The Journal of Organic Chemistry
194.5–195.5 °C. IR νmax (neat)/cmꢀ1: 2991, 2879, 1722, 1702,
Page 6 of 10
(t, J = 5.2 Hz, 1H), 7.23–7.21 (m, 4H), 7.08–7.04 (m, 2H),
1655, 1571, 1489, 1344, 1267, 1183, 1070, 941, 752; 1H NMR
(400 MHz, CDCl3): δ 7.83 (d, J = 5.2 Hz, 2H), 7.56 (d, J = 5.2
Hz, 4H), 7.53 (d, J = 5.2 Hz, 2H), 7.48 (d, J = 5.6 Hz, 2H),
7.44 (t, J = 5.2 Hz, 2H), 7.39 (t, J = 5.2 Hz, 2H), 7.25–7.24
(m, 2H), 6.94 (d, J = 5.6 Hz, 2H), 6.56 (d, J = 5.6 Hz, 2H),
6.29 (s, 1H), 5.67 (s, 1H), 5.49 (d, J = 8.8 Hz, 1H), 4.58 (s,
1H), 4.19 (d, J = 8.8 Hz, 1H), 3.64 (s, 3H), 2.35 (s, 3H), 2.18
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 175.1, 172.0,
166.4, 163.0, 159.0, 138.3, 137.8, 137.6, 137.0, 134.0, 131.9,
129.8, 128.9, 128.5, 126.1, 125.5, 120.0, 119.3, 94.3, 93.5,
66.4, 66.0, 54.9, 53.0, 52.0, 44.6, 16.5, 13.5. HRMS (ESI,
m/z): calcd for C39H32I2N4O4Na+, [M + H]+, 897.0405, found
897.0404.
6.93 (d, J = 5.2 Hz, 1H), 6.84 (dd, J = 0.8, 5.2 Hz, 1H), 6.79
(dd, J = 0.8, 5.2 Hz, 1H), 6.73 (d, J = 5.2 Hz, 1H), 6.67 (d, J =
4.8 Hz, 1H), 6.20 (s, 1H), 5.68 (d, J = 8.8 Hz, 1H), 5.67 (s,
1H), 4.88 (d, J = 8.8 Hz, 1H), 4.79 (s, 1H), 3.74 (s, 3H), 3.73
(s, 3H), 3.36 (s, 3H), 2.34 (s, 3H), 1.91 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 176.1, 173.0, 166.8, 161.7, 158.1, 156.9,
138.0, 137.8, 133.0, 129.5, 128.9, 128.8, 128.5, 128.3, 126.6,
125.5, 124.1, 123.4, 122.1, 120.5, 120.3, 119.9, 118.4, 109.8,
109.7, 65.4, 55.0, 54.5, 52.0, 49.7, 46.0, 42.7, 15.7, 14.1, 14.0.
HRMS (ESI, m/z): calcd for C41H38N4O6Na+, [M + H]+,
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7 0 5 . 2 6 8 4 ,
f o u n d
7 0 5 . 2 6 8 4 .
Methyl 2ꢀ((5S,6S,7S,12S,13R)ꢀ6,13ꢀbis(3ꢀmethoxyphenyl)ꢀ
1,11ꢀdimethylꢀ4,8ꢀdioxoꢀ3,9ꢀdiphenylꢀ2,3,9,10ꢀtetraazadispiro
[4.1.47.25]tridecaꢀ1,10ꢀdienꢀ12ꢀyl)acrylate (3ia). The reaction
was carried out on a 0.2 mmol scale following the General
Procedure. The annulation product 3ia and 3ib were purified
through column chromatography (hexanes/EtOAc: from 6:1 to
4:1) as white solid (total 3i: 126 mg, dr = 2.4:1, 92% yield).
M. p. 184.7–185.7 °C. IR νmax (neat)/cmꢀ1: 2947, 2838, 1711,
1596, 1584, 1502, 1433, 1410, 1382, 1298, 1233, 1155, 1049,
Methyl
2ꢀ((5S,6S,7S,12S,13R)ꢀ1,11ꢀdimethylꢀ6,13ꢀbis(3ꢀ
nitrophenyl)ꢀ4,8ꢀdioxoꢀ3,9ꢀdiphenyl ꢀ2,3,9,10ꢀtetraazadispiro
[4.1.47.25]tridecaꢀ1,10ꢀdienꢀ12ꢀyl)acrylate (3ga). The reacꢀ
tion was carried out on a 0.2 mmol scale following the Gen-
eral Procedure. The annulation product 3ga and 3gb were
purified through column chromatography (hexanes/EtOAc:
from 6:1 to 4:1) as white solid (total 3g: 137 mg, dr 1:1, 96%
yield). M. p. 178.5–179.5 °C. IR νmax (neat)/cmꢀ1: 2981, 2962,
2938, 1736, 1711, 1704, 1595, 1530, 1487, 1386, 1355, 1249,
1
922, 774; H NMR (400 MHz, CDCl3): δ 7.85 (d, J = 5.2 Hz,
2H), 7.48–7.45 (m, 4H), 7.31–7.26 (m, 3H), 7.15–7.09 (m,
3H), 6.77–6.73 (m, 3H), 6.68 (dd, J = 1.2, 5.2 Hz, 1H), 6.40
(d, J = 5.2 Hz, 1H), 6.36 (s, 1H), 6.28 (s, 1H), 5.81 (s, 1H),
5.05 (d, J = 8.8 Hz, 1H), 4.85 (d, J = 8.8 Hz, 1H), 4.79 (s, 1H),
3.75 (s, 3H), 3.72 (s, 3H), 3.54 (s, 3H), 2.39 (s, 3H), 2.20 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3): δ 175.4, 172.6, 166.7,
161.6, 161.5, 160.0, 159.5, 137.7, 137.4, 136.1, 134.7, 130.1,
129.5, 129.3, 128.9, 128.6, 125.7, 125.2, 120.6, 119.7, 119.3,
118.6, 114.0, 113.9, 113.7, 111.5, 67.5, 65.9, 55.2, 54.9, 52.2,
50.9, 46.0, 16.1, 13.8. HRMS (ESI, m/z): calcd for
1
1152, 931, 763; H NMR (400 MHz, CDCl3): δ 8.13 (d, J =
5.2 Hz, 1H), 8.04 (s, 1H), 8.03 (d, J = 5.6 Hz, 1H), 7.83 (d, J =
5.2 Hz, 2H), 7.82 (s, 1H), 7.55–7.42 (m, 7H), 7.34–7.28 (m,
3H), 7.17 (t, J = 4.8 Hz, 1H), 7.11 (d, J = 4.8 Hz, 1H), 6.34 (s,
1H), 5.84 (s, 1H), 5.21 (d, J = 8.8 Hz, 1H), 4.96 (d, J = 8.8 Hz,
1H), 4.85 (s, 1H), 3.79 (s, 3H), 2.41 (s, 3H), 2.21 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 174.5, 171.9, 166.3,
160.4, 160.3, 148.7, 148.3, 137.1, 136.8, 136.5, 135.3, 134.1,
132.7, 132.4, 130.4, 130.0, 129.6, 128.8, 126.4, 125.9, 123.3,
123.1, 121.5, 120.3, 119.1, 67.1, 65.6, 54.2, 52.6, 50.3, 45.9,
C41H39N4O6 , [M + H]+, 683.2864, found 683.2861.
+
+
16.2, 13.8. HRMS (ESI, m/z): calcd for C39H33N6O8 , [M +
Methyl 2ꢀ((5S,6R,7S,12S,13R)ꢀ6,13ꢀbis(3ꢀmethoxyphenyl)ꢀ
1,11ꢀdimethylꢀ4,8ꢀdioxoꢀ3,9ꢀdiphenylꢀ2,3,9,10ꢀtetraazadispiro
[4.1.47.25]tridecaꢀ1,10ꢀdienꢀ12ꢀyl)acrylate (3ib). M. p.
187.9–188.9 °C. IR νmax (neat)/cmꢀ1: 2962, 2873, 1715, 1622,
1546, 1498, 1403, 1355, 1288, 1210, 1134, 1017, 944, 758; 1H
NMR (400 MHz, CDCl3): δ 7.85 (d, J = 5.2 Hz, 2H), 7.56 (d,
J = 5.2 Hz, 2H), 7.43 (t, J = 5.2 Hz, 2H), 7.35 (t, J = 5.2 Hz,
2H), 7.24 (t, J = 4.8 Hz, 1H), 7.19 (t, J = 4.8 Hz, 1H), 7.15 (t,
J = 5.2 Hz, 1H), 7.09 (t, J = 5.2 Hz, 1H), 6.81 (d, J = 5.2 Hz,
1H), 6.76 (s, 1H), 6.75–6.71 (m, 2H), 6.39 (d, J = 5.2 Hz, 1H),
6.35 (s, 1H), 6.30 (s, 1H), 5.73 (s, 1H), 5.53 (d, J = 8.8 Hz,
1H), 4.66 (s, 1H), 4.22 (d, J = 8.8 Hz, 1H), 3.69 (s, 3H), 3.65
(s, 3H), 3.52 (s, 3H), 2.38 (s, 3H), 2.20 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 175.5, 172.5, 166.5, 163.7, 160.0, 159.7,
137.8, 137.4, 135.9, 133.8, 130.1, 129.5, 128.8, 128.7, 125.6,
125.4, 120.4, 119.9, 119.3, 118.7, 114.2, 113.9, 113.8, 111.6,
66.5, 66.2, 55.3, 55.2, 54.9, 53.6, 51.9, 44.7, 16.5, 13.5.
H]+, 713.2354, found 713.2358.
Methyl
2ꢀ((5S,6R,7S,12S,13R)ꢀ1,11ꢀdimethylꢀ6,13ꢀbis(3ꢀ
nitrophenyl)ꢀ4,8ꢀdioxoꢀ3,9ꢀdiphenylꢀ2,3,9,10ꢀtetraazadispiro
[4. 1.47.25]tridecaꢀ1,10ꢀdienꢀ12ꢀyl)acrylate (3gb). M. p.
181.5–182.5 °C. IR νmax (neat)/cmꢀ1: 2973, 2895, 1722, 1714,
1697, 1568, 1492, 1377, 1320, 1232, 1149, 957, 733; 1H NMR
(400 MHz, CDCl3): δ 8.13–8.09 (m, 3H), 7.83 (d, J = 4.8 Hz,
2H), 7.77 (s, 1H), 7.61 (d, J = 4.8 Hz, 1H), 7.52 (d, J = 5.6 Hz,
2H), 7.48–7.43 (m, 4H), 7.37 (t, J = 5.2 Hz, 2H), 7.28 (t, J =
5.2 Hz, 1H), 7.23 (t, J = 5.2 Hz, 1H), 7.12 (d, J = 5.2 Hz, 1H),
6.34 (s, 1H), 5.76 (s, 1H), 5.63 (d, J = 8.8 Hz, 1H), 4.77 (s,
1H), 4.42 (d, J = 8.8 Hz, 1H), 3.68 (s, 3H), 2.45 (s, 3H), 2.17
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 174.8, 171.5,
166.2, 162.2, 158.5, 148.7, 148.4, 137.4, 136.3, 134.3, 133.6,
132.6, 130.4, 130.1, 129.9, 129.0, 129.0, 126.4, 126.0, 123.7,
123.3, 123.1, 121.6, 120.0, 119.6, 66.3, 65.8, 54.4, 52.9, 52.2,
+
+
44.6, 16.4, 13.5. HRMS (ESI, m/z): calcd for C39H33N6O8 , [M
HRMS (ESI, m/z): calcd for C41H39N4O6 , [M + H]+,
683.2864, found 683.2862.
+ H]+, 713.2354, found 713.2357.
Methyl 2ꢀ((5S,7S,12R)ꢀ6,13ꢀbis(2ꢀmethoxyphenyl)ꢀ1,11ꢀ
dimethylꢀ4,8ꢀdioxoꢀ3,9ꢀdiphenylꢀ2,3,9,10ꢀtetraazadispiro[4.1.
47.25]tridecaꢀ1,10ꢀdienꢀ12ꢀyl)acrylate (3ha). The reaction
was carried out on a 0.2 mmol scale following the General
Procedure. The annulation product 3ha was purified through
column chromatography (hexanes/EtOAc: from 6:1 to 4:1) as
white solid (total 3h: 132 mg, dr = 4:1, 94% yield). M. p.
193.2–194.2 °C. IR νmax (neat)/cmꢀ1: 3081, 3033, 2975, 2932,
2847, 1726, 1219, 1696, 1634, 1593, 1489, 1377, 1292, 1256,
Methyl 2ꢀ((5S,6S,7S,12S,13R)ꢀ6,13ꢀbis(4ꢀmethoxyphenyl)ꢀ
1,11ꢀdimethylꢀ4,8ꢀdioxoꢀ3,9ꢀdiphenylꢀ2,3,9,10ꢀtetraazadispiro
[4.1.47.25]tridecaꢀ1,10ꢀdienꢀ12ꢀyl)acrylate (3ja). The reaction
was carried out on a 0.2 mmol scale following the General
Procedure. The annulation product 3ja and 3jb were purified
through column chromatography (hexanes/EtOAc: from 6:1 to
4:1) as white solid (total 3j: 120 mg, dr = 3.3:1, 88% yield).
M. p. 185.4–186.5 °C. IR νmax (neat)/cmꢀ1: 3175, 3008, 2920,
2887, 1712, 1609, 1593, 1534, 1498, 1375, 1290, 1231, 940,
1
1
1121, 1025, 775; H NMR (400 MHz, CDCl3): δ 7.85 (d, J =
914, 852; H NMR (400 MHz, CDCl3): δ 7.84 (d, J = 5.2 Hz,
4.8 Hz, 2H), 7.51–7.46 (m, 3H), 7.32 (d, J = 4.4 Hz, 1H), 7.27
2H), 7.47 (t, J = 5.2 Hz, 4H), 7.31–7.28 (m, 3H), 7.13 (t, J =
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