D. Wu et al.
Molecular Catalysis 503 (2021) 111415
102.34, 52.64, 46.81, 21.90, 20.93, 11.35, 10.78, ppm. IR (KBr): 1670,
NMR (400 MHz, CDCl3) δ 7.43ꢀ 7.40 (m, 2 H), 7.36ꢀ 7.33 (m, 4 H),
7.32ꢀ 7.28 (m, 1 H), 7.44ꢀ 7.40 (m, 2 H), 4.31 (s, 2 H), 4.10 (s, 1 H),
ppm; 13C NMR (100 MHz, CDCl3) δ 147.65, 138.84, 137.82, 128.74,
127.41, 115.10, 78.15, 48.08, ppm.
1457, 761 cmꢀ 1
.
N1-(6-(1H-pyrazol-1-yl)pyridin-2-yl)-N1-methyl-N2-pro-
pylbenzene-1,2-diamine (B): Purification by flash chromatography
(petroleum ether/EtOAc = 5:1) gave a colorless oil (154 mg, 50 %). 1H
NMR (400 MHz, CDCl3) δ 8.57 (m, 1 H), 7.72 (m, 1 H), 7.44ꢀ 7.40 (m, 1
H), 7.26ꢀ 7.21 (m, 2 H), 7.09ꢀ 7.07 (m, 1 H), 6.79ꢀ 6.73 (m, 2 H),
6.45ꢀ 6.44 (m, 1 H), 6.09ꢀ 6.07 (m, 1 H), 2.29 (s, 2 H), 3.13ꢀ 3.10 (m, 2
H), 1.60ꢀ 1.55 (m, 3 H), 1.26ꢀ 1.23 (m, 1 H), 0.92ꢀ 0.88 (m, 3 H), ppm;
13C NMR (100 MHz, CDCl3) δ 157.89, 150.04, 145.20, 141.69, 139.56,
131.14, 128.73, 128.31, 126.95, 117.22, 111.43, 107.14, 105.85,
100.06, 45.36, 37.00, 22.64, 11.66, ppm. IR (KBr): 1614, 1484, 1326,
1041, 748 cmꢀ 1. HRMS (ESI) m/z calcd for C18H22N5 [M+H]+
308.1870, found 308.1873.
N-benzyl-4-methylaniline (3f) [31]: Purification by flash chroma-
tography (petroleum ether/EtOAc = 50:1) gave a colorless oil (89 mg,
90 %). 1H NMR (400 MHz, CDCl3) δ 7.49ꢀ 7.43 (m, 4 H), 7.40ꢀ 7.36 (m,
1 H), 7.11 (d, J =8.0 Hz, 2 H), 6.67 (d, J =6.8 Hz, 2 H), 4.40 (s, 2 H), 3.97
(s, 1 H), 2.36 (s, 3 H), ppm. 13C NMR (100 MHz, CDCl3) δ 146.00,
139.76, 129.84, 128.68, 127.59, 127.24, 126.82, 113.11, 48.72, 20.50,
ppm.
N-benzyl-4-(tert-butyl)aniline (3 g) [31]: Purification by flash
chromatography (petroleum ether/EtOAc = 50:1) gave acolorless oil
(111 mg, 93 %). 1H NMR (400 MHz, CDCl3) δ 7.38ꢀ 7.31 (m, 4 H),
7.28ꢀ 7.24 (m, 1 H), 7.20 (d, J =8.8 Hz, 2 H), 6.59 (d, J =8.4 Hz, 2 H),
4.30 (s, 2 H), 3.91 (s, 1 H), 1.27 (s, 9 H), ppm; 13C NMR (100 MHz,
CDCl3) δ 145.99, 140.41, 139.83, 128.71, 127.67, 127.28, 126.13,
112.68, 48.73, 33.97, 31.68, ppm.
N1-propyl-N2-(pyridin-2-yl)benzene-1,2-diamine (C): Purifica-
tion by flash chromatography (petroleum ether/EtOAc = 5:1) gave a
colorless oil (195 mg, 86 %). 1H NMR (400 MHz, CDCl3) δ 7.96ꢀ 7.94 (m,
1 H), 7.69 (s, 1 H), 7.23ꢀ 7.19 (m, 1 H), 7.08ꢀ 7.00 (m, 2 H), 6.61ꢀ 6.53
(m, 2 H), 6.47ꢀ 6.44 (m, 1 H), 6.25ꢀ 6.23 (m, 1 H), 4.15 (m, 1 H),
4-fluoro-N-(3-methylbenzyl)aniline (3 h) [65]: Purification by
flash chromatography (petroleum ether/ EtOAc = 50:1) gave a yellow
oil (82 mg, 76 %). 1H NMR (400 MHz, CDCl3) δ 7.21ꢀ 7.01 (m, 4H),
6.87ꢀ 6.77 (m, 2 H), 6.50ꢀ 6.45(m, 2H), 4.16 (s, 2 H), 3.80 (s, 1 H), 2.27
(s, 3 H), ppm; 13C NMR (100 MHz, CDCl3) δ 157.15, 154.82, 144.67,
144.65, 139.26, 138.49, 128.70, 128.42, 128.20, 124.69, 115.90,
115.68, 113.79, 113.71, 49.08, 21.57, ppm. 19F NMR (376 MHz, CDCl3):
δ -127.96, ppm.
2.97ꢀ 2.93 (m, 2 H), 1.46ꢀ 1.41 (m, 2 H), 0.79ꢀ 0.76 (m, 3 H), ppm; 13
C
NMR (100 MHz, CDCl3) δ 158.53, 148.02, 144.93, 137.74, 127.27,
126.85, 125.46, 116.46, 113.79, 110.79, 107.02, 45.39, 22.49, 11.58,
ppm. IR (KBr): 3191, 2962, 1596, 1432, 1149, 740 cmꢀ 1. HRMS (ESI) m/
z calcd for C14H18N3 [M+H]+ 228.1495, found 228.1497.
N1-phenyl-N2-propylbenzene-1,2-diamine (D): Purification by
flash chromatography (petroleum ether/EtOAc = 10:1) gave a yellow oil
(102 mg, 45 %). 1H NMR (400 MHz, CDCl3) δ 7.10ꢀ 7.06 (m, 2 H),
7.03ꢀ 6.99 (m, 2 H), 6.72ꢀ 6.68 (m, 1 H), 6.64ꢀ 6.56 (m, 4 H), 4.94 (s, 1
H), 3.94 (s, 1 H), 3.00ꢀ 2.96 (m, 2 H), 1.52ꢀ 1.47 (m, 2 H), 0.85ꢀ 0.81
(m, 3 H), ppm; 13C NMR (100 MHz, CDCl3) δ 1 45.93, 144.33, 129.35,
128.13, 126.34, 125.08, 119.27, 117.05, 115.30, 111.16, 45.74, 22.73,
11.76, ppm. IR (KBr): 2963, 1596, 1496, 1259, 746 cmꢀ 1. HRMS (ESI)
m/z calcd for C15H19N2 [M+H]+ 227.1543, found 227.1548.
4-methyl-N-(3-methylbenzyl)aniline (3i)[65]: Purification by
flash chromatography (petroleum ether/EtOAc = 50:1) gave a yellow oil
(97 mg, 92 %).1H NMR (400 MHz, CDCl3) δ 7.38ꢀ 7.29 (m, 3H),
7.23ꢀ 7.21 (m, 1 H), 7.14ꢀ 7.12(m, 2H), 6.69 (d, J =2.0 Hz, 2 H), 4.38 (s,
2 H), 3.97 (s, 1 H), 2.49 (s, 3 H), 2.39(s, 3 H), ppm; 13C NMR (100 MHz,
CDCl3) δ 146.10, 139.68, 138.33, 129.83, 128.59, 128.37, 128.01,
126.75, 124.67, 113.07, 48.75, 21.54, 20.51, ppm.
Synthetic Procedures for the Synthesis of Amines: A mixture of
aryl amines (0.5 mmol), benzyl alcohol (0.6 mmol), Mo(CO)6 (0.02
mmol, 4 mol%), L1 (0.02 mmol, 4 mol%), and KOtBu (0.75 mmol) in
toluene (2.0 mL) were allowed to react at 120 ◦C for 24 h under a air
atmosphere. The solvent was concentrated under vacuum, and the
amines were isolated by flash chromatography.
N-benzyl-3-bromoaniline (3 j) [31]: Purification by flash chroma-
tography (petroleum ether/EtOAc = 50:1) gave a colorless oil (113 mg,
86 %). 1H NMR (400 MHz, CDCl3) δ 7.44ꢀ 7.36 (m, 4 H), 7.35ꢀ 7.30 (m,
1 H), 7.04 (t, J =8.0 Hz, 1 H), 6.86 (d, J =8.0 Hz, 1 H), 6.81 (t, J =2.0 Hz,
2 H), 6.56 (dd, J =8.4 Hz, J =2.4 Hz, 1 H), 4.32 (s, 2 H), 4.10 (s, 1 H),
ppm; 13C NMR (100 MHz, CDCl3) δ 149.46, 138.80, 130.61, 128.83,
127.56, 127.54, 123.36, 120.39, 115.50, 111.60, 48.14, ppm.
N-benzyl-3,5-dichloroaniline (3k): Purification by flash chroma-
tography (petroleum ether/EtOAc = 50:1) gave a colorless oil (110 mg,
87 %). 1H NMR (400 MHz, CDCl3) δ 7.30ꢀ 7.26 (m, 2 H), 7.24ꢀ 7.21 (m,
3 H), 6.59 (t, J =1.6 Hz, 1 H), 6.38 (d, J =1.6 Hz 1 H), 4.18 (s, 2 H), 4.06
(s, 1 H), ppm. 13C NMR (100 MHz, CDCl3) δ 149.73, 138.18, 135.57,
128.94, 127.75, 127.54, 117.34, 111.07, 48.01, ppm.
N-benzylaniline (3a)[31]: Purification by flash chromatography
(petroleum ether/EtOAc = 50:1) gave a colorless oil (88 mg, 96 %). 1H
NMR (400 MHz, CDCl3) δ 7.38ꢀ 7.34 (m, 4 H), 7.30ꢀ 7.26 (m, 1 H),
7.20ꢀ 7.16 (m, 2 H), 6.75ꢀ 6.71 (m, 1 H), 6.64ꢀ 6.62 (m, 2 H), 4.31 (s, 2
H), 3.99 (s, 1 H), ppm; 13C NMR (100 MHz, CDCl3) δ 148.23, 139.53,
129.34, 128.70, 127.57, 127.29, 117.61, 112.91, 48.34, ppm.
N-benzyl-4-fluoroaniline (3b) [31]: Purification by flash chroma-
tography (petroleum ether/EtOAc = 50:1) gave a colorless oil (99 mg,
98 %). 1H NMR (400 MHz, CDCl3) δ 7.39ꢀ 7.33 (m, 4 H), 7.32ꢀ 7.27 (m,
1 H), 6.92–8.86 (m, 2 H), 6.60ꢀ 6.54 (m, 2 H), 4.30 (s, 2 H), 3.94 (s, 1 H),
ppm; 13C NMR (100 MHz, CDCl3) δ 157.19, 154.85, 144.61, 139.37,
128.80, 127.62, 127.44, 115.91, 115.69, 113.80, 113.73, 49.06. 19F
NMR (376 MHz, CDCl3): δ -127.90, ppm.
N-benzyl-3-methylaniline (3 L) [31]: Purification by flash chro-
matography (petroleum ether/EtOAc = 50:1) gave a colorless oil (64
mg, 65 %). 1H NMR (400 MHz, CDCl3) δ 7.41ꢀ 7.36 (m, 4 H), 7.33ꢀ 7.29
(m, 1 H), 7.10 (t, J =8.0 Hz, 1 H), 6.58 (d, J = 7.6 Hz, 1 H), 6.51ꢀ 6.47
(m, 2 H), 4.35 (s, 2 H), 3.98 (s, 1 H), 2.31 (s, 3 H), ppm; 13C NMR (100
MHz, CDCl3) δ 148.35, 139.68, 139.16, 129.27, 128.74, 127.65, 127.31,
118.65, 113.75, 110.08, 48.47, 21.76, ppm.
N-benzyl-4-chloroaniline (3c) [31]: Purification by flash chroma-
tography (petroleum ether/EtOAc = 50:1) gave a colorless oil (103 mg,
95 %). 1H NMR (400 MHz, CDCl3) δ 7.29ꢀ 7.23 (d, J =4.0 Hz, 4 H),
7.22ꢀ 7.17 (m, 1 H), 7.05ꢀ 7.01 (m, 2 H), 6.49ꢀ 6.45 (m, 2 H), 4.22 (s, 2
H), 4.14 (s, 1 H), ppm; 13C NMR (100 MHz, CDCl3) δ 146.47, 138.85,
129.22, 128.85, 127.63, 127.56, 122.54, 114.30, 48.65, ppm.
N-benzyl-4-bromoaniline (3d) [31]: Purification by flash chroma-
tography (petroleum ether/EtOAc = 50:1) gave a colorless oil (119 mg,
91 %). 1H NMR (400 MHz, CDCl3) δ 7.29ꢀ 7.25 (m, 4 H), 7.22ꢀ 7.19 (m,
1 H), 7.18ꢀ 7.14 (m, 2 H), 6.43ꢀ 6.40 (m, 2 H), 4.21 (s, 2 H), 3.99 (s, 1
H), ppm; 13C NMR (100 MHz, CDCl3) δ 147.14, 138.96, 132.03, 128.81,
127.50, 127.48, 114.54, 109.22, 48.32, ppm.
N-benzyl-2-methylaniline (3 m) [31]: Purification by flash chro-
matography (petroleum ether/EtOAc = 50:1) gave a colorless oil (30
mg, 30 %). 1H NMR (400 MHz, CDCl3) δ 7.41ꢀ 7.35 (m, 4 H), 7.35ꢀ 7.27
(m, 1 H), 7.13ꢀ 7.08 (m, 2 H), 6.70 (t, J = 7.6 Hz, 1 H), 6.64 (d, J =8.0
Hz, 1 H), 4.39 (s, 2 H), 3.97 (s, 1 H), 2.18 (s, 3 H), ppm; 13C NMR (100
MHz, CDCl3) δ 146.20, 139.63, 130.20, 128.79, 127.67, 127.38, 127.29,
122.04, 117.30, 110.10, 48.44, 17.68, ppm.
N-benzyl-[1,1′-biphenyl]-2-amine (3n)[31]: Purification by flash
chromatography (petroleum ether/ EtOAc = 50:1) gave a colorless oil
(53 mg, 45 %). 1H NMR (400 MHz, CDCl3) δ 7.54ꢀ 7.47 (m, 4 H),
7.43ꢀ 7.34 (m, 5 H), 7.32ꢀ 7.27 (m, 1 H), 7.26ꢀ 7.22 (m, 1 H), 7.17 (dd,
J =7.2 Hz, J =1.6 Hz, 1 H), 6.83 (t, J =7.2 Hz, 1 H), 6.72 (d, J =8.0 Hz, 1
H), 4.45 (s, 1H), 4.38 (s, 2 H), ppm; 13C NMR (100 MHz, CDCl3) δ
N-benzyl-4-iodoaniline (3e): Purification by flash chromatography
(petroleum ether/EtOAc = 50:1) gave a colorless oil (116 mg, 75 %). 1H
10