9
ACCEPTED MANUSCRIPT
+
(
CH ), 29.4 (CH), 28.9 (CH), 28.8 (CH), 26.7 (CH), 22.1 (CH), 13.9 (CH ). HRMS (ESI): [M+H] , found
2
3
3
34.3221. C H N requires 334.3217.
2
1
39
3
4.2.10. N,N'-Dicyclohexyl-2,6-diaminopyridine (10). Prepared according to general procedure A.
1
Product was obtained as yellow oil. H NMR (CDCl ) δ: 7.20 (t, J = 8.1 Hz, 1H, Py), 5.66 (d, J = 8.0
3
Hz, 2H, Py), 4.16 (d, J = 8.2 Hz, 2H, NH), 3.42 (quint, 2H, CH), 2.05 (m, 4H, CH ), 1.76 (m, 6H, CH ),
2
2
1
3
1
1
.24 (m, 10H, CH2). C{ H} NMR (CDCl ) δ: 157.7 (Py), 139.1 (ArH), 94.3 (Py), 50.4 (CH), 33.6 (CH ),
3 2
+
2
6.0 (CH ), 25.1 (CH ). HRMS (ESI): [M+H] , found 274.2274. C H N requires 274.2278.
2
2
17 27
3
4.2.11. N,N'-Bis-(S-1-phenylethyl)-2,6-diaminopyridine (11). Prepared according to general procedure
1
A with 4.2 equivs of amine. Product was obtained as colorless oil. H NMR (DMSO-d ) δ: 7.38-7.12
6
(m, 10H, Ph), 6.92 (t, J = 7.3 Hz, 1H, Py), 6.33 (d, J = 7.9 Hz, 2H, NH), 5.56 (d, J = 7.9 Hz, 2H, Ph),
1
3
1
4
.87 (quint, 2H, CH), 1.27 (d, J = 6.8 Hz, 6H, CH3). C{ H} NMR (DMSO-d ) δ: 157.0 (Py), 146.9 (Ph),
6
+
1
37.3 (Py), 128.0 (Ph), 126.0 (Ph), 126.0 (Ph), 94.8 (Py), 49.6 (CH), 23.6 (CH ). HRMS (ESI): [M+H] ,
3
found 318.1956. C H N requires 318.1965.
2
1
23
3
4.2.12. N,N'-Bis-((R)-1-phenylethyl)-2,6-diaminopyridine (12). Prepared according to general
1
procedure A with 4.2 equivs of amine. Product was obtained as colorless oil. H NMR (DMSO-d ) δ:
6
7.38-7.13 (m, 10H, Ph), 6.91 (t, J = 7.3 Hz, 1H, Py), 6.33 (d, J = 7.9 Hz, 2H, NH), 5.57 (d, J = 7.9 Hz,
1
3
1
2
H, Py), 4.83 (m, 2H, CH), 1.27 (d, J = 6.8 Hz, 6H, CH3). C{ H} NMR (DMSO-d ) δ: 157.0 (Py), 146.9
6
(
q, Ph), 137.3 (Py), 128.0 (Ph), 126.0 (Ph), 126.0 (Ph), 94.8 (Py), 49.6 (CH), 23.6 (CH ). HRMS (ESI):
3
+
[
M+H] , found 318.1956. C H N requires 318.1965.
2
1
23
3
4.2.13. N,N'-Diphenethylpyridine-2,6-diamine (13). Prepared according to general procedure A with
1
4
.2 equivs of amine. Product was obtained as white solid. Mp: 90-91 °C . H NMR (DMSO-d ) δ: 7.22
6
(m, 10H, ArH), 7.03 (t, J = 8.0 Hz, 1H, ArH), 6.06 (t, J = 5.0 Hz, 2H, NH), 5.62 (d, J = 7.8 Hz, 2H, ArH),
1
3
1
3
.38 (q, 4H, CH ), 2.82 (t, J= 7.3 Hz, 4H, CH ). C{ H} NMR (DMSO-d ) δ: 157.9 (Py), 140.1 (Ph),
2 2 6
1
37.6 (Py), 128.6 (Ph), 128.2 (Ph), 125.8 (Ph), 94.3 (Py), 42.8 (CH ), 35.7 (CH ). HRMS (ESI):
2
2
+
[
M+H] , found 318.1957. C H N requires 318.1965.
21 23 3
4.2.14. N,N'-Diphenyl-pyridine-2,6-diamine (14). Prepared according to general procedure A with
1
Pd(PPh ) (10 mg). Product was obtained as fawn crystals. Mp: 102-103 °C . H NMR (DMSO-d ) δ:
3
4
6
8.78 (s, 2H, NH), 7.59 (d, 4H, Ph), 7.36 (t, J = 8.2 Hz, 1H, Py), 7.22 (m, 4H, Ph), 6.87 (t, 2H, Ph), 6.22
1
3
1
(
d, 2H, Py). C{ H} NMR (DMSO-d ) δ: 154.4 (Py), 141.7 (Ph), 138.4 (Py), 128.4 (Ph), 120.2 (Ph),
6
+
19,20
1
18.6 (Ph), 99.7 (Py). HRMS (ESI): [M+H] , found 262.1327. C H N requires 262.1339.
17 15 3
4.2.15. N,N'-Bis-(2,6-dimethylphenyl)-pyridine-2,6-diamine (15). Prepared according to general
procedure A with Pd(PPh ) (10 mg). Product was obtained as fawn crystals. crystals. Mp: 183-
3
4
1
1
85 °C . H NMR (DMSO-d ) δ: 7.44 (s, 2H, NH), 7.08-7.03 (m, 7H, Ph, Py), 5.35 (d, J = 7.9 Hz, 2H,
6
1
3
1
Py), 2.15 (s, 12H, CH3). C{ H} NMR (DMSO-d ) δ: 157.0 (Py), 138.5 (Py), 137.9 (Ph), 136.0 (Ph),
6
+
1
27.9 (Ph), 125.4 (Ph), 94.3 (Py), 18.3 (CH ). HRMS (ESI): [M+H] , found 318.1955. C H N
3
21 23
3
2
0
requires 318.1965.