10.1002/ejoc.201700471
European Journal of Organic Chemistry
FULL PAPER
and 2an as solid. Mp: 188 °C; 1H NMR (300 MHz, DMSO–D6): δ
9.27 (s, 1H),7.28–7.25 (m, 2H),7.11–7.09 (m, 2H), 6.52 (s, 1H), 5.93
(s, 2H), 5.21 (s, 1H), 3.57 (s, 3H), 3.56–3.55 (s, 1H), 3.22–3.17 (m,
1H), 2.98–2.96 (m, 2H), 2.54 (s, 3H); 13C NMR (75 MHz, DMSO–D6):
δ 189.0, 147.6, 139.7, 134.8, 129.5, 125.7, 117.3, 108.6, 101.9,
100.8, 59.1, 54.4, 48.9, 46.8, 34.0, 31.1, 26.5; MS (ESI) m/z [M+H]+
calcd for C21H20NO5 366.13, found 366.15.
7.21–7.16 (m, 2H), 6.33 (s, 1H), 5.86 (s, 2H), 4.55–4.51 (m, 1H),
3.97 (s, 3H), 3.94 (s, 3H), 3.32–3.00 (m, 2H), 3.24–3.15 (m, 1H),
2.95–2.74 (m, 2H), 2.48–2.42 (m, 1H), 2.38 (s, 3H); 13C NMR (75
MHz, CDCl3): δ 198.5, 159.5, 147.7, 140.2, 137.1, 133.8, 132.7,
131.1, 129.7, 128.0, 127.8, 126.9, 125.0, 122.4, 119.5, 105.7, 102.6,
100.4, 59.2, 55.5, 55.2, 50.8, 44.4, 43.5, 41.9, 23.7; MS (ESI) m/z
[M+H]+ calcd for C25H26NO5 420.18, found 420.18.
1-(4,7-dimethoxybenzofuran-5-yl)-2-(4-methoxy-6-methyl-5,6,7,8-
tetrahydro-[1,3]dioxolo[4,5-g]isoquinolin-5-yl)ethan-1-one (3ai).
Following general procedure GP-3A, 3ai (793 mg, 90%) was
obtained from 1 and 2ai as white flake [alternatively, following GP-
3B, 3ai (75%) was obtained from 7b and 2ai]. Mp: 167 °C; 1H NMR
(300 MHz, CDCl3): δ 7.61 (d, J = 1.8 Hz, 1H), 2.38 (s, 3H), 7.22 (s,
1H), 6.93 (d, J = 2.1 Hz, 1H), 6.30 (s, 1H), 5.84 (s, 2H), 4.51 (dd, J =
5.4, 2.7 Hz, 1H), 4.06 (s, 3H), 4.06 (s, 3H), 3.93 (s, 3H), 3.48–3.43
(m, 1H), 3.41–3.24 (m, 1H), 3.10–3.04 (m, 1H), 2.88–2.85 (m, 1H),
2.77–2.69 (m, 1H), 2.45–2.44 (m, 1H); 13C NMR (75 MHz, CDCl3): δ
200.2, 147.7, 147.6, 144.9, 141.5, 140.3, 134.0, 128.1, 125.9, 122.8,
121.2, 107.4, 105.7, 102.5, 100.4, 61.5, 59.1, 56.3, 54.6, 47.7, 44.6,
41.9, 24.0; MS (ESI) m/z [M+H]+ calcd for C24H26NO7 440.17, found
440.21.
3-(4-methoxy-6-methyl-5,6,7,8-tetrahydro-[1,3]dioxolo[4,5-
g]isoquinolin-5-yl)benzofuran-2(3H)-one (3ao). Following general
procedure GP-3A, 3ao (659 mg, 93%, inseparable dr = 85: 15) was
obtained from 1 and 2ao as white solid [alternatively, following GP-
3B, 3ao (90%, inseparable dr = 85: 15) was obtained from 7b and
2ao]. Mp:158-160 °C; 1H (300 MHz,CDCl3): δ 7.20 (d, J = 7.8 Hz,
1H), 7.07 (d, J = 8.1 Hz, 1H), 6.90–6.84 (m, 1H), 6.33 (s, 1H), 6.25
(s, 1H), 5.95 (d, J = 6.3 Hz, 2H), 4.51 (d, J = 4.5 Hz, 1H), 4.42 (d, J =
4.5 Hz, 1H), 4.07 (s, 1H), 3.63 (s, 1H), 2.86–2.80 (m, 1H), 2.43 (s,
3H), 2.30–2.24 (m, 1H), 2.05–2.00 (m, 1H); 13C NMR (75 MHz,
CDCl3): δ (Mixture of diastereomers): 176.2, 154.4, 148.4, 148.1,
133.8, 128.3, 124.9, 123.4, 117.4, 110.5, 102.5, 100.7, 60.0, 59.4,
49.1, 46.3, 44.1, 22.6; MS (ESI) m/z [M+H]+ calcd for C20H20NO5
354.13, found 354.15.
1,3-bis(4-methoxy-6-methyl-5,6,7,8-tetrahydro-[1,3]dioxolo[4,5-
g]isoquinolin-5-yl)propan-2-one
(3aj).
Following
general
3-(4-methoxy-6-methyl-5,6,7,8-tetrahydro-[1,3]dioxolo[4,5-
procedure GP-3A, 3aj (437 mg, 92%) was obtained from 1 and 2aj
(in excess) as grey solid. Mp: 168 °C; H NMR (300MHz, CDCl3): δ
g]isoquinolin-5-yl)indolin-2-one
(3ap).
Following
general
1
procedure GP-3A, 3ap (636 mg, 90%, inseparable dr = 75: 25) was
obtained from 1 and 2ap as white solid. Mp: 167-169 °C; 1H NMR
(300 MHz; CDCl3): δ 7.98 (s, 1H), 7.13 (d, J = 7.2 Hz, 1H), 6.82 (d, J
= 7.5 Hz, 1H), 6.75 (d, J = 7.5 Hz, 1H), 6.34 (s, 1H), 6.19 (d, J = 7.5
Hz, 1H), 5.94 (d, J = 6.0 Hz, 2H), 4.59 (d, J = 4.5 Hz, 1H), 4.15 (d,
1H, J = 4.5 Hz), 4.06 (s, 3H), 3.55 (s, 1H), 2.95–2.78 (m, 1H), 2.74–
2.66 (m, 1H), 2.44 (s, 3H), 2.11–2.04 (m, 1H); 13C NMR (75 MHz,
CDCl3): δ (Mixture of diastereomers): 178.9, 148.1, 142.1, 140.6,
133.9, 130.9, 130.0, 128.8, 127.4, 124.9, 122.3, 121.6, 118.6, 109.5,
102.4, 100.6, 59.5, 59.4, 51.0, 46.4, 43.9, 22.7; MS (ESI) m/z [M+H]+
6.30 (s, 2H), 5.86 (s, 4H), 4.43 (d, J = 9.9 Hz, 1H), 4.00 (s, 6H),
3.17–3.09 (m, 2H), 2.92–2.83 (m, 4H), 2.77–2.59 (m, 4H), 2.43 (s,
6H), 2.39–2.33 (m, 2H); 13C NMR (75 MHz, CDCl3): δ 208.4, 147.6,
140.3, 133.8, 127.8, 122.2, 121.9, 102.7, 100.4, 59.1, 54.7, 48.6,
47.3, 47.0, 44.2, 43.7, 41.7, 41.5, 22.9; MS (ESI) m/z [M+H]+ calcd
for C27H33N2O7 497.23, found 497.19.
3-acetyl-3-(4-methoxy-6-methyl-5,6,7,8-tetrahydro-
[1,3]dioxolo[4,5-g]isoquinolin-5-yl)-6-methyl-2H-pyran-2,4(3H)-
dione (3ak). Following general procedure GP-3A, 3ak (707 mg, 91%, calcd for C20H20N2O4 353.15, Found 353.18.
inseparable dr = 9:1) was obtained from 1 and 2ak as white solid.
1
Mp: 117 °C; H NMR (300 MHz, CDCl3): δ 6.30 (s, 1H), 5.86 (s, 2H),
5.73 (s, 1H), 4.79–4.76 (m, 1H), 3.94 (s, 3H), 3.80–3.71 (m, 1H),
3.46 (s, 3H), 3.14–2.93 (m, 3H), 2.67 (s, 3H), 2.13 (s, 3H); 13C NMR
(75 MHz, CDCl3): δ 200.6, 181.9, 164.5, 163.7, 148.5, 140.0, 134.1,
126.0, 119.2, 105.2, 102.5, 102.2, 101.3, 100.7, 59.2, 55.2, 50.7,
45.0, 44.7, 41.0, 23.1, 20.1; MS (ESI) m/z [M+H]+ calcd for
C20H22NO7 388.14, found 388.12.
2-(4-methoxy-6-methyl-5,6,7,8-tetrahydro-[1,3]dioxolo[4,5-
g]isoquinolin-5-yl)naphtho[2,1-b]furan-1(2H)-one
(3aq).
Following general procedure GP-3A, 3aq (744 mg, 92%, inseparable
dr = 85: 15) was obtained from 1 and 2aq as grey solid. Mp: 188 °C;
1H NMR (300 MHz, CDCl3): δ 8.84 (d, J = 8.1 Hz, 1H), 8.03 (d, J =
9.0 Hz, 1H), 7.83–7.81 (m, 1H),7.68–7.63 (m, 1H), 7.47–7.42 (m,
1H), 7.23–7.20 (m, 1H), 6.39 (s, 1H), 5.90 (s, 2H), 5.09 (d, J= 3.0 Hz,
1H), 4.53 (d, J = 2.7 Hz, 1H), 4.02 (s, 3H), 3.18–3.08 (m, 1H), 2.81–
2.72 (m, 1H), 2.59–2.49 (m, 2H), 2.39 (s, 3H); 13C NMR (75 MHz,
CDCl3): δ 200.2, 148.1, 140.1, 133.6, 130.9, 129.6, 128.5, 125.0,
123.4, 117.4, 102.6, 100.6, 89.7, 59.5, 59.2, 47.9, 44.3, 24.4; MS
(ESI) m/z [M+H]+ calcd for C24H22NO5 404.15, found 404.13.
2-(4-methoxy-6-methyl-5,6,7,8-tetrahydro-[1,3]dioxolo[4,5-
g]isoquinolin-5-yl)cyclopentane-1,3-dione
(3am).
Following
general procedure GP-3A, 3am (579 mg, 91%) was obtained from 1
and 2am as white solid. Mp: 156 °C; 1H NMR (300 MHz, CDCl3): δ
6.33 (s, 1H), 5.89–5.86 (m, 2H), 5.07 (s, 1H), 3.79 (s, 3H), 3.73 (m,
1H), 3.25–3.11 (m, 1H), 3.02–2.71 (m, 5H), 2.16 (s, 3H), 2.13 (s,
1H); 13C NMR (75 MHz, DMSO–d6): δ 198.4, 147.4, 135.0, 125.8,
109.1, 101.0, 100.8, 66.9, 65.5, 58.9, 49.2, 47.1, 36.6, 35.8, 34.8,
1-(2-bromo-6-hydroxyphenyl)-2-(4-methoxy-6-methyl-5,6,7,8-
tetrahydro-[1,3]dioxolo[4,5-g]isoquinolin-5-yl)ethan-1-one (9a).
Following general procedure GP-3B, 9a (729 mg, 84%) was
o
1
obtained from 7b and 8a as white solid. Mp= 106 C; H NMR (300
30.3; MS (ESI) m/z [M+H]+ calcd for C17H20NO5 318.13, found 318.25. MHz, CDCl3): δ 7.70 (d, J = 8.4 Hz, 1H), 7.18 (s, 1H), 7.03(d, J =
8.4 Hz, 1H), 6.31 (s, 1H), 5.86 (s, 2H), 4.38 (t, J =6.0 Hz, 1H), 3.95
2-(4-methoxy-6-methyl-5,6,7,8-tetrahydro-[1,3]dioxolo[4,5-
g]isoquinolin-5-yl)cyclohexane-1,3-dione (3al). Following general
procedure GP-3A, 3al (598 mg, 90%) was obtained from 1 and 2al
as white solid [alternatively, following GP-3B, 3al (82%) was
obtained from 7b and 2al]. Mp: 187 °C; 1H NMR (300 MHz, DMSO–
D6): δ 6.27 (s, 1H), 5.89–5.83 (m, 2H), 5.21 (m, 2H), 3.33–3.26 (m,
2H), 2.86–2.76 (m, 1H), 2.71–2.66 (m, 1H), 2.62 (s, 3H), 2.41–2.22
(m, 5H), 1.90–1.81 (m, 2H); 13C NMR (75 MHz, CDCl3): δ 189.6,
148.0, 140.9, 135.9, 126.6, 120.9, 110.5, 102.0, 100.9, 59.5, 59.0,
51.2, 41.5, 34.7, 28.4, 20.6; MS (ESI) m/z [M+H]+ calcd for
C17H19NO5 332.15, found 332.16.
(s, 3H), 3.18–3.10 (m, 3H), 2.93–2.75 (m, 2H), 2.47–2.41 (m, 1H),
2.39(s, 3H); 13C NMR (75 MHz, CDCl3): δ 205.2, 163.4, 148.4, 140.4,
134.0, 131.5, 130.5, 128.4, 122.6, 122.0, 121.6, 119.2, 103.0, 100.9,
59.5, 56.1, 44.8, 44.0, 42.3, 23.8; HRMS (ESI) m/z [M+H]+ calcd for
C20H21BrNO5 434.0603, 436.0582, found 434.0598, 436.0580.
1-(4-fluoro-2-hydroxyphenyl)-2-(4-methoxy-6-methyl-5,6,7,8-
tetrahydro-[1,3]dioxolo[4,5-g]isoquinolin-5-yl)ethan-1-one (9b).
Following general procedure GP-3B, 9b (641 mg, 86%) was
obtained from 7b and 8b as white solid. Mp= 127 C; H NMR (300
MHz, CDCl3): δ 7.87–7.82 (m, 1H), 6.68–6.55 (m, 2H), 6.32 (s, 1H),
5.86 (s, 2H), 4.42 (dd, J = 6.3, 3.0 Hz, 1H), 3.96 (s, 3H), 3.20–3.09
(m, 3H), 2.94–2.75 (m, 2H), 2.47–2.45 (m, 1H), 2.39 (s, 3H); 13C
NMR (75 MHz, CDCl3): δ 204.1, 168.8, 165.4, 165.0, 148.0, 140.1,
133.7, 132.5 ,132.3, 128.1, 121.3, 117.0, 117.0, 107.0, 106.7, 105.1,
104.8, 102.6, 100.5, 59.1, 55.6, 44.4, 43.5, 41.9, 23.4; HRMS (ESI)
o
1
2-(4-methoxy-6-methyl-5,6,7,8-tetrahydro-[1,3]dioxolo[4,5-
g]isoquinolin-5-yl)-1H-indene-1,3(2H)-dione
(3an).
Following
general procedure GP-3A, 3an (681 mg, 93%) was obtained from 1
This article is protected by copyright. All rights reserved.