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J.-J. YU ET AL.
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afford product 3j as a white solid (273 mg, 0.80 mmol, 80%), mp 103–105 ꢂC H
NMR (CDCl3, 400 MHz): d ¼ 7.42–7.32 (m, 6H), 7.32–7.24 (m, 4H), 7.17 (d,
J ¼ 8.4 Hz, 2H), 6.87 (d, J ¼ 8.8 Hz, 2H), 5.96 (d, J ¼ 6.0 Hz, 1H), 5.40 (Br s, 1H),
5.14 (s, 2H), 3.80 (s, 3H) ppm; 13C NMR (CDCl3, 100 MHz): d ¼ 159.0 155.6,
141.9, 136.4, 133.9, 128.6, 128.5, 128.2, 127.4, 127.1, 114.1, 67.0, 58.4, 55.3 ppm;
HRMS (EI): m=z calcd. for C22H21NO3 (Mþ): 347.1521; found: 347.1506.
Representative Procedure for the Synthesis of Compound 4b
Pd-C 7%, (40 mg) was added to a solution of compound 3j (173 mg, 0.5 mmol)
in MeOH (10 mL). The mixture was stirred under a hydrogen atmosphere (1 bar) for
1.5 h, the catalyst was filtered off, and the filtrate was evaporated to dryness. The
residue was redissolved in CH2Cl2 (15 mL) and dried over Na2SO4. The solvent
was removed under vacuum to give pure product (4-methoxyphenyl)(phenyl)metha-
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namine (4b) as a colorless oil (110 mg, quant yield). H NMR (400 MHz, CDCl3):
d ¼ 7.39 (d, J ¼ 7.6 Hz, 2H), 7.30–7.35 (m, 4H), 7.24 (t, J ¼ 7.2 Hz, 1H), 6.88 (d,
J ¼ 8.8 Hz, 2H), 5.18 (s, 1H), 3.98 (s, 3H), 2.08 (s, 2H) ppm. 13C NMR (100 MHz,
CDCl3): d ¼ 158.6, 145.8, 137.7, 128.4, 128.0, 126.9, 126.8, 113.8, 59.1, 55.2 ppm.
HRMS (EI): m=z calcd. for C14H15NO (Mþ): 213.1154; found: 213.1153.
Selected Data
Benzyl (4-methoxyphenyl)(phenyl)methylcarbamate (3l). White solid;
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mp 83–85 ꢂC; yield 224 mg (90%). H NMR (CDCl3, 400 MHz): d ¼ 7.42–7.30 (m,
5H), 7.25 (d, J ¼ 8.0 Hz, 2H), 6.88 (d, J ¼ 8.4 Hz, 2H), 5.06–5.17 (m, 2H), 5.00 (Br
s, 1H), 4.83 (m, 1H), 3.81 (s, 3H),1.48 (d, J ¼ 6.4 Hz, 3H) ppm; 13C NMR
(100 MHz, CDCl3): d ¼ 158.8, 155.8, 136.5, 128.5, 128.2, 128.1, 127.2, 127.1, 114.0,
66.7, 58.3, 55.3, 22.3 ppm. HRMS (EI) m=z calcd. for C17H19NO3 (Mþ): 285.1365;
found 285.1368.
N-(1-(4-methoxyphenyl)ethyl)-4-nitroaniline (3p). Milk-white solid; mp
125–127 ꢂC; yield 246 mg (91%). 1H NMR (400 MHz, CDCl3): d ¼ 8.01 (d,
J ¼ 8.8 Hz, 2H), 7.25 (d, J ¼ 8.8 Hz, 2H), 6.89 (d, J ¼ 8.8 Hz, 2H), 6.47 (d, J ¼ 9.2 Hz,
Hz, 2H), 4.95 (br s, 1H), 4.57 (m, 1H), 3.80 (s, 3H), 1.56 (d, J ¼ 6.8 Hz, 3H) ppm; 13
C
NMR (100 MHz, CDCl3): d ¼ 158.9, 152.4, 138.0, 135.2, 126.7, 126.2, 114.3, 111.8,
55.3, 52.7, 24.5 ppm. HRMS (EI): m=z calcd. for C15H16N2O3 (Mþ): 272.1161;
found: 273.1162.
CONCLUSION
In conclusion, we have developed an efficient procedure to obtain benzylic
amines starting from the corresponding alcohols under solvent-free conditions. This
methodology tolerates various benzylic alcohols bearing electron-donating but also
mild electron-withdrawing groups. Several catalytic systems were compared, evi-
dencing the higher selectivity of FeCl3 over others. Among the nitrogen-based
nucleophiles used, CbzNH2 proved useful as an intermediate in the amidation–
reduction sequence leading to the direct preparation of benzylic amines.