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3H); 13C NMR (100 MHz, CDCl3) δ 158.96, 148.31, 131.51, 126.78, 125.73, 124.64, 123.40, 119.84, 116.92, 104.17, 50.90, 37.54,
DOI: 10.1039/D0NJ01423K
31.66, 26.71, 26.13 ppm. HRMS(EI-MS) Calcd for C17H21N : 239.1674,
129.35, 128.91, 117.59, 114.12, 112.93, 55.40, 47.89 ppm.
N-(4-fluorobenzyl)aniline (2h)13 Pale yellow oil. Yield. 199 mg (99%). Found: 239.1673.
1H NMR(400 MHz, CDCl3) δ 7.33 (dd, J = 8.3, 5.5 Hz, 2H), 7.18 (t, J = Methyl 4-((phenylamino)methyl)benzoate (4a)16 Pale yellow solid.
7.7 Hz, 2H), 7.02 (t, J = 8.6 Hz, 2H), 6.72 (t, J = 7.3 Hz, 1H), 6.62 (d, J = Yield. 229 mg (95%). 1H NMR (400 MHz, CDCl3) δ 8.03 – 7.96 (m, 2H),
8.5 Hz, 2H), 4.30 (s, 2H), 4.02 (bs, 1H); 13C NMR (100 MHz, CDCl3) δ 7.43 (d, J = 8.5 Hz, 2H), 7.16 (t, J = 8.6 Hz, 2H), 6.72 (tt, J = 7.4, 1.0 Hz,
162.12, (d, JC-F = 246.44 Hz), 148.01, 135.17 (d, JC-F = 3.03 Hz), 129.40, 1H), 6.60 (dd, J = 8.6, 1.0 Hz, 2H), 4.40 (s, 2H), 4.14 (bs, 1H), 3.90 (s,
129.10 (d, JC-F = 8.08 Hz), 117.82, 115.55 (d, JC-F = 21.21 Hz ), 112.94, 3H); 13C NMR (100 MHz, CDCl3) δ 167.07, 147.85, 145.07, 130.06,
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47.68 ppm; 19F NMR (376 MHz, CDCl3) δ -115.52 ppm.
129.42, 129.16, 127.24, 117.94, 112.98, 52.21, 48.07 ppm.
N-(4-(trifluoromethyl)benzyl)aniline (2i)14 Pale yellow oil. Yield. 248
mg (99%). 1H NMR(400 MHz, CDCl3) δ 7.60 (d, J = 8.2 Hz, 2H), 7.49 (d,
J = 8.0 Hz, 2H), 7.19 (tt, J = 7.6, 2.2 Hz, 2H), 6.79 – 6.69 (m, 1H), 6.61
(d, J = 7.6 Hz, 2H), 4.42 (s, 2H), 4.15 (bs, 1H); 13C NMR (100 MHz, CDCl3)
δ 147.76, 143.84, 129.45, 127.53, 125.67 (q, J = 4.04 Hz), 118.05,
112.98, 47.86 ppm; 19F NMR (376 MHz, CDCl3) δ -62.27ppm
N-(4-chlorobenzyl)aniline (2j)11 Pale yellow solid. Yield. 216 mg
(99%). 1H NMR (400 MHz, CDCl3) δ 7.30 (s, 4H), 7.20 – 7.14 (m, 2H),
6.72 (tt, J = 7.4, 1.1 Hz, 1H), 6.63 – 6.58 (m, 2H), 4.31 (s, 2H), 4.05 (bs, AUTHOR INFORMATION
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI:
Experimental details, spectroscopic data for all compounds,
(PDF)
1H); 13C NMR (100 MHz, CDCl3) δ 147.90, 138.07, 132.95, 129.40,
128.84, 128.78, 117.89, 112.96, 47.69 ppm.
Corresponding Author
* E-mail: dkan@kangwon ac.kr
N-(4-bromobenzyl)aniline (2k)11 Pale yellow soild. Yield. 260 mg
Author Contributions
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(99%). H NMR (400 MHz, CDCl3) δ 7.51 – 7.37 (m, 2H), 7.29 – 7.21
The manuscript was written through contributions of all
authors. / All authors have given approval to the final version of
the manuscript
(m, 2H), 7.21 – 7.12 (m, 2H), 6.72 (tt, J = 7.4, 1.0 Hz, 1H), 6.65 – 6.55
(m, 2H), 4.29 (s, 2H), 4.06 (bs, 1H); 13C NMR (100 MHz, CDCl3) δ
147.87, 138.62, 131.79, 129.40, 129.14, 121.01, 117.90, 112.96,
47.73 ppm.
N-(naphthalen-2-ylmethyl)aniline (2l)11 Pale yellow solid. Yield.
231 mg (99%). 1H NMR (400 MHz, CDCl3) δ 7.93 – 7.76 (m, 4H),
7.58 – 7.40 (m, 3H), 7.19 (t, J = 7.5 Hz, 2H), 6.74 (t, J = 6.9 Hz,
1H), 6.69 (d, J = 8.5 Hz, 2H), 4.50 (s, 2H), 4.14 (bs, 1H); 13C NMR
(100 MHz, CDCl3) δ 148.27, 137.05, 133.60, 132.87, 129.40,
128.48, 127.86, 127.81, 126.26, 126.02, 125.84, 117.74, 113.05,
48.61 ppm.
N-(pyren-1-ylmethyl)aniline (2m)15 Yellow solid. Yield. 306 mg
(99%). 1H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 9.2 Hz, 1H), 8.23
– 8.17 (m, 2H), 8.17 – 8.10 (m, 2H), 8.10 – 8.04 (m, 3H), 8.02 (t,
J = 8.0 Hz, 1H), 7.26 – 7.20 (m, 2H), 6.82 – 6.70 (m, 3H), 4.99 (s,
2H), 4.10 (bs, 1H); 13C NMR (100 MHz, CDCl3) δ 148.36, 132.19,
131.38, 131.10, 130.88, 129.47, 129.07, 128.03, 127.53, 127.44,
126.81, 126.13, 125.40, 125.33, 125.13, 124.93, 124.88, 123.09,
117.79, 112.90, 46.85 ppm
4-bromo-N-(thiophen-3-ylmethyl)aniline (2n) Pale yellow
solid. Yield. 265 mg (99%). 1H NMR (400 MHz, CDCl3) δ 7.31 (dd,
J = 4.9, 3.0 Hz, 1H), 7.27 – 7.22 (m, 2H), 7.17 (dt, J = 2.1, 1.1 Hz,
1H), 7.05 (dd, J = 4.9, 1.1 Hz, 1H), 6.56 – 6.45 (m, 2H), 4.30 (s,
2H), 4.01 (bs, 1H); 13C NMR (100 MHz, CDCl3) δ 147.03, 139.99,
132.04, 127.09, 126.44, 121.92, 114.56, 109.35, 43.80 ppm.
HRMS(EI-MS) Calcd for C11H10BrNS : 266.9717, Found: 266.9719.
N-(cyclohexylmethyl)naphthalen-1-amine (2o) Pale yellow liquid.
Yield. 237 mg (99%). 1H NMR (400 MHz, CDCl3) δ 7.80 (td, J = 6.6, 2.1
Hz, 2H), 7.49 – 7.39 (m, 2H), 7.35 (t, J = 7.9 Hz, 1H), 7.21 (d, J = 8.2 Hz,
1H), 6.59 (d, J = 7.5 Hz, 1H), 4.42 (bs, 1H), 3.13 (d, J = 6.7 Hz, 2H), 2.02
– 1.87 (m, 2H), 1.82 – 1.69 (m, 4H), 1.36 – 1.16 (m, 3H), 1.08 (qd, J =
12.2, 3.0 Hz, 2H);13C NMR (100 MHz, CDCl3) δ 143.78, 134.43, 128.79,
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This study was supported by the National Research Foundation
of Korea Grant funded by the Korean Government
(2017R1D1A1B03035412).
Notes and references
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Nugent, T. C.; El‐Shazly, M. Chiral amine synthesis–recent
developments and trends for enamide reduction, reductive
amination, and imine reduction. Adv. Synth. Catal. 2010, 352,
753 – 819.
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(a) Hayes, K. Industrial processes for manufacturing amines.
Appl. Catal. A 2001, 221, 187-195.; (b) Muller, T. E.; Hultzsch,
K. C.; Yus, M.; Foubelo, F.; Tada, M. Hydroamination: direct
addition of amines to alkenes and alkynes. Chem. Rev. 2008,
108, 3795-3892.; (c) Nishimura, S. Handbook of
heterogeneous catalytic hydrogenation for organic synthesis;
Wiley New York etc: 2001.; (d) Spindler, F.; Blaser, H.; Vries, J.
d.; Elsevier, C. The Handbook of Homogeneous
Hydrogenation. 2007.; (e) Brown, H. C.; Choi, Y. M.;
Narasimhan, S. Convenient procedure for the conversion of
sodium borohydride into lithium borohydride in simple ether
solvents. Inorg. Chem. 1981, 20, 4454-4456.
(a) Chong, C. C.; Kinjo, R. Catalytic hydroboration of carbonyl
derivatives, imines, and carbon dioxide. ACS Catalysis 2015, 5,
3238-3259.; (b) Kaithal, A.; Chatterjee, B.; Gunanathan, C.
Ruthenium-catalyzed selective hydroboration of nitriles and
imines. J. Org. Chem. 2016, 81, 11153-11161.; (c) Wu, J.; Zeng,
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