E
Synthesis
E. Carlson, W. Tam
Paper
Cyclopropanated N-Butoxycarbonyl-7-azabenzonorbornadiene
10a)
IR (neat): 3270, 3004, 1627, 1446, 1230, 1204, 1082, 1033, 811 cm–1
.
(
1
H NMR (400 MHz, CDCl ): δ = 7.34–7.29 (m, 2 H), 7.15–7.13 (m, 2 H),
3
Yield: 1.61 g (98%); white solid; mp 48–50 °C; Rf = 0.30 (EtOAc–
hexanes, 1:9).
5.47 (s, 1 H), 4.94 (s, 1 H), 1.98 (s, 3 H), 1.30–1.28 (m, 2 H), 1.17–1.14
(m, 1 H), 1.08–1.04 (m, 1 H).
1
3
IR (NaCl): 3053, 3011, 2978, 2931, 1698 (C=O), 1367, 1172, 1093,
C NMR (100 MHz, CDCl , JMOD): δ = 166.8, 147.4, 146.8, 126.1,
3
–1
1050, 739 cm
.
125.8, 120.2, 119.4, 61.6, 58.2, 21.5, 21.1, 20.0, 15.9.
1
+
H NMR (400 MHz, CDCl ): δ = 7.28–7.26 (br s, 2 H), 7.11–7.07 (m, 2
HRMS (EI): m/z [M] calcd for C13H13NO: 199.0997; found: 199.0999.
3
H), 5.05 (br s, 1 H), 4.94 (br s, 1 H), 1.37 (s, 9 H), 1.34–1.31 (m, 1 H),
1
.21–1.19 (m, 2 H), 1.01–0.96 (m, 1 H).
Cyclopropanated N-Pivaloyl-7-azabenzonorbornadiene (10f)
13
C NMR (100 MHz, CDCl ): δ = 154.9, (148.0, 147.6), 125.7, (120.1,
3
Yield: 348 mg (86%); white solid; mp 160–162 °C; R = 0.38 (EtOAc–
f
119.6), 79.9, (61.0, 60.2), 28.3, (21.5, 20.8), 15.9.
hexanes, 3:7).
+
HRMS (EI): m/z [M] calcd for C 6H NO : 257.1416; found: 257.1412.
1
19
2
IR (NaCl): 3046, 3030, 2978, 2965, 1613 (C=O), 1454, 1199, 1044, 746
–1
cm
.
Cyclopropanated N-Methoxycarbonyl-7-azabenzonorbornadiene
10b)
1
H NMR (400 MHz, CDCl ): δ = 7.28–7.26 (m, 2 H), 7.11–7.08 (m, 2 H),
.44 (br s, 1 H), 5.40 (br s, 1 H), 1.25–1.20 (m, 3 H), 1.17 (s, 9 H), 1.01–
3
(
5
Yield: 511 mg (95%); white solid; mp 162–163 °C; R = 0.28 (EtOAc–
0.96 (m, 1 H).
f
hexanes, 1:4).
13
C NMR (100 MHz, CDCl ): δ = 174.3, (147.7, 147.0), 125.9, (120.2,
3
IR (NaCl): 3077, 3028, 2957, 1697 (C=O), 1450, 1368, 1257, 1106 cm–1
.
119.1), (61.6, 59.1), 38.7, 27.7, (21.3, 19.5), 15.7.
1
+
H NMR (400 MHz, CDCl ): δ = 7.31 (br s, 2 H), 7.12 (m, 2 H), 5.14 (br
HRMS (EI): m/z [M] calcd for C16H19NO: 241.1467; found: 241.1471.
3
s, 1 H), 5.03 (br s, 1 H), 3.61 (s, 3 H), 1.43 (m, 1 H), 1.25 (m, 2 H), 1.01
(
1
m, 1 H).
Cyclopropanated N-Phenyl-7-azabenzonorbornadiene (10g)
3
C NMR (100 MHz, CDCl , JMOD): δ = 156.0, (147.9, 147.4), 125.9,
3
Yield: 968 mg (92%); white solid; mp 116–118 °C; R = 0.47 (EtOAc–
f
(120.2, 119.7), (60.7, 60.5), 52.5, (21.3, 20.7), 16.0.
hexanes, 1:9).
+
HRMS (EI): m/z [M] calcd for C 3H NO : 215.0946; found: 215.0941.
1
13
2
IR (neat): 3056, 2998, 1595, 1497, 1451, 1317, 1247, 1077, 945, 822
–1
cm
.
Cyclopropanated N-Carboxybenzyl-7-azabenzonorbornadiene
10c)
1
H NMR (400 MHz, CDCl ): δ = 7.39–7.37 (m, 2 H), 7.22–7.14 (m, 4 H),
.85–6.81 (m, 3 H), 4.99 (s, 2 H), 2.15–2.12 (m, 1 H), 1.44–1.41 (m, 2
3
(
6
Yield: 178 mg (98%); white solid; mp 79–82 °C; R = 0.20 (EtOAc–
H), 1.11–1.06 (m, 1 H).
f
hexanes, 1:9).
13
C NMR (100 MHz, CDCl , JMOD): δ = 147.9, 147.4, 128.9, 125.8,
3
IR (NaCl): 3031, 3012, 2944, 1702 (C=O), 1453, 1392, 1338, 1246,
121.2, 119.8, 117.2, 63.5, 21.7, 16.0.
–1
1080, 819 cm
.
+
HRMS (EI): m/z [M] calcd for C17H15N: 233.1204; found: 233.1201.
1
H NMR (400 MHz, CDCl ): δ = 7.39–7.24 (m, 7 H), 7.18–7.11 (m, 2 H),
3
5
.20 (s, 1 H), 5.11 (s, 1 H), 5.09 (s, 1 H), 5.03 (s, 1 H), 1.41–1.39 (m, 1
Cyclopropanated N-Butoxycarbonyl-7-azanaphthonorbornadiene
H), 1.27–1.24 (m, 2 H), 1.08–1.03 (m, 1 H).
(10h)
13
C NMR (100 MHz, CDCl , JMOD): δ = 155.3, (147.8, 147.4), 136.5,
3
Yield: 243 mg (80%); white solid; mp 168–169 °C; R = 0.35 (EtOAc–
f
128.5, 127.9, 127.7, 125.9, 120.2, 119.7, 66.8, (60.8, 60.7), (21.3, 20.7),
hexanes, 1:9).
16.0.
IR (neat): 3005, 2970, 2932, 1682 (C=O), 1423, 1365, 1253, 1161,
+
HRMS (EI): m/z [M] calcd for C19H17NO : 291.1259; found: 291.1260.
–1
2
1092, 872 cm .
1
H NMR (400 MHz, CDCl ): δ = 7.82–7.80 (m, 2 H), 7.68 (br s, 1 H),
3
Cyclopropanated N-p-Toluenesulfonyl-7-azabenzonorbornadiene
7
.65 (br s, 1 H), 7.48–7.46 (m, 2 H), 5.19 (br s, 1 H), 5.08 (br s, 1 H),
(10d)
1.38 (s, 9 H), 1.33–1.30 (m, 1 H), 1.27–1.25 (m, 2 H), 0.97–0.93 (m, 1
Yield: 660 mg (90%); beige solid; mp 193–195 °C; R = 0.62 (EtOAc–
H).
f
hexanes, 1:1).
13
C NMR (100 MHz, CDCl , JMOD): δ = 155.2, 145.1, 132.3, (128.2,
3
IR (NaCl): 3066, 2994, 1337, 1161, 1093, 1042, 1024, 908, 776, 732,
128.0), 125.7, (118.4, 117.8), 80.1, (60.8, 60.0), 28.3, (20.6, 20.0), 13.4.
–1
693 cm
.
+
HRMS (EI): m/z [M] calcd for C20H21NO : 307.1572; found: 307.1569.
2
1
H NMR (400 MHz, CDCl ): δ = 7.27–7.25 (m, 2 H), 6.91–6.89 (m, 4 H),
3
6
.81–6.79 (m, 2 H), 4.89 (s, 2 H), 2.25 (s, 3 H), 2.03–2.02 (m, 1 H),
Cyclopropanated N-Butoxycarbonyl-o-dimethyl-7-azabenzonor-
bornadiene (10i)
1.27–1.24 (m, 2 H), 1.06 (q, J = 6.4 Hz, 1 H).
13
C NMR (100 MHz, CDCl , JMOD): δ = 145.7, 142.7, 135.3, 128.9,
3
Yield: 560 mg (87%); white solid; mp 121–122 °C; R = 0.50 (EtOAc–
f
127.7, 125.7, 120.3, 63.2, 21.7, 21.4, 16.5.
hexanes, 1:4).
HRMS (EI): m/z [M]+ calcd for C18H17NSO2: 311.0980; found:
11.0985.
IR (NaCl): 3007, 2975, 2929, 1701, 1392, 1366, 1253, 1173, 1092 cm–1
.
3
1
H NMR (400 MHz, CDCl ): δ = 7.09 (br d, J = 3.4 Hz, 2 H), 5.01 (br s, 1
3
H), 4.91 (br s, 1 H), 2.25 (s, 6 H), 1.39 (s, 9 H), 1.31–1.27 (m, 1 H), 1.21–
Cyclopropanated N-Acetyl-7-azabenzonorbornadiene (10e)
1.19 (m, 2 H), 0.97 (q, J = 6.4 Hz, 1 H).
Yield: 517 mg (91%); beige solid; mp 103–105 °C; R = 0.08 (EtOAc–
hexanes, 1:1).
13
f
C NMR (100 MHz, CDCl , JMOD): δ = 154.7, (145.7, 145.4), 133.4,
3
(121.7, 121.1), 79.8, (60.8, 59.9), 28.3, (21.6, 21.0), 19.9, 15.7.
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–F