Arkivoc 2017, v, 244-256
Albayrak, F. et al.
2
3
4
1
3
6
H, H10s), 2.12-2.30 (m, 2H, CH
.13 (brd, J 4.72 Hz, 8H, CH ), 3.22-3.26 (m, 3H, H
.60 (d, J 11.98 Hz, 1H, CH), 6.83-6.86 (m, 4H, Har), 7.10-7.15 (m, 4H, Har), 9.29 (brs, 1H, NH); C NMR (CDCl
25 MHz) δ 10.1 (CH ), 15.3 (CH ), 25.4 (CH ), 32.0 (CH), 32.3 (CH), 33.1 (CH ), 33.4 (CH ), 39.5 (CH ), 39.8 (CH),
9.9 (CH ), 40.6 (CH), 41.0 (CH), 45.4 (CH), 46.5 (CH), 47.0 (CH), 48.1 (CH), 48.2 (CH), 48.7 (CH), 49.6 (4×CH ),
1.2 (CH), 66.9 (4×CH ), 115.7 (4×Car), 127.8 (4×Car), 136.4 (2×C ), 149.4 (2×C ), 166.9 (C=O), 167.0 (C=O), 167.1
2
), 2.75-2.79 (m, 1H, CH), 2.80-2.84 (m, 1H, H8n), 2.89-2.98 (m, 5H, H
, H ), 3.31-,3.34 (m, 1H, H ), 3.87 (brd, J 4.09 Hz, 8H, CH ),
1
, H , H8n),
7
2
2
6
6
2
13
3
,
3
3
2
2
2
2
2
2
2
q
q
+
(C=O), 174.0 (C=O), 174.1 (C=O); HRMS (ESI): calcd for [C44
H
53
N
5
O ] ([M] ): m/z 763.9209, found 764.4006
7
+
[M+H] .
N-[8-(2-Thienyl)-4-azabicyclo[2.2.1]heptane-3-endo,5-endo-dicarboximide-4-yl]-2-(8-(2-thienyl)-4-aza-
bicyclo[2.2.1]heptane-3-endo,5-endo-dicarboximide-4-yl)-3-methylpentanamide (6d). Brown oil, yield 514.8
2
2
mg (85%), [α]
D
+11.0° (c 0.010, CH
2
Cl
2
), R
f
: 0.43 (ethyl acetate/n-hexane 1:1), FTIR (ATR) ν 3282 (N-H), 3010,
1
2
7
8
967, 2880, 1727 (C=O), 1699 (C=O), 1494, 1470, 1430, 1381, 1182, 1137; H NMR (CDCl
3
, 500 MHz) δ 0.91 (t, J
), 1.35-1.41 (m, 1H, CH ), 1.60 (d, J
), 1.98-2.05 (m, 2H, CH ), 2.06-2.09 (m, 1H,
), 2.75-2.80 (m, 1H, CH), 2.91-2.99 (m, 4H, H and H ), 3.06-3.10 (m, 1H, H8n), 3.18-3.19
m, 1H, H8n), 3.21-3.28 (m, 3H, H and H ), 3.30-3.34 (m, 1H, H ), 4.58 (d, J 11.98 Hz, 1H, CH), 6.77-6.81 (m, 1H,
ar), 6.84-6.86 (m, 1H, Har), 6.89-6.93 (m, 2H, Har), 7.11-7.15 (m, 2H, Har), 9.23 (brs, 1H, NH); C NMR (CDCl
.25 Hz, 3H, CH
.82 Hz, 1H, H ), 1.67 (d, J 10.4 Hz, 1H, H
), 2.18-2.26 (m, 1H, H
3
), 1.10 (p, J 7.25 Hz, 1H, CH
2
), 1.18 ( d, J 6.93 Hz, 3H, CH
3
2
a
a
), 1.82-1.91 (m, 2H, CH
2
2
H
s
s
1
7
(
H
2
6
6
13
3
,
1
3
1
25 MHz) δ 9.9 (CH
3
), 15.3 (CH
), 39.8 (CH), 40.3 (CH
3
), 20.7 (CH), 25.4 (CH
), 46.2 (CH), 46.6 (CH), 46.9 (CH), 47.9 (CH), 48.3 (CH), 60.9 (CH),
2
), 32.1 (CH), 34.9 (CH
2
), 35.5 (CH ), 37.7 (CH), 38.1 (CH),
2
9.5 (CH), 39.6 (CH
2
2
23.1 (Car), 123.2 (Car), 123.6 (Car), 123.7 (Car), 126.7 (Car), 126.8 (Car), 149.3 (C
q
), 149.5 (C
q
), 166.9 (C=O), 167.0
+
(C=O), 173.7 (C=O), 173.9 (C=O), 176.3 (C=O); HRMS (ESI): calcd for [C32
35
H N
3
O
5
S
2
] ([M] ): m/z 605.7674, found
+
606.2095 [M+H] .
N-[8-(3-Bromomethylphenyl)-4-azabicyclo[2.2.1]heptane-3-endo,5-endo-dicarboximide-4-yl] 2-(8-(3-bromo-
methylphenyl)-4-azabicyclo[2.2.1]heptane-3-endo,5-endo-dicarboximide-4-yl)-3-methylpentanamide (6e).
2
2
Colorless oil, yield 545.3 mg (70%), [α]
(
D
+11.4° (c 0.010, CH
2
Cl
2
), R
f
: 0.70 (ethyl acetate/n-hexane 1:1), FTIR
1
ATR) ν 3270 (NH), 3056, 2964, 2878, 1704 (C=O), 1607, 1588, 1514, 1455, 1438, 1379, 1182, 1042; H NMR
(
CDCl
3
, 500 MHz) δ 0.83 (t, J 7.25 Hz, 3H, CH
.35 (m, 1H, CH ), 1.48-1.57 (m, 2H, H10a), 1.69-1.75 (m, 2H, H10s), 1.80-1.91 (m, 3H, H
.66-2.74 (m, 1H, CH), 2.77-2.82 (m, 1H, H8n), 2.86 (brs, 2H, H ), 2.91-2.94 (m, 2H, H ), 3.08-3.11 (m, 1H, H8n),
.14-3.18 (m, 2H, H ), 3.23-3.27 (m, 2H, H ), 4.51 (d, J 11.98 Hz, 1H, CH), 5.09 (d, J 7.25 Hz, 4H, CH ), 7.09-7.11
, 125 MHz) δ
), 40.1 (CH), 41.2 (CH),
1.4 (CH), 44.9 (CH), 45.2 (CH), 46.3 (CH), 46.9 (CH), 47.0 (CH), 48.1 (CH), 48.6 (CH), 61.0 (CH), 65.7 (CH ), 65.8
), 124.7 (Car), 126.0 (Car), 126.8 (Car), 127.0 (Car), 127.1 (Car), 127.3 (Car), 128.7 (Car), 128.8 (Car), 135.2 (C ),
3
), 1.00 (p, J 7.25 Hz, 1H, CH
2
), 1.18 (d, J 7.25 Hz, 3H, CH
3
), 1.29-
1
2
3
2
9
), 2.09-2.18 (m, 1H, H
9
),
1
7
2
6
2
13
(m, 4H, Har), 7.16-7.19 (m, 2H, Har), 8.04 (d, J 4.04 Hz, 2H, Har), 9.12 (brs, 1H, NH); C NMR (CDCl
3
1
4
0.0 (CH
3
), 15.3 (CH
3
), 25.4 (CH
2
), 32.0 (CH), 32.9 (CH), 39.4 (CH
2
), 39.8 (CH), 40.0 (CH
2
2
(CH
2
q
1
45.3 (C
q
), 145.4 (C
q
), 160.7 (C
q
), 166.9 (C=O), 167.0 (C=O), 173.8 (C=O), 173.9 (C=O), 174.1 (C=O); HRMS (ESI):
+
+
calcd for [C38
H41Br
2
N
3
O
5
] ([M] ): m/z 779.1319, 780.1599 found [M+H] .
N-[8-Phenyl-4-azabicyclo[2.2.1]heptane-3-endo,5-endo-dicarboximide-4-yl]-2-(4-azabicyclo[2.2.1]hept-8-
ene-3-endo,5-endo-dicarboximide-4-yl)-3-methylpentanamide (7a). Colorless oil, yield 438.26 mg (85%),
2
2
[
1
(
1
(
H
α]
D
+14.6° (c 0.012, CH
2
Cl
2
), R
f
: 0.30 (ethyl acetate/n-hexane 1:1), FTIR (ATR) ν 3283 (N-H), 3010, 2968, 2810,
1
727 (C=O), 1703 (C=O), 1494, 1383, 1184, 1136; H NMR (CDCl
3
, 500 MHz) δ 0.76 (t, J 7.25 Hz, 3H, CH
), 1.49 ( d, J 8.82 Hz, 2H, H10a), 1.57-
), 1.85 ( d, J 10.4 Hz, 1H, H10s), 2.51-2.57
), 3.08-3.10 (m, 1H, H ), 3.14-3.16 (m, 1H,
), 3.35-3.37 (m, 2H, H ), 4.32 (d, J 11.98 Hz, 1H, CH), 6.13 (dd, J
3
), 0.90
p, J 6.62 Hz, 1H, CH
2
), 1.03 (d, J 6.62 Hz, 3H, CH
), 1.69 ( d, J 8.82 Hz, 1H, H10s), 1.74-1.75 (m, 1H, CH
), 2.88 (brd, J 5.67 Hz, 1H, H
), 3.21-3.24 (m, 1H, H8n), 3.29- 3.30 (m, 2H, H
3
), 1.21-1.27 (m, 1H, CH
2
.64 (m, 1H, CH
2
2
m, 1H, CH), 2.84 (brd, J 4.41 Hz, 1H, H
1
1
7
7
2
6
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