3016
W. Zhang, G. Pugh / Tetrahedron 59 (2003) 3009–3018
NMR (75 MHz, CDCl3) d 32.3, 63.9, 114.9, 121. 4, 122.9,
123.3, 123.8, 126.5, 127.2, 131.0, 1327, 134.5, 139.1, 144.5,
166.9; LRMS (APþ) m/z (rel. intensity) 222 (MþþH, 100);
HRMS calcd for C15H11NO 211.0841, found 211.0843.
348 (MþþH, 100); HRMS calcd for C23H25NO2 347.1885,
found 347.1889.
3.3.14. Compound 38. 20% Yield as a semisolid; IR nmax
(neat) 2952, 1658, 1608, 158, 1320, 1234, 750, 725 cm21
;
3.3.9. Compound 24. 71% Yield as a yellow solid mp 164–
1658C; IR nmax (neat) 1699, 1487, 1370, 1279, 1226, 1138,
1065, 1016, 749 cm21; 1H NMR (300 MHz, CDCl3) d 3.02
(dd, J¼15.2, 10.4 Hz, 1H), 3.41 (dd, J¼15.2, 8.7 Hz, 1H),
5.05 (s, 2H), 5.60 (dd, J¼10.4, 8.7 Hz, 1H), 6.90 (m, 2H),
7.38–7.59 (m, 9H), 7.85 (d, J¼7.4 Hz, 1H); 13C NMR
(75 MHz, CDCl3) d 32.6, 64.3, 69.1, 111.6, 112.0, 115.3,
121.2, 123.2, 125.9, 126.5, 127.1, 130.8, 132.8, 133.0,
135.4, 136.1, 144.4, 154.7, 166.8; LRMS (APþ) m/z (rel.
intensity) 328 (MþþH, 88), 153 (100); HRMS calcd for
C22H17NO2 327.1259, found 327.1259.
1H NMR (300 MHz, CDCl3) d 2.10–2.80 (6H), 6.20 (s, 1H),
7.15 (d, J¼8.3 Hz, 1H), 7.37 (m, 1H), 7.47 (m, 1H), 7.64 (t,
J¼7.7 Hz, 1H), 7.82 (t, J¼7.7 Hz, 1H), 8.32 (d, J¼7.8 Hz,
2H), 8.52 (d, J¼7.7 Hz, 1H); 13C NMR (75 MHz, CDCl3) d
21.8, 28.7, 37.2, 118.0, 119.1, 121.9, 123.3, 123.6, 125.3,
128.3, 128.6, 129.7, 131.0, 133.2, 133.8, 136.1, 158.9,
160.0, 199.1; LRMS (APþ) m/z(rel. intensity) 290 (MþþH,
100); HRMS calcd for C19H15NO2 289.1103, found
289.1108.
3.3.15. Compound 39. 51% Yield; IR nmax (neat) 3278,
3232, 1693, 1628, 1511, 1237, 1181, 1132, 745, 700 cm21
;
3.3.10. Compound 26. 59% Yield; IR nmax (neat) 1705,
1640, 1494, 1453, 1435, 1398, 1328, 1286, 1244, 1142,
1H NMR (300 MHz, CDCl3) d 1.70–2.05 (m, 4H), 2.28 (t,
J¼6.3 Hz, 2H), 6.40 (s, 1H), 6.58 (br s, 1H), 7.40–7.60
(9H),7.83 (d, J¼7.7 Hz, 1H); 13C NMR (75 MHz, CDCl3) d
21.3, 28.0, 36.5, 111.6, 127.8, 128.2, 128.7 (2C), 128.9
(2C), 129.4, 130.3, 131.2, 134.3, 139.5, 139.8, 154.9, 168.0,
199.9; LRMS (APþ) m/z (rel. intensity) 292 (MþþH, 100),
HRMS calcd for C19H17NO2 291.1259, found 291.1259.
1
1026, 777, 739 cm21; H NMR (300 MHz, CDCl3) d 2.62
(dd, J¼15.0, 3.3 Hz, 1H), 3.42 (dd, J¼15.0, 3.1 Hz, 1H),
3.89 (s, 3H), 4.80 (dd, J¼13.3, 3.1 Hz, 1H), 7.20–7.55
(7H); 13C NMR (75 MHz, CDCl3) d 32.9, 40.8, 51.6,
54.2, 105.6, 116.0, 119.2, 121.8, 125.3, 126.0, 126.5, 127.6,
128.3, 130.6, 136.3, 158.9, 165.1; LRMS (APþ) m/z (rel.
intensity) 291 (MþþH, 100); HRMS calcd for C18H14N2O2
290.1055, found 290.1065.
3.3.16. Compound 40. 29% Yield; IR nmax (neat) 1698,
1
1493, 1467, 1382, 763, 698 cm21; H NMR (300 MHz,
CDCl3) d 1.92–2.40 (m, 6H), 2.58 (m 2H), 2.88 (d, J¼
13.7 Hz, 1H), 7.23–736 (3H), 7.50–7.60 (5H), 7.98 (d,
J¼7.5 Hz, 1H); 13C NMR (75 MHz, CDCl3) d 18.7, 32.7,
38.3, 48.6, 66.7, 121.1, 123.1, 127.3, 127.5, 128.3 (2C),
129.1, 129.4 (2C), 130.5, 133.3, 146.8, 165.9, 206.6; LRMS
(APþ) m/z (rel. intensity) 292 (MþþH, 100); HRMS calcd
for C19H17NO2 291.1259, found 291.1266.
3.3.11. Compound 28. 77% Yield; IR nmax (neat) 1760,
1717, 1354, 1260, 764 cm21; 1H NMR (300 MHz, CDCl3) d
0.81 (t, J¼7.3 Hz, 3H), 1.03 (t, J¼7.3 Hz, 3H), 1.80–2.03
(m, 2H), 2.08–2.33 (m, 2H), 2.52 (dd, J¼16.1, 13.4 Hz,
1H), 2.75 (dd, J¼16.1, 2.8 Hz, 1H), 5.55 (dd, J¼13.4,
2.8 Hz, 1H), 7.72 (m, 2H), 7.90–8.10 (m, 4H); 13C NMR
(75 MHz, CDCl3) d 8.3, 8.4, 28.4, 29.3, 45.2, 52.1, 62.7,
119.0, 121.9, 125.7, 126.4, 126.6, 127.6, 128.3, 129.5,
135.0, 140.6, 164.6, 168.9, 205.6; LRMS (APþ) m/z (rel.
intensity) 322 (MþþH, 100); HRMS calcd for C20H19NO3
321.1365, found 321.1378.
3.3.17. Compound 44a. 47% Yield; analytical data is
consistent with those reported in literature.17c
3.3.18. Compound 44b. 49% Yield; IR nmax (neat) 1641,
1
1607, 1515, 1484, 1393, 1254, 1160, 840, 764 cm21; H
3.3.12. Compound 30a. 35% Yield; IR nmax (neat) 2958,
1
NMR (300 MHz, CDCl3) d 3.32 (dd, J¼12.5, 3.7 Hz, 1H),
3.95 (dd, J¼12.5, 10.2 Hz, 1H), 5.99 (dd, J¼10.2, 3.7 Hz,
1H), 6.99 (t, J¼8.9 Hz, 2H), 7.11 (d, J¼8.1 Hz, 1H), 7.13
(m, 2H), 7.63 (m, 2H), 7.78 (t, J¼8.0 Hz, 1H), 8.16 (d, J¼
8.0 Hz, 1H), 8.48 (d, J¼8.0 Hz, 1H); 13C NMR (75 MHz,
CDCl3) d 39.3, 63.4, 107.4, 114.2, 116.9, 117.9, 123.4,
128.7, 128.8, 129.8, 131.8, 133.4, 134.3, 137.2, 138.4,
160.1, 162.2, 164.6; LRMS (APþ) m/z (rel. intensity) 334
(MþþH, 100); HRMS calcd for C21H13F2NO 333.0965,
found 333.0965.
1694, 1470, 1418, 1387, 1277, 1943, 764, 695 cm21; H
NMR (300 MHz, CDCl3) d 1.23 (s, 3H), 1.27 (s, 3H), 1.97
(d, J¼15.6 Hz, 1H), 2.08 (d, J¼15.6 Hz, 1H), 2.43 (d, J¼
15.6 Hz, 1H), 2.50 (d, J¼15.6 Hz, 1H), 2.64 (d, J¼16.5 Hz,
1H), 2.76 (d, J¼16.5 Hz, 1H), 3.04 (s, 3H), 7.38–7.60 (3H),
7.80 (d, J¼7.5 Hz, 1H); 13C NMR (75 MHz, CDCl3) d 23.0,
28.8, 30.7, 30.8, 42.9, 44.9, 50.6, 63.7, 120.0, 122.2, 126.8,
128.7, 130.6, 150.1, 165.3, 207.3; LRMS (APþ) m/z (rel.
intensity) 258 (MþþH, 100); HRMS calcd for C16H19NO2
257.1416, found 257.1420.
3.3.19. Compound 45. 53% Yield; IR nmax (neat) 1806,
1697, 1313, 1141, 756 cm21; 1H NMR (300 MHz, CDCl3) d
7.28 (m, 2H), 7.51 (t, J¼6.2 Hz, 2H), 7.65 (t, J¼6.2 Hz,
1H), 7.80–7.90 (2H); 13C NMR (75 MHz, CDCl3) d 108.5,
113.7, 123.5, 123.9, 127.0, 128.0, 130.7, 132.0, 141.3,
149.5, 166.3; LRMS (APþ) m/z (rel. intensity) 238 (MþþH,
80), 196 (100); HRMS calcd for C14H7NO3 237.0426, found
237.0428.
3.3.13. Compound 30b. 41% Yield; IR nmax (neat) 2960,
1690, 1469, 1399, 1275, 751, 700 cm21
;
1H NMR
(300 MHz, CDCl3) d 1.15 (s, 3H), 1.21 (s, 3H), 1.83 (d,
J¼15.6 Hz, 1H), 1.94 (d, J¼15.6 Hz, 1H), 2.40 (d, J¼
15.6 Hz, 1H), 2.45 (d, J¼15.6 Hz, 1H), 2.52 (d, J¼16.5 Hz,
1H), 2.62 (d, J¼16.5 Hz, 1H), 3.00 (m, 1H), 3.23 (m, 1H),
3.39 (m, 1H), 3.78 (m, 1H), 7.20–7.37 (6H), 7.40–7.55 (m
2H), 7.83 (d, J¼8.6 Hz, 1H); 13C NMR (75 MHz, CDCl3) d
26.1, 28.4, 30.1, 30.6, 31.3, 33.3, 41.4, 43.5, 45.6, 50.7,
64.8, 120.3, 122.0, 125.1, 126.8, 127.1, 127.4, 129.0, 130.5,
137.5, 150.0, 165.9, 207.3; LRMS (APþ) m/z (rel. intensity)
3.3.20. Compound 48. 35% Yield; IR nmax (neat) 1694,
1
1335, 761 cm21; H NMR (300 MHz, CDCl3) d 1.75 (m,
1H), 1.85 (m, 1H), 2.12 (m, 1H), 2.56 (m, 1H), 3.18 (m, 1H),