Page 5 of 7
The Journal of Organic Chemistry
27
1
3
021, 2958, 2871, 1600, 1502, 1452, 1367, 1313, 1267,
N-(1-cyclohexylethyl)aniline (21) 72% (146 mg), H
NMR (400 MHz, CDCl ) δ 7.18 (dd, J = 8.5, 7.3 Hz, 2H),
-1
1
2
3
4
5
6
7
8
9
1178, 1078, 1027, 756, 690 cm .
3
24
6.68 (tt, J = 7.3, 1.0 Hz, 1H), 6.60 (dd, J = 8.8, 1.1 Hz,
2H), 3.50 (s, 1H), 3.35 (p, J = 6.5 Hz, 1H), 1.89 – 1.70
2
-methoxy-N-(1-phenylethyl)aniline (15) 64% (145
1
3
mg), H NMR (400 MHz, CDCl ) δ 7.40 – 7.31 (m, 4H),
(
(
(
m, 5H), 1.53 – 1.44 (m, 1H), 1.34 – 1.19 (m, 3H), 1.15
7.25 – 7.22 (m, 1H), 6.79 (d, J = 7.8 Hz, 1H), 6.72 (t, J =
7.7 Hz, 1H), 6.63 (t, J = 7.7 Hz, 1H), 6.36 (d, J = 7.8 Hz,
1H), 4.67 (s, 1H), 4.50 (q, J = 6.7 Hz, 1H), 3.90 (s, 3H),
.57 (d, J = 6.7 Hz, 3H). C{ H} NMR (100 MHz, CDCl
δ 146.6, 145.6, 137.3, 128.7, 126.9, 125.9, 121.3, 116.4,
11.0, 109.3, 55.5, 53.4, 25.3. IR (ATR) 3424, 3062,
962, 2832, 1735, 1685, 1602, 1509, 1454, 1427, 1349,
249, 1222, 1176, 1143, 1108, 1049, 1025, 900, 759,
13
1
d, J = 6.5 Hz, 3H), 1.10 – 1.06 (m, 1H). C{ H} NMR
100 MHz, CDCl ) δ 148.0, 129.3, 116.5, 113.0, 53.0,
3
13
1
43.0, 29.8, 28.4, 26.7, 26.5, 26.4, 17.5. IR (ATR) 3413,
1
3
)
2
921, 2850, 1600, 1504, 1448, 1429, 1373,1317, 1253,
-1
1155, 1074, 991, 863, 744, 690 cm .
1
2
1
7
Ethyl 2-((2-methoxyphenyl)amino)-2-
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
29
1
phenylacetate (22) 61% (155 mg), H NMR (300 MHz,
CDCl ) δ 7.53 (dd, J = 8.0, 1.5 2H), 7.39 – 7.31 (m, 3H),
-1
34, 700 cm .
3
25
6.82 – 6.66 (m, 3H), 6.37 (dd, J = 7.5, 1.5 Hz, 1H), 5.50
(d, J = 6 Hz, 1H), 5.08 (d, J = 6.3, 1H), 4.313 – 4.10 (m,
N-(1-(4-nitrophenyl)ethyl)aniline (16) 30% (70 mg),
) δ 8.20 (d, J = 8.8 Hz, 2H),
.55 (d, J = 8.4 Hz, 2H), 7.10 (dd, J = 8.7, 7.4 Hz, 2H),
.70 (tt, J = 7.4, 1.0 Hz, 1H), 6.46 (dd, J = 8.7, 1.1 Hz,
H), 4.58 (q, J = 6.9 Hz, 1H), 4.17 (s, 1H), 1.56 (d, J =
3
6.9 Hz, 3H). C{ H} NMR (100 MHz, CDCl ) δ 153.2,
147.1, 146.5, 129.3, 126.7, 124.1, 118.0, 113.3, 53.4,
24.9 IR (ATR) 3409, 3052, 2971, 2927, 1598, 1513,
504, 1450, 1430, 1340, 1317, 1280, 1257, 1205, 1180,
1
H NMR (400 MHz, CDCl
3
13
1
2H), 3.91 (s, 3H), 1.23 (t, J = 7.2 Hz, 3H. C{ H} NMR
(75 MHz, CDCl ) δ 171.8, 147.1, 137.8, 136.0, 128.8,
7
6
1
3
128.1, 127.2, 121.0, 117.3, 110.7, 109.6, 61.7, 60.8,
55.5, 14.1. IR (ATR) 3423, 2937, 1733, 1602, 1511,
13
1
1
456,1429, 1315, 1247, 1222, 1178, 1139, 1025, 730,
-1
696 cm .
1
1
-1
ASSOCIATED CONTENT
Supporting Information
143, 1106, 1012, 854, 748, 692 cm .
26
N-(1-(4-methoxyphenyl)ethyl)aniline (17) 70% (161
1
mg), H NMR (400 MHz, CDCl
3
) δ 7.30 (d, J = 8.4 Hz,
H), 7.11 (dd, J = 8.7, 7.3 Hz, 2H), 6.88 (d, J = 8.8 Hz,
H), 6.67 (tt, J = 7.3, 1.1 Hz, 1H), 6.54 (dd, J = 8.7, 1.0
The Supporting Information is available free of charge on
the ACS Publications website.
2
2
,
Hz, 2H), 4.47 (q, J = 6.8 Hz, 1H), 4.07 (br, 1H), 3.80 (s,
Synthetic details and NMR characterization for select
catalysts and full range of products, chiral GCMS data
(PDF)
13
1
3
H), 1.51 (d, J = 6.8 Hz, 3H). C{ H} NMR (100 MHz,
) δ 158.5, 147.3, 137.2, 129.1, 126.9, 117.3,
14.0, 113.4, 55.3, 52.9, 25.0. IR (ATR): 3405, 2962,
602, 1504, 1461, 1317, 1284, 1241, 1176, 1105, 1031,
CDCl
3
1
1
AUTHOR INFORMATION
Corresponding Author
-1
993, 829, 748, 692, 545 cm .
27
N-(1-(4-fluorophenyl)ethyl)aniline (18) 97% (235
mg) H NMR (300 MHz, CDCl ) δ 7.38 – 7.34 (m, 2H),
3
*
Prof. Marc J. Adler, Department of Chemistry & Biology,
1
Ryerson University, 350 Victoria St, Toronto, ON, M5B 2K3,
Canada. E-mail: marcjadler@ryerson.ca
7.13 (t, J = 8 Hz, 2H), 7.03 (t, J = 8.7 Hz, 2H), 6.69 (t, J =
7.2 Hz, 1H), 6.52 (d, J = 7.8 Hz, 2H), 4.50 (q, J = 7 Hz,
1
Author Contributions
1
(
1
2
1
7
H), 4.03 (s, 1H), 1.53 (d, J = 6.6 Hz, 3H). 13C{ H} NMR
75 MHz, CDCl
3
) δ 147.1, 140.9, 129.1, 127.3 (d, JCF
=
The manuscript was written through contributions of all
authors.
2.5 Hz), 117.4, 115.4 (d, JCF = 36.25 Hz), 113.3, 52.9,
5.2. IR (ATR) 3411, 3050, 2969, 1600, 1504, 1429,
373, 1315, 1257, 1218, 1155, 1139, 1093, 1014, 833,
ACKNOWLEDGMENT
The authors are grateful for financial support provided by
Northern Illinois University (NIU).
-1
48, 690 cm .
2
1
N-(1-(4-bromophenyl)ethyl)aniline (19) 96% (282
1
mg), H NMR (300 MHz, CDCl
3
) δ 7.47 (d, J = 8.4 Hz,
H), 7.28 (d, J = 8.4 2H), 7.13 (dd, J = 8.5, 7.4 Hz, 2H),
.69 (t, 7.3 Hz, 1H), 6.50 (dd, J = 8.5, 1.2 Hz, 2H), 4.47
q, J = 6.6 Hz, 1H), 4.03 (s, 1H), 1.52 (d, J = 7 Hz, 3H).
3
C{ H} NMR (75 MHz, CDCl ) δ 147.0, 144.4, 131.8,
2
6
REFERENCES
1 a) Dewick, P.M. Medicinal Natural Products: A Biosynthetic
Approach, Wiley, Chichester, 2002, p. 315; b) Bentley, K.W. β-
Phenylethylamines and the isoquinoline alkaloids. Nat Prod
Rep 2006, 23, 444-463.
(
13
1
129.2, 127.7, 120.5, 117.6, 113.3, 53.1, 25.1. IR (ATR)
3415, 2966, 1600, 1502, 1429, 1402, 1317, 1255, 1180,
2
a) Tang, W.; Zhang, X. New Chiral Phosphorus Ligands for
-
1
1
139, 1070, 1008, 908, 821, 748, 690 cm .
Enantioselective Hydrogenation. Chem Rev 2003, 103, 3029-
3070; b) Handbook of Homogeneous Hydrogenation (Ed.: I.
Ojima), Wiley-VCH, Hoboken, 2010; c) Xie, J.-H.; Zhu, S.-F.;
Zhou, Q.-L. Transition metal-catalyzed enantioselective
hydrogenation of enamines and imines. Chem Rev 2011, 111,
28
N-(1-(pyridin-2-yl)ethyl)aniline (20) 79% (172 mg),
3
) δ 8.60 (d, J = 4.1 Hz, 1H),
.63 (td, J = 7.65, 1.2 Hz, 1H), 7.37 (d, J = 7.8 Hz, 1H),
.14 (m, 3H), 6.68 (t, J = 7.2 Hz, 1H), 6.58 (d, J = 8.4 Hz,
H), 4.64 (q, J = 6.6 Hz, 1H), 4.47 (s, 1H), 1.57 (d, J =
3
.6 Hz, 3H). C{ H} NMR (75 MHz, CDCl ) δ 163.9,
49.3, 147.1, 136.8, 129.2, 122.0, 120.3, 117.4, 113.4,
4.8, 23.2. IR (ATR) 3403, 2969, 1600, 1502, 1471,
432, 1317, 1259, 1180, 1153, 1025, 993, 869, 784,
1
H NMR (300 MHz, CDCl
7
7
2
6
1
5
1
7
1713-1760; d) Wang, D.-S.; Chen, Q.-A.; Lu, S.-M.; Zhou, Y.-G.
Asymmetric hydrogenation of heteroarenes and arenes. Chem
Rev 2012, 112, 2557-2590.
13
1
3
Huang, H.; Liu, X.; Zhou, L.; Chang, M.; Zhang, X. Direct
Asymmetric Reductive Amination for the Synthesis of Chiral β-
Arylamines. Angew Chem Int Ed 2016, 55, 5309-5312.
4 Huang, H.; Zhao, Y.; Yang, Y.; Zhou, L.; Chang, M. Direct
Catalytic Asymmetric Reductive Amination of Aliphatic Ketones
-1
46, 692 cm .
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