 125.53, 126.22, 126.97,
127.54, 128.67, 138.06, 151.19; HR-MS (EI): m/z=277.1826,
calcd. for C20H23N: 277.1830.
2-Methyl-1-(4-phenylphenyl)piperidine (4e): Light yellow
solid; mp 56–588C; 1H NMR: d=0.94 (d, J=6.6 Hz, 3H,
CH3), 1.44–1.58 (m, 4H, CH2), 1.63–1.69 (m, 1H, CH), 1.71–
1.84 (m, 1H, CH2), 2.89 (t, J=9.8 Hz, 1H, CH2), 3.21 (d, J=
12.2 Hz, 1H, CH2), 3.90 (s, 1H, CH2), 6.87 (d, J=8 Hz, 2H,
C6H4), 7.15 (t, J=7.3 Hz, 1H, C6H5), 7.28 (t, J=7.6 Hz, 2H,
C6H5), 7.39 (d, J=7.6 Hz, 2H, C6H5), 7.46 (d, J=8 Hz, 2H,
C6H4); 13C NMR: d=13.83, 19.65, 26.19, 31.69, 44.44, 51.07,
117.21, 126.32, 126.52, 127.73, 128.75, 131.48, 141.22, 150.71;
HR-MS (EI): m/z=251.1685, calcd. for C18H21N: 251.1674.
1-(4-Trifluoromethylphenyl) pyrrolidine (4f):[27] 1H NMR:
d=1.96–2.05 (m, 4H, CH2), 3.29 (t, J=6.6 Hz, 4H, CH2),
6.52 (d, J=8.8 Hz, 2H, C6H4), 7.42 (t, J=8.8 Hz, 2H, C6H4);
13C NMR: d=25.58, 47.66, 111.00, 116.80 (m), 126.50 (q, J=
3.8 Hz), 127.33, 149.93.
N,N-diethyl-4-morpholinobenzamide (3i): Light yellow oil.
1H NMR: d=1.18 (t, J=6.9 Hz, 6H, CH3), 3.19 (t, J=
4.8 Hz, 4H, CH2), 3.41 (b, 4H, CH2), 3.85 (t, J=4.8 Hz, 4H,
CH2), 6.88 (d, J=8.7 Hz, 2H, C6H4), 7.33 (d, J=8.7 Hz, 2H,
C6H4); 13C NMR: d=13.73, 48.70, 66.78, 114.63, 128.02,
128.13, 151.84, 171.42; HR-MS (EI) m/z=262.1674, calcd.
for C15H22N2O2: 262.1681.
4-(4-Trifluoromethylphenyl)morpholine (3j):[23] 1H NMR:
d=3.22 (t, J=4.8 Hz, 4H, CH2), 3.85 (t, J=4.8 Hz, 4H,
CH2), 6.90 (d, J=8.7 Hz, 2H, C6H4), 7.49 (d, J=8.7 Hz, 2H,
C6H4); 13C NMR: d=48.26, 66.73, 114.41, 121.07 (q, J=
33.5 Hz), 123.04, 126.54 (q, J=3.9 Hz), 153.45.
4-(2-Pyridyl)morpholine (3k):[24] 1H NMR: d=3.49 (t, J=
4.9 Hz, 4H, CH2), 3.82 (t, J=4.8 Hz, 4H, CH2), 6.62–6.68
(m, 2H, C5H4N), 7.47–7.52 (m, 1H, C5H4N), 8.20 (d, J=
4.8 Hz, 1H, C5H4N); 13C NMR: d=45.70, 66.83, 107.00,
113.87, 137.57, 148.04, 159.69.
4-(4-Methyl-2-pyridinyl)morpholine (3l):[23] 1H NMR: d=
2.27 (s, 3H, CH3), 3.48 (t, J=4.8 Hz, 4H, CH2), 3.81 (t, J=
4.8 Hz, 4H, CH2), 6.45 (s, 1H, C5H4N), 6.50 (d, J=4.8 Hz,
1H, C5H4N), 8.06 (d, J=4.8 Hz, 1H, C5H4N); 13C NMR: d=
21.42, 45.79, 66.82, 107.45, 115.41, 147.64, 148.46, 159.99.
4-(3-Pyridyl)morpholine (3m):[24] 1H NMR (CDCl3): d=
3.18 (t, J=4.8 Hz, 4H, CH2), 3.87 (t, J=4.7 Hz, 4H, CH2),
7.18 (s, 2H, C5H4N), 8.14 (s, 1H, C5H4N), 8.32 (s, 1H,
C5H4N); 13C NMR: d=48.69, 66.74, 122.21, 123.63, 138.31,
141.10, 147.03.
4-[4-(1-Isopropylindol-3-yl)phenyl]morpholine
(3n):
1-(1-Naphthyl)pyrrolidine (4g):[21] 1H NMR: d=1.84–1.92
(m, 4H, CH2), 3.23 (t, J=5.6 Hz, 4H, CH2), 6.84 (d, J=
7.6 Hz, 1H, C10H7), 7.23 (t, J=7.8 Hz, 1H, C10H7), 7.31 (d,
J=7.2 Hz, 3H, C10H7), 7.66–7.69 (m, 1H, C10H7), 8.08–8.11
(m, 1H, C10H7); 13C NMR: d=24.91, 52.82, 111.56, 121.41,
124.39, 124.91, 125.63, 126.02, 128.31, 128.37, 135.13, 147.89.
1-(4-Methoxyphenyl)pyrrolidine (4h):[28] 1H NMR: d=
1.87–1.94 (m, 4H, CH2), 3.15 (t, J=6.4 Hz, 4H, CH2), 3.67
(s, 3H, OCH3), 6.46 (d, J=9 Hz, 2H, C6H4), 6.77 (d, J=
8.8 Hz, 2H, C6H4); 13C NMR: d=25.43, 49.04, 56.10, 113.43,
115.18, 142.75, 151.57.
1
White solid; mp 127–129; H NMR: d=1.50 (d, J=6.6 Hz,
6H, CH3), 3.12 (t, J=4.7 Hz, 4H, CH2), 3.82 (t, J=4.7 Hz,
4H, CH2), 4.56–4.70 (m, 1H, CH), 6.95 (d, J=8.4 Hz, 2H,
C6H4), 7.14 (t, J=6.9 Hz, 1H, Ar), 7.22 (t, J=7.5 Hz, 1H,
Ar), 7.29 (s, 1H, Ar), 7.36 (d, J=8.1 Hz, 1H, Ar), 7.56 (d,
J=8.7 Hz, 2H, C6H4), 7.90 (d, J=7.8 Hz, 1H, Ar);
13C NMR: d=22.82, 47.03, 49.62, 66.98, 109.72, 116.21,
116.69, 119.67, 120.05, 120.76, 121.60, 126.43, 127.86, 128.16,
136.31, 149.41; HR-MS (EI): m/z=320.1883, calcd. for
C21H24N2O: 320.1889.
1-[1,1’-Biphenyl]-4-yl-4-methylpiperidine
(4a):[25]
1-[1,1’-Biphenyl]-4-yl-4-methylpiperazine
(4i):[25]
1H NMR: d=0.90 (d, J=6.4 Hz, 3H, CH3), 1.21–1.35 (m,
2H, CH2), 1.37–1.49 (m, 1H, CH), 1.66 (d, J=12.8 Hz, 2H),
2.64 (dt, J=2.4, 12.4 Hz, 2H), 3.62 (d, J=12.4 Hz, 2H), 6.90
(d, J=8.8 Hz, 2H, C6H4), 7.15–7.19 (m, 1H, C6H5), 7.30 (t,
J=7.6 Hz, 2H, C6H5), 7.41 (d, J=8.8 Hz, 2H, C6H4), 7.47
(dd, J=1.6, 8.8 Hz, 2H, C6H5); 13C NMR: d=22.02, 30.88,
34.18, 49.86, 116.52, 126.39, 126.57, 127.76, 128.77, 131.69,
141.17, 151.28.
1H NMR: d=2.32 (s, 3H, CH3), 2.55 (t, J=4.8 Hz, 4H,
CH2), 3.23 (t, J=4.8 Hz, 4H, CH2), 6.95 (d, J=8.7 Hz, 2H,
C6H4), 7.25 (t, J=7.3 Hz, 1H, C6H5), 7.37 (t, J=7.5 Hz, 2H,
C6H5), 7.49 (d, J=8.7 Hz, 2H, C6H4), 7.54 (d, J=7.5 Hz,
2H, C6H5); 13C NMR: d=46.18, 48.88, 55.10, 116.06, 126.43,
126.51, 127.73, 128.71, 132.21, 140.92, 150.56.
1-Methyl-4-(1-naphthyl)piperazine (4j):[26] 1H NMR: d=
2.38 (s, 3H, CH3), 2.68 (s, 4H, CH2), 3.12 (s, 4H, CH2), 7.06
(d, J=7.5 Hz, 1H, C10H7), 7.36 (t, J=7.8 Hz, 1H, C10H7),
7.40–7.47 (m, 2H, C10H7), 7.51 (d, J=8.1 Hz, 1H, C10H7),
7.76–7.80 (m, 1H, C10H7), 8.17–8.20 (m, 1H, C10H7);
13C NMR: d=46.23, 52.94, 55.69, 114.73, 123.52, 123.61,
125.33, 125.81, 125.91, 128.43, 128.97, 134.81, 149.67.
4-Methyl-1-(1-naphthalenyl)piperidine (4b):[26] 1H NMR:
d=1.03 (d, J=4.8 Hz, 3H, CH3), 1.49–1.63(m, 3H, CH+
CH2), 1.77 (d, J=8.8 Hz, 2H), 2.70 (t, J=11.2 Hz, 2H,
CH2), 3.36 (d, J=11.2 Hz, 2H, CH2), 7.02 (d, J=7.2 Hz, 1H,
Ar), 7.33 (t, J=7.6 Hz, 1H, Ar), 7.39–7.46 (m, 2H, Ar), 7.48
(d, J=8 Hz, 1H, Ar), 7.77 (d, J=8.4 Hz, 1H, Ar), 8.17 (d,
J=8 Hz, 1H, Ar); 13C NMR: d=22.21, 31.16, 35.14, 54.06,
114.62, 123.10, 123.96, 125.26, 125.79, 125.97, 128.42, 129.25,
134.89, 150.83.
1-(4-Methoxylphenyl)-4-(pyridin-2-yl)piperazine (4k):[29]
1H NMR: d=3.17 (t, J=5 Hz, 4H, CH2), 3.68 (t, J=5 Hz,
4H, CH2), 3.76 (s, 3H, OCH3), 6.61–6.70 (m, 2H, C5H4N),
6.85 (d, J=9.3 Hz, 2H, C6H4), 6.94 (d, J=9.1 Hz, 2H,
C6H4), 7.48 (t, J=7.8 Hz, 1H, C5H4N), 8.21 (d, J=4.2 Hz,
4-Methyl-1-(4-methoxyphenyl)piperidine (4c): Yellow
1
solid; mp 328C; H NMR: d=0.98 (d, J=6 Hz, 3H, CH3),
Adv. Synth. Catal. 2013, 355, 3694 – 3702
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3699