6
X.-Y. Liu et al. / Tetrahedron xxx (xxxx) xxx
half an hour, ArCH
2
Br (2 mmol) was added. The reaction mixture
2H), 7.58 (d, J ¼ 7.2 Hz, 1H); 13C NMR
d 15.4, 42.6, 46.0, 55.1, 64.3,
was stirred at room temperature overnight. The solvent was
removed in vacuo, and the residue was purified by column chro-
matography on silica with ethyl acetate/petroleum ether (V/
69.9, 100.9, 113.3, 123.0, 124.0, 127.5, 127.9, 130.3, 131.2, 132.1, 147.2,
þ
158.4, 169.1; HRMS (ESI) calcd for C30
H35NO
5
[MþH] : 490.2593,
found: 490.2580.
1
V ¼ 1:3) as the eluent to afford products 2ae2u.
Data of 2i. Yellow oil. H NMR
d
1.10 (t, J ¼ 7.0 Hz, 6H), 2.24 (s,
1
Data of 2a. Yellow oil. H NMR
d
1.19 (t, J ¼ 7.0 Hz, 6H), 3.16 (d,
3H), 3.06 (d, J ¼ 14.1 Hz, 2H), 3.39 (d, J ¼ 14.1 Hz, 2H), 3.53e3.56 (m,
2H), 3.57 (d, J ¼ 5.0 Hz, 2H), 3.70e3.78 (m, 2H), 5.01 (t, J ¼ 5.1 Hz,
1H), 6.48 (s, 1H), 6.73 (dd, J ¼ 7.4, 1.7 Hz, 4H), 7.00e7.05 (m, 7H),
J ¼ 14.1 Hz, 2H), 3.48 (d, J ¼ 14.1 Hz, 2H), 3.58e3.65 (m, 2H), 3.69 (d,
J ¼ 5.1 Hz, 2H), 3.79e3.86 (m, 2H), 5.11 (t, J ¼ 5.0 Hz, 1H), 6.79e6.81
1
3
(
1
m, 5H), 7.08e7.14 (m, 6H), 7.28e7.36 (m, 2H), 7.57 (d, J ¼ 7.0 Hz,
7.38 (d, J ¼ 7.7 Hz, 1H); C NMR
d 15.4, 22.0, 43.7, 46.0, 64.3, 69.4,
1
3
H); C NMR
d
15.4, 43.6, 46.0, 64.4, 69.8, 100.8, 123.0, 124.1, 126.8,
100.9, 122.8, 124.6, 126.8, 127.8, 128.9, 129.5, 130.3, 135.7, 140.8,
þ
127.9,128.0,130.3,130.4,132.0,135.5,146.9,169.0; HRMS (ESI) calcd
147.2, 169.1; HRMS (ESI) calcd for C29
H34NO
3
[MþH] : 444.2539,
þ
for C28
H
32NO
3
[MþH] : 430.2382, found: 430.2372.
found: 444.2525.
1
1
Data of 2b. Yellow oil. H NMR
d
1.17 (t, J ¼ 7.0 Hz, 6H), 3.51 (d,
Data of 2j. Yellow oil. H NMR
d
1.17 (t, J ¼ 7.0 Hz, 6H), 2.21 (s,
J ¼ 14.8 Hz, 2H), 3.56e3.64 (m, 2H), 3.73 (d, J ¼ 5.1 Hz, 2H),
.77e3.85 (m, 4H), 5.17 (t, J ¼ 5.1 Hz, 1H), 6.77e6.81 (m, 3H), 6.95
td, J ¼ 7.6, 1.5 Hz, 2H), 7.02 (t, J ¼ 7.0 Hz, 2H), 7.22 (t, J ¼ 7.4 Hz, 1H),
.27 (t, J ¼ 7.2 Hz,1H), 7.40 (d, J ¼ 7.2 Hz, 2H), 7.63 (d, J ¼ 7.3 Hz,1H);
3H), 3.49 (d, J ¼ 14.8 Hz, 2H), 3.54e3.62 (m, 2H), 3.70 (d, J ¼ 5.0 Hz,
2H), 3.74 (d, J ¼ 14.8 Hz, 2H), 3.76e3.84 (m, 2H), 5.14 (t, J ¼ 5.0 Hz,
1H), 6.57 (s, 1H), 6.80 (d, J ¼ 7.6 Hz, 2H), 6.96 (t, J ¼ 7.6 Hz, 2H),
3
(
7
13
7.01e7.08 (m, 3H), 7.41 (d, J ¼ 7.9 Hz, 2H), 7.50 (d, J ¼ 7.7 Hz,1H);
C
13
C NMR
d
15.3, 41.8, 45.9, 63.9, 69.7, 100.5, 122.9, 123.7, 126.3, 127.0,
NMR d 15.3, 21.8, 41.9, 45.8, 63.9, 69.4, 100.6, 122.6, 124.3, 126.3,
1
28.1,128.4,130.7,130.8,131.8,132.9,135.5,146.3,169.3; HRMS (ESI)
127.0, 128.3, 129.0, 129.2, 130.7, 132.8, 135.6, 141.2, 146.5, 169.5;
þ
þ
calcd for C28
H
29Br
2
NNaO
3
[MþNa] : 610.0391, found: 610.0378.
HRMS (ESI) calcd for C29
H
32Br
2
NO
3
[MþH] : 602.0728, found:
1
Data of 2c. Yellow oil. H NMR
d
1.19 (t, J ¼ 7.8 Hz, 6H), 3.17 (d,
602.0717.
1
J ¼ 14.2 Hz, 2H), 3.39 (d, J ¼ 14.1 Hz, 2H), 3.58e3.66 (m, 4H),
Data of 2k. Yellow oil. H NMR
d
1.18 (t, J ¼ 7.0 Hz, 6H), 2.34 (s,
3
6
.79e3.87 (m, 2H), 5.08 (t, J ¼ 4.2 Hz, 1H), 6.75 (d, J ¼ 7.6 Hz, 2H),
.87 (d, J ¼ 7.5 Hz, 1H), 6.93 (s, 2H), 6.97 (td, J ¼ 7.9, 1.4 Hz, 2H), 7.26
3H), 3.11 (d, J ¼ 14.1 Hz, 2H), 3.45 (d, J ¼ 14.1 Hz, 2H), 3.59 (s, 6H),
3.60e3.64 (m, 2H), 3.77e3.85 (m, 2H), 5.07 (t, J ¼ 5.0 Hz, 1H), 6.28
(
(
1
d, J ¼ 8.1 Hz, 2H), 7.36 (t, J ¼ 7.5 Hz, 1H), 7.44 (t, J ¼ 7.5 Hz, 1H), 7.62
(s, 2H), 6.47 (d, J ¼ 7.5 Hz, 2H), 6.67e6.69 (m, 3H), 7.04 (t, J ¼ 7.9 Hz,
13
13
d, J ¼ 7.4 Hz, 1H); C NMR
d
15.3, 43.0, 46.0, 64.3, 69.4, 100.7, 121.9,
2H), 7.15 (d, J ¼ 7.7 Hz, 1H), 7.50 (d, J ¼ 7.7 Hz, 1H); C NMR
d 15.4,
23.4, 123.6, 128.5, 128.7, 129.5, 130.0, 130.8, 131.9, 133.2, 137.6,
21.9, 43.7, 45.9, 55.0, 64.3, 69.4, 100.9, 112.7, 115.5, 122.8, 122.9,
þ
146.2, 168.9; HRMS (ESI) calcd for
C
28
H
30Br
2
NO
3
[MþH] :
124.6, 128.8, 128.9, 129.7, 137.1, 140.7, 147.5, 159.0, 169.0; HRMS (ESI)
þ
5
88.0572, found: 588.0560.
calcd for C31
H
38NO
5
[MþH] : 504.2750, found: 504.2743.
1
1
Data of 2d. Yellow oil. H NMR
d
1.18 (t, J ¼ 7.0 Hz, 6H), 3.14 (d,
Data of 2l. Yellow oil. H NMR
d
1.19 (t, J ¼ 7.0 Hz, 6H), 3.18 (d,
J ¼ 14.2 Hz, 2H), 3.38 (d, J ¼ 14.2 Hz, 2H), 3.57e3.64 (m, 4H),
J ¼ 14.1 Hz, 2H), 3.45 (d, J ¼ 14.1 Hz, 2H), 3.61e3.67 (m, 2H), 3.68 (d,
J ¼ 5.1 Hz, 2H), 3.79e3.86 (m, 2H), 5.08 (t, J ¼ 5.1 Hz, 1H), 6.45 (dd,
J ¼ 8.7, 2.1 Hz, 1H), 6.83 (dd, J ¼ 7.2, 2.2 Hz, 4H), 6.99 (td, J ¼ 8.8,
3
6
.79e3.86 (m, 2H), 5.09 (t, J ¼ 4.8 Hz, 1H), 6.67 (d, J ¼ 7.7 Hz, 4H),
.85 (d, J ¼ 7.3 Hz, 1H), 7.22 (d, J ¼ 7.4 Hz, 4H), 7.32e7.41 (m, 2H),
13
13
7
.60 (d, J ¼ 7.4 Hz, 1H); C NMR
d
15.3, 42.9, 46.0, 64.4, 69.3, 100.7,
2.2 Hz, 1H), 7.10e7.15 (m, 6H), 7.53 (dd, J ¼ 8.3, 5.1 Hz, 1H); C NMR
121.0,123.4,123.6,128.4,130.7,131.1,131.8,131.9,134.3,146.3,168.9;
d
15.4, 43.4, 46.1, 64.3, 69.5, 100.7, 111.4 (d, JF-C ¼ 24.4 Hz), 115.6,
þ
HRMS (ESI) calcd for C28
5
H30Br
2
NO
3
[MþH] : 588.0572, found:
115.8, 125.0 (d, JF-C ¼ 9.7 Hz), 127.0, 128.0, 130.2, 135.1, 149.4 (d, JF-
88.0551.
Data of 2e. Yellow oil. H NMR
C
¼ 9.1 Hz), 164.1 (d, JF-C ¼ 250.6 Hz), 167.9; HRMS (ESI) calcd for
1
þ
d
1.19 (t, J ¼ 7.0 Hz, 6H), 3.17 (d,
C
28
H31FNO
3
[MþH] : 448.2288, found: 448.2280.
1
J ¼ 14.2 Hz, 2H), 3.41 (d, J ¼ 14.2 Hz, 2H), 3.61e3.64 (m, 2H), 3.65 (d,
Data of 2m. Yellow oil. H NMR
d
1.18 (t, J ¼ 7.0 Hz, 6H), 3.49 (d,
J ¼ 5.0 Hz, 2H), 3.79e3.87 (m, 2H), 5.10 (t, J ¼ 5.1 Hz, 1H), 6.76e6.84
J ¼ 14.7 Hz, 2H), 3.57e3.65 (m, 2H), 3.73 (d, J ¼ 5.1 Hz, 2H), 3.76 (d,
J ¼ 14.7 Hz, 2H), 3.80e3.86 (m, 2H), 5.16 (t, J ¼ 5.1 Hz, 1H), 6.42 (dd,
J ¼ 8.8, 2.1 Hz, 1H), 6.88 (dd, J ¼ 7.7, 1.5 Hz, 2H), 6.93e7.02 (m, 3H),
7.08 (t, J ¼ 7.5 Hz, 2H), 7.43 (dd, J ¼ 7.9, 1.2 Hz, 2H), 7.58 (dd, J ¼ 8.3,
13
(
4
m, 9H), 7.31e7.40 (m, 2H), 7.59 (d, J ¼ 7.2 Hz, 1H); C NMR
d 15.3,
2.6, 46.0, 64.4, 69.6, 100.7, 114.8 (d, JF-C ¼ 21.1 Hz), 123.3, 123.7,
1
28.2, 130.6, 131.1 (d, JF-C ¼ 3.3 Hz), 131.6 (d, JF-C ¼ 7.9 Hz), 132.0,
1
3
146.5, 161.8 (d, JF-C ¼ 245.6 Hz), 169.0; HRMS (ESI) calcd for
5.1 Hz, 1H); C NMR d 15.3, 41.6, 45.9, 64.0, 69.3, 100.4, 111.3 (d, JF-
þ
C
H
28 30
F
2
NO
3
[MþH] : 466.2194, found: 466.2179.
C
¼ 24.9 Hz), 115.8 (d, JF-C ¼ 23.4 Hz), 124.8 (d, JF-C ¼ 9.6 Hz), 126.3,
1
Data of 2f. Yellow oil. H NMR
d
1.20 (t, J ¼ 7.9 Hz, 6H), 2.17 (s,
127.2, 127.7,128.7, 130.7, 133.1,135.1, 148.6 (d, JF-C ¼ 9.8 Hz),164.3 (d,
6
4
6
H), 3.09 (d, J ¼ 14.0 Hz, 2H), 3.45 (d, J ¼ 14.0 Hz, 2H), 3.62e3.66 (m,
H), 3.79e3.86 (m, 2H), 5.10 (t, J ¼ 4.0 Hz, 1H), 6.60e6.62 (m, 4H),
.81 (d, J ¼ 7.3 Hz,1H), 6.93 (d, J ¼ 7.3 Hz, 2H), 6.99 (t, J ¼ 7.3 Hz, 2H),
J
F-C ¼ 250.9 Hz), 168.3; HRMS (ESI) calcd for C28
2 3
H28Br FNNaO
þ
[MþNa] : 628.0297, found: 628.0322.
1
Data of 2n. Yellow oil. H NMR
d
1.19 (t, J ¼ 7.0 Hz, 6H), 3.14 (d,
13
7
4
.32e7.37 (m, 2H), 7.59 (d, J ¼ 7.0 Hz, 1H); C NMR
d
15.4, 21.3, 43.6,
J ¼ 14.1 Hz, 2H), 3.43 (d, J ¼ 14.1 Hz, 2H), 3.57e3.66 (m, 10H),
3.78e3.86 (m, 2H), 5.07 (t, J ¼ 5.1 Hz, 1H), 6.32 (s, 2H), 6.46 (d,
6.0, 64.3, 69.8, 100.9, 122.9, 124.3, 127.3, 127.5, 127.7, 127.9, 130.1,
131.2, 132.1, 135.5, 137.3, 147.1, 169.0; HRMS (ESI) calcd for
J ¼ 7.5 Hz, 2H), 6.56 (dd, J ¼ 8.7, 2.0 Hz, 1H), 6.69 (dd, J ¼ 8.2, 2.0 Hz,
þ
13
C
30
H
36NO
3
[MþH] : 458.2695, found: 458.2676.
2H), 7.00e7.08 (m, 3H), 7.57 (dd, J ¼ 8.3, 5.1 Hz, 1H); C NMR
d 15.4,
1
Data of 2g. Yellow oil. H NMR
d
1.19 (t, J ¼ 7.0 Hz, 6H), 3.13 (d,
43.5, 46.0, 55.1, 64.3, 69.4, 100.7, 111.4 (d, JF-C ¼ 24.4 Hz), 112.7,
115.68, 115.7 (d, JF-C ¼ 23.4 Hz), 122.7, 125.1 (d, JF-C ¼ 9.6 Hz), 128.2,
J ¼ 14.1 Hz, 2H), 3.48 (d, J ¼ 14.1 Hz, 2H), 3.58 (s, 6H), 3.60e3.66 (m,
H), 3.78e3.84 (m, 2H), 5.09 (t, J ¼ 5.0 Hz, 1H), 6.27 (s, 2H), 6.47 (d,
J ¼ 7.5 Hz, 2H), 6.67 (d, J ¼ 8.2 Hz, 2H), 6.90 (d, J ¼ 7.4 Hz,1H), 7.04 (t,
4
129.0, 136.6, 149.6 (d, JF-C ¼ 9.3 Hz), 159.1, 164.1 (d, JF-C ¼ 252.2 Hz),
þ
167.9; HRMS (ESI) calcd for C30
H
34FNNaO
5
[MþNa] : 530.2319,
13
J ¼ 7.9 Hz, 2H), 7.34e7.39 (m, 2H), 7.61 (d, J ¼ 7.2 Hz, 1H); C NMR
found: 530.2307.
1
d
15.4, 43.7, 46.0, 55.0, 64.3, 69.7, 100.8, 112.6, 115.6, 122.8, 123.1,
24.1, 128.1, 128.8, 130.3, 132.2, 137.0, 147.1, 159.0, 168.9; HRMS (ESI)
Data of 2o. Yellow oil. H NMR
d
1.19 (t, J ¼ 7.0 Hz, 6H), 3.14 (d,
1
J ¼ 14.1 Hz, 2H), 3.47 (d, J ¼ 14.1 Hz, 2H), 3.63e3.65 (m, 4H), 3.67 (s,
3H), 3.78e3.86 (m, 2H), 5.08 (t, J ¼ 5.1 Hz, 1H), 6.21 (d, J ¼ 2.1 Hz,
1H), 6.82e6.86 (m, 5H), 7.09e7.13 (m, 6H), 7.49 (d, J ¼ 8.4 Hz, 1H);
þ
calcd for C30
H
35NNaO
5
[MþNa] : 512.2413, found: 512.2408.
1
Data of 2h. Yellow oil. H NMR
d
1.19 (t, J ¼ 7.0 Hz, 6H), 3.07 (d,
1
3
J ¼ 14.2 Hz, 2H), 3.41 (d, J ¼ 14.2 Hz, 2H), 3.58e3.66 (m, 4H), 3.70 (s,
C NMR d 15.4, 43.7, 46.0, 55.4, 64.4, 69.2, 100.9, 108.5, 115.1, 124.3,
6
4
H), 3.79e3.86 (m, 2H), 5.10 (t, J ¼ 5.0 Hz, 1H), 6.63 (d, J ¼ 8.4 Hz,
H), 6.72 (d, J ¼ 8.5 Hz, 4H), 6.83 (d, J ¼ 7.2 Hz, 1H), 7.29e7.37 (m,
124.7, 126.9, 127.9, 130.3, 135.6, 149.1, 161.6, 168.8; HRMS (ESI) calcd
þ
for C29
H
34NO
4
[MþH] : 460.2488, found: 460.2478.
Please cite this article as: X.-Y. Liu et al., Synthesis of benzazepinoisoindolinone and bridged tricyclic isoindolinone derivatives, Tetrahedron,