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( )-3: 62% from ( )-exo-41b, a white solid, mp >300 °C (MeOH);
m/z 448 [M]+; HRMS (FAB) m/z Calcd for C27H21N4O3 [M+H]+
449.1614; found: 449.1570.
1H NMR (DMSO-d6, 400 MHz) d: 1.16 (s, 3H), 2.40 (s, 2H), 5.55 (s,
1H), 6.91 (d, J = 7.6 Hz, 1H), 7.10 (t, J = 7.6 Hz, 1H), 7.17 (d,
J = 6.8 Hz, 1H), 7.31 (t, J = 7.2 Hz, 1H), 7.72 (d, J = 8.8 Hz, 1H), 7.89
(d, J = 8.8 Hz, 1H), 8.15 (s, 1H), 9.60 (s, 1H), 10.66 (s, 1H); 13C
NMR (DMSO-d6, 100 MHz) d: 13.3, 35.9, 52.2, 54.7, 61.8, 109.9,
121.4, 122.4, 123.8, 125.3, 129.2, 129.8, 129.9, 131.5, 134.8,
( )-9: 27% (2 steps) from 34f and 35a, a white solid, mp >300 °C
(MeOH); 1H NMR (DMSO-d6, 400 MHz) d: 1.14 (d, J = 6.8 Hz, 3H),
1.22 (d, J = 6.4 Hz, 3H), 2.01 (qui, J = 6.8 Hz, 1H), 2.24 (d,
J = 14.0 Hz, 1H), 2.43 (dd, J = 4.0, 14.0 Hz, 1H), 5.56 (br s, 1H),
6.92 (d, J = 7.6 Hz, 1H), 7.10 (t, J = 7.6 Hz, 1H), 7.30 (d, J = 7.6 Hz,
1H), 7.33 (d, J = 6.8 Hz, 1H), 7.61 (t, J = 7.6 Hz, 1H), 7.69 (d,
J = 8.0 Hz, 1H), 7.88 (t, J = 7.6 Hz, 1H), 8.21 (d, J = 8.0 Hz, 1H), 9.52
(br s, 1H), 10.65 (br s, 1H); 13C NMR (DMSO-d6, 100 MHz) d:
16.4, 18.3, 30.7, 48.5, 51.2, 54.1, 66.9, 110.1, 119.9, 122.2, 123.9,
126.1, 127.1, 127.8, 129.0, 130.2, 134.5, 141.7, 146.5, 150.9,
142.6, 145.6, 153.5, 157.4, 169.4, 176.6; IR (KBr) m: 3217, 1726,
1619, 1470 cmꢀ1; LRMS (EI) m/z 406 [M]+; HRMS (FAB) m/z Calcd
for C21H1635ClN4O3 [M+H]+ 407.0911; found: 407.0920.
( )-4: 90% from ( )-exo-41c, a white solid, mp >300 °C (MeOH);
1H NMR (DMSO-d6, 400 MHz) d: 1.18 (s, 3H), 2.41 (s, 2H), 5.57 (d,
J = 2.0 Hz, 1H), 6.93 (d, J = 8.0 Hz, 1H), 7.12 (t, J = 7.6 Hz, 1H), 7.19
(d, J = 6.8 Hz, 1H), 7.33 (t, J = 7.6 Hz, 1H), 7.76–7.80 (m, 2H), 7.90
(dd, J = 2.4, 8.8 Hz, 1H), 9.58 (s, 1H), 10.65 (s, 1H); 13C NMR
(DMSO-d6, 100 MHz) d: 13.3, 35.8, 52.1, 54.6, 61.7, 109.8, 111.0
(d, J = 23 Hz), 121.3 (d, J = 8.0 Hz), 122.3, 123.0, 123.7, 129.1,
129.8, 130.4 (d, J = 9 Hz), 142.5, 143.6, 152.4, 157.6 (d, J = 3 Hz),
158.5, 169.7, 177.8; IR (KBr)
m: 3183, 1709, 1617, 1471, 1370,
1331 cmꢀ1; LRMS (EI) m/z 400 [M]+; HRMS (FAB) m/z Calcd for
C23H21N4O3 [M+H]+ 401.1614; found: 401.1637.
( )-10: quant. from ( )-exo-41i, a colorless solid, mp >300 °C
(MeOH); 1H NMR (DMSO-d6, 400 MHz) d: 0.81 (d, J = 6.4 Hz, 3H),
0.88 (d, J = 6.4 Hz, 3H), 1.02 (dd, J = 5.2, 14.0 Hz, 1H), 2.07–2.18
(m, 2H), 2.34 (s, 2H), 5.59 (s, 1H), 6.91 (d, J = 7.6 Hz, 1H), 7.10 (t,
J = 7.6 Hz, 1H), 7.23 (d, J = 7.6 Hz, 1H), 7.32 (t, J = 7.6 Hz, 1H), 7.61
(t, J = 7.6 Hz, 1H), 7.69 (d, J = 7.6 Hz, 1H), 7.88 (t, J = 7.6 Hz, 1H),
8.22 (d, J = 7.6 Hz, 1H), 9.17 (s, 1H), 10.61 (s, 1H); 13C NMR
(DMSO-d6, 100 MHz) d: 23.1, 23.9 (2C), 33.6, 37.0, 51.5, 55.9,
65.3, 109.6, 119.9, 122.3, 124.6, 126.2, 127.1, 127.7, 129.1, 129.9,
160.2 (d, J = 244 Hz), 169.4, 176.6; IR (KBr) m: 3252, 1705, 1629,
1486, 1334 cmꢀ1; LRMS (EI) m/z 390 [M]+; HRMS (FAB) m/z Calcd
for C21H16FN4O3 [M+H]+ 391.1206; found: 391.1202.
( )-5: 60% from ( )-exo-41d, a white solid, mp >300 °C (MeOH);
1H NMR (DMSO-d6, 400 MHz) d: 1.15 (s, 3H), 2.40 (d, J = 2.4 Hz,
2H), 5.55 (d, J = 2.4 Hz, 1H), 6.91 (d, J = 7.6 Hz, 1H), 7.10 (ddd,
J = 1.2, 7.5, 7.6 Hz, 1H), 7.17 (d, J = 6.8 Hz, 1H), 7.31 (ddd, J = 1.2,
7.6, 7.8 Hz, 1H), 7.63 (dd, J = 2.0, 8.4 Hz, 1H), 7.77 (d, J = 2.0 Hz,
1H), 8.20 (d, J = 8.8 Hz, 1H), 9.59 (d, J = 1.6 Hz, 1H), 10.67 (s, 1H);
13C NMR (DMSO-d6, 100 MHz) d: 13.3, 35.8, 52.0, 54.7, 61.8,
109.9, 118.9, 121.4, 122.4, 123.8, 126.9, 127.5, 128.4, 129.2,
134.6, 142.5, 146.5, 151.4, 158.3, 170.0, 176.4; IR (KBr) m: 3318,
1700, 1665, 1619, 1467 cmꢀ1; LRMS (EI) m/z 414 [M]+; HRMS
(FAB) m/z Calcd for C24H23N4O3 [M+H]+ 415.1770; found:
415.1751.
( )-16: 10% (2 steps) from from 34a and 35c, a colorless solid,
mp 275-277 °C (MeOH);1H NMR (CDCl3, 400 MHz) d: 1.72 (s, 3H),
2.94–3.02 (m, 2H), 3.60 (s, 3H), 5.84 (d, J = 2.4 Hz, 1H), 6.45 (s,
1H), 7.19 (d, J = 6.8 Hz, 2H), 7.30–7.39 (m, 3H), 7.52 (ddd, J = 1.2,
7.4, 7.4 Hz, 1H), 7.78 (ddd, J = 1.2, 7.4, 7.6 Hz, 1H), 7.82 (t,
J = 7.6 Hz, 1H), 8.30 (d, J = 7.6 Hz, 1H); 13C NMR (CDCl3, 100 MHz)
d: 16.3, 37.8, 52.1, 52.7, 58.5, 62.6, 120.3, 126.9, 127.4, 128.1
(2C), 128.2, 128.3, 128.5 (2C), 134.6, 137.0, 147.4, 153.2, 159.1,
129.8, 139.3, 142.6, 147.9, 154.4, 169.4, 176.6; IR (KBr) m: 3199,
1712, 1662, 1599 cmꢀ1; LRMS (EI) m/z 406 [M]+; HRMS (FAB) m/z
Calcd for C21H1537ClN4O3 [M+H]+ 409.0890; found: 409.0902.
( )-6: 72% from ( )-exo-41e, a white solid, 1H NMR (DMSO-d6,
400 MHz) d: 1.21 (s, 3H), 2.41 (dd, J = 3.6, 14.4 Hz, 1H), 2.50 (d,
J = 14.4 Hz, 1H), 5.58 (s, 1H), 6.95 (d, J = 8.0 Hz, 1H), 7.17 (d,
J = 2.0 Hz, 1H), 7.39 (dd, J = 2.0, 8.0 Hz, 1H), 7.61 (t, J = 8.0 Hz,
1H), 7.70 (d, J = 8.0 Hz, 1H), 7.88 (ddd, J = 1.2, 7.8, 8.4 Hz, 1H),
8.21 (dd, J = 1.2, 8.0 Hz, 1H), 9.69 (d, J = 1.2 Hz, 1H), 10.81 (s, 1H);
13C NMR (DMSO-d6, 100 MHz) d: 13.3, 35.6, 51.7, 55.0, 61.7,
111.2, 119.9, 123.9, 126.0, 126.3, 127.2, 127.6, 129.0, 131.7,
169.7, 172.7; IR (KBr)
m: 1739, 1626, 1458, 1389, 1331,
1242 cmꢀ1; LRMS (EI) m/z 389 [M]+; HRMS (FAB) m/z Calcd for
C22H20N3O4 [M+H]+ 390.1454; found: 390.1436.
( )-17: 59% from ( )-41j-MP, a colorless amorphus solid, 1H
NMR (CDCl3, 400 MHz) d: 1.34 (t, J = 7.2 Hz, 3H), 1.96 (s, 3H),
2.12–2.19 (m, 1H), 2.35 (td, J = 2.8, 13.6 Hz, 1H), 2.84 (dd, J = 4.0,
13.6 Hz, 1H), 3.77 (s, 3H), 4.12–4.30 (m, 2H), 5.89 (s, 1H), 7.47–
7.50 (m, 1H), 7.75–7.78 (m, 2H), 8.27 (d, J = 7.6 Hz, 1H); 13C NMR
(CDCl3, 100 MHz) d: 13.9, 20.8, 30.0, 45.0, 47.5, 52.2, 63.4, 63.6,
120.1, 126.7, 126.9, 127.8, 134.4, 147.5, 155.7, 159.0, 170.6,
134.6, 141.5, 146.7, 152.5, 158.2, 169.5, 176.2; IR (KBr) m: 1719,
1686, 1624, 1475 cmꢀ1; LRMS (FAB) m/z 407 [M+H]+; HRMS
(FAB) m/z Calcd for C21H1635ClN4O3 [M+H]+ 407.0911; found:
407.0887.
( )-7: 90% from ( )-exo-41f, a white solid, mp >300 °C (MeOH);
1H NMR (DMSO-d6, 400 MHz) d: 1.20 (s, 3H), 2.41 (dd, J = 3.2,
14.8 Hz, 1H), 2.49 (d, J = 14.8 Hz, 1H), 5.57 (s, 1H), 6.95 (d,
J = 8.4 Hz, 1H), 7.17 (s, 1H), 7.40 (ddd, J = 0.8, 2.4, 8.4 Hz, 1H),
7.73 (dd, J = 0.8, 8.4 Hz, 1H), 7.90 (ddd, J = 1.6, 2.4, 8.4 Hz, 1H),
8.15 (dd, J = 1.2, 2.4 Hz, 1H), 9.71 (s, 1H), 10.82 (s, 1H); 13C NMR
(DMSO-d6, 100 MHz) d: 13.2, 35.5, 51.9, 55.0, 61.6, 111.3, 121.3,
123.9, 125.3, 126.1, 129.0, 129.8, 131.5, 131.6, 134.8, 141.5,
171.9; IR (KBr) m
: 1674, 1641, 1473, 1431, 1373 cmꢀ1; LRMS (EI)
m/z 341 [M]+; HRMS (FAB) m/z Calcd for C18H20N3O4 [M+H]+
342.1454; found: 342.1451.
( )-18: 82% from ( )-exo-41l-LP, a colorless solid, mp >300 °C
(MeOH); 1H NMR (DMSO-d6, 400 MHz) d: 1.94 (s, 3H), 3.42 (d,
J = 8.4 Hz, 1H), 4.02 (dd, J = 4.0, 8.0 Hz, 1H), 5.62 (dd, J = 2.0,
4.0 Hz, 1H), 7.21 (d, J = 7.6 Hz, 2H), 7.48 (t, J = 7.6 Hz, 1H), 7.56 (t,
J = 7.6 Hz, 2H), 7.63 (t, J = 7.6 Hz, 1H), 7.78 (d, J = 7.6 Hz, 1H), 7.90
(ddd, J = 1.2, 7.2, 7.6 Hz, 1H), 8.21 (d, J = 8.0 Hz, 1H), 9.64 (d,
J = 1.2 Hz, 1H); 13C NMR (DMSO-d6, 150 MHz) d: 16.4, 44.6, 48.3,
53.1, 59.1, 121.0, 127.0, 127.4 (2C), 128.2, 128.3, 129.5, 129.7
(2C), 132.4, 135.4, 147.3, 154.1, 158.9, 166.8, 173.3, 173.8; IR
145.4, 153.0, 157.3, 169.3, 176.2; IR (KBr) m: 1672, 1626, 1464,
1319 cmꢀ1; LRMS (EI) m/z 440 [M]+; HRMS (FAB) m/z Calcd for
C21H1535Cl2N4O3 [M+H]+ 441.0521; found: 441.0509.
( )-8: 17% (2 steps) from from 34e and 35a, a colorless solid, mp
>300 °C (MeOH); 1H NMR (DMSO-d6, 400 MHz) d: 2.37–2.47 (m,
2H), 2.71 (d, J = 14.8 Hz, 1H), 3.45 (d, J = 14.8 Hz, 1H), 5.60 (br s,
1H), 6.87 (d, J = 7.6 Hz, 1H), 7.12–7.15 (m, 4H), 7.27 (d, J = 7.6 Hz,
1H), 7.28 (d, J = 7.6 Hz, 1H), 7.33 (d, J = 7.6 Hz, 1H), 7.35 (t,
J = 7.6 Hz, 1H), 7.62 (t, J = 7.6 Hz, 1H), 7.71 (d, J = 8.0 Hz, 1H), 7.89
(t, J = 8.0 Hz, 1H), 8.22 (d, J = 8.0 Hz, 1H), 9.11 (s, 1H), 10.51 (s,
1H); 13C NMR (DMSO-d6, 100 MHz) d: 32.4, 37.5, 51.8, 55.3, 65.2,
110.0, 120.0, 122.4, 124.3, 126.4, 126.6, 127.4, 127.5 (2C), 127.7,
129.3, 129.7, 131.3 (2C), 134.0, 134.8, 142.8, 146.5, 151.5, 158.4,
(KBr) m
: 1717, 1623, 1468, 1389, 1182 cmꢀ1; LRMS (FAB) m/z 401
[M+H]+; HRMS (FAB) m/z Calcd for C22H17N4O4 [M+H]+ 401.1250;
found: 401.1221.
( )-20: 60% from ( )-endo-41b, a white solid, mp >300 °C
(MeOH); 1H NMR (DMSO-d6, 400 MHz) d: 1.22, (s, 3H), 2.31 (dd,
J = 3.6, 14. Hz, 1H), 2.55 (d, J = 14 Hz, 1H), 5.55 (s, 1H), 5.92 (d,
J = 7.6 Hz, 1H), 6.68 (t, J = 7.6 Hz, 1H), 6.86 (t, J = 7.6 Hz, 1H), 7.16
(t, J = 7.6 Hz, 1H), 7.72 (t, J = 8.8 Hz, 1H), 7.90 (dd, J = 2.8, 8.8 Hz,
169.7, 170.4; IR (KBr) m
: 3264, 1701, 1628, 1473 cmꢀ1; LRMS (EI)