Y. Yamamoto et al. / Tetrahedron 61 (2005) 11501–11510
11507
124.89, 125.58, 127.22, 128.13, 129.61, 129.83, 136.12,
136.38, 138.07, 138.55, 140.47, 141.85; MS (EI): m/z (%):
310 (41) [MC], 292 (100) [MCKH2O], 267 (11) [MCK
COCH3], 249 (43) [MCKCOCH3–H2O]; EA calcd (%) for
C22H30O (310.47): C, 85.11; H, 9.74; found: C, 85.24; H,
9.84.
7.8 Hz, 1H), 7.18 (s, 1H), 7.21 (d, JZ16.5 Hz, 1H), 7.29
(dd, JZ15.5, 7.8 Hz, 1H); 13C NMR (75 MHz, CDCl3): d
14.08, 14.10, 22.57, 22.76, 33.26, 33.51, 33.71, 35.48,
55.26, 63.93, 111.76, 112.97, 118.92, 125.69, 125.97,
128.75, 129.52, 133.19, 134.06, 138.37, 138.75, 141.34,
141.81, 159.68; MS (EI): m/z (%): 352 (100) [MC], 334 (27)
[MCKH2O], 321 (13) [MCKOCH3], 291 (12) [MCK
H2O–COCH3]; EA calcd (%) for C24H32O2 (352.51): C,
81.77; H, 9.15; found: C, 81.97; H, 9.17.
4.1.6. Compound 9aaaf. Yield 67%; oil (Rf 0.25, hexane/
1
AcOEt 3:1); IR (neat) 3389 cmK1; H NMR (300 MHz,
CDCl3): d 0.76 (t, JZ7.5 Hz, 3H), 0.98 (t, JZ7.5 Hz, 3H),
1.17 (sext, JZ7.5 Hz, 2H), 1.32–1.50 (m, 4H), 1.64–1.74
(m, 2H), 2.03 (br s, 1H), 2.20–2.40 (m, 2H), 2.67 (t, JZ
7.5 Hz, 2H), 3.74 (s, 3H), 4.26 (d, JZ12.0 Hz, 1H), 4.31 (d,
JZ12.0 Hz, 1H), 6.99–7.10 (m, 4H), 7.20 (d, JZ1.8 Hz,
1H), 7.36 (ddd, JZ8.4, 7.2, 2.1 Hz, 1H); 13C NMR
(75 MHz, CDCl3): d 13.90, 14.11, 22.53, 22.70, 33.14,
33.24, 33.58, 35.57, 55.35, 64.37, 110.80, 120.64, 125.77,
127.85, 128.50, 128.66, 131.28, 133.72, 138.92, 141.27,
142.07, 156.50; MS (EI): m/z (%): 326 (100) [MC], 308 (36)
[MCKH2O], 265 (12) [MCKCOCH3–H2O]; EA calcd (%)
for C22H30O2 (326.47): C, 80.94; H, 9.26; found: C, 80.92;
H, 9.36.
4.1.10. Compound 9aaba. Yield 69%; oil (Rf 0.3, hexane/
1
AcOEt 2:1); IR (neat) 3384, 1681, 1604 cmK1; H NMR
(300 MHz, CDCl3): d 0.74 (t, JZ7.5 Hz, 3H), 1.14 (sext,
JZ7.2 Hz, 2H), 1.32–1.42 (m, 2H), 2.02 (br s, 1H), 2.30 (t,
JZ7.5 Hz, 2H), 2.64 (s, 3H), 3.43 (s, 3H), 4.28 (s, 2H), 4.48
(s, 2H), 7.21 (d, JZ1.8 Hz, 1H), 7.27 (d, JZ8.1 Hz, 2H),
7.35 (d, JZ1.8 Hz, 1H), 8.00 (d, JZ8.1 Hz, 2H); 13C NMR
(75 MHz, CDCl3): d 13.82, 22.51, 26.66, 33.00, 33.46,
58.32, 63.20, 74.53, 124.30, 127.48, 128.13, 129.71, 135.73,
137.76, 138.33, 138.46, 140.80, 144.33, 197.66; MS (EI):
m/z (%): 326 (100) [MC], 311 (20) [MCKCH3], 295 (88)
[MCKOCH3], 281 (14) [MCKCH2OCH3], 265 (69)
[MCKOCH3–CH2O]; EA calcd (%) for C21H26O3
(326.43): C, 77.27; H, 8.03; found: C, 77.11; H, 8.19.
4.1.7. Compound 9aaag. Yield 53%; oil (Rf 0.15, hexane/
1
AcOEt 2:1); IR (neat) 3362 cmK1; H NMR (300 MHz,
CDCl3): d 0.76 (t, JZ7.5 Hz, 3H), 0.95 (t, JZ7.5 Hz, 3H),
1.17 (sext, JZ7.5 Hz, 2H), 1.32–1.46 (m, 4H), 1.59–1.69
(m, 2H), 2.47 (t, JZ7.8 Hz, 2H), 2.63 (t, JZ7.8 Hz, 2H),
4.18 (s, 2H), 4.45 (br s, 1H), 7.08 (d, JZ1.8 Hz, 1H), 7.14
(d, JZ1.8 Hz, 1H), 7.30 (ddd, JZ7.5, 4.8, 1.2 Hz, 1H), 7.37
(dt, JZ7.5, 1.0 Hz, 1H), 7.77 (dt, JZ7.5, 1.8 Hz, 1H), 8.65
(ddd, JZ4.8, 1.8, 0.9 Hz, 1H); 13C NMR (75 MHz, CDCl3):
d 13.83, 14.07, 22.55 (2 C), 33.13, 33.56, 33.65, 35.47,
64.56, 121.92, 125.33, 127.41, 129.05, 136.06, 136.91,
139.78, 140.68, 143.26, 148.67, 158.53; MS (EI): m/z (%):
297 (100) [MC], 279 (49) [MCKH2O], 268 (21) [MCK
CH2CH3], 250 (96) [MCKH2O–CH2CH3]; EA calcd (%)
for C20H27NO (297.43): C, 80.76; H, 9.15; N, 4.71; found:
C, 80.39; H, 9.29; N, 4.40.
4.1.11. Compound 9aaca. Yield 76%; oil (Rf 0.3, hexane/
1
AcOEt 2:1); IR (neat) 3435, 1681, 1604 cmK1; H NMR
(300 MHz, CDCl3): d 0.75 (t, JZ7.5 Hz, 3H), 1.15 (sext,
JZ7.2 Hz, 2H), 1.31–1.41 (m, 2H), 1.56 (br s, 1H), 2.09–
2.19 (m, 2H), 2.29 (t, JZ7.8 Hz, 2H), 2.66 (s, 3H), 2.82 (t,
JZ7.8 Hz, 2H), 3.59 (t, JZ6.5 Hz, 2H), 4.31 (s, 2H), 7.08
(d, JZ1.6 Hz, 1H), 7.21 (d, JZ1.6 Hz, 1H), 7.30 (d, JZ
8.4 Hz, 2H), 8.02 (d, JZ8.4 Hz, 2H); 13C NMR (75 MHz,
CDCl3): d 13.85, 22.52, 26.68, 32.70, 33.02, 33.55, 35.99,
44.35, 63.33, 125.14, 128.14, 128.48, 129.84, 135.72,
136.91, 138.36, 140.38, 140.79, 144.45, 197.66; MS (EI):
m/z (%): 358 (100) [MC], 343 (24) [MCKCH3], 297 (58)
[MHCKCH2CHCl], 255 (64) [MHCKCH2CHCl–CH2-
CHCH3]; EA calcd (%) for C22H27ClO2 (358.90): C,
73.62; H, 7.58; found: C, 73.54; H, 7.68.
4.1.8. Compound 9aaah. Yield 69%; oil (Rf 0.35, hexane/
1
AcOEt 3:1); IR (neat) 3330 cmK1; H NMR (300 MHz,
4.1.12. Compound 9aada. Yield 73%; oil (Rf 0.3, hexane/
1
CDCl3): d 0.83 (t, JZ7.5 Hz, 3H), 0.97 (t, JZ7.5 Hz, 3H),
1.25 (sext, JZ7.5 Hz, 2H), 1.36–1.53 (m, 4H), 1.60–1.71
(m, 2H), 1.74 (br s, 1H), 2.43 (t, JZ7.8 Hz, 2H), 2.65 (t, JZ
7.8 Hz, 2H), 4.45 (s, 2H), 6.89 (dd, JZ3.3, 1.2 Hz, 1H),
7.07 (s, 1H), 7.10 (dd, JZ5.1, 3.3 Hz, 1H), 7.20 (s, 1H),
7.38 (dd, JZ5.1, 1.2 Hz, 1H); 13C NMR (75 MHz, CDCl3):
d 13.94, 14.07, 22.60, 22.69, 33.23, 33.63, 34.12, 35.59,
63.74, 125.22, 125.56, 126.84, 127.36, 128.30, 129.19,
139.21, 140.64, 143.27, 143.33; MS (EI): m/z (%): 302
(100) [MC], 284 (11) [MCKH2O], 269 (20) [MCKH2O–
CH3], 255 (42) [MCKH2O–CH2CH3], 241 (30) [MCK
H2O–CH2CH2CH3]; EA calcd (%) for C19H26OS (302.48):
C, 75.45; H, 8.66; found: C, 75.54; H, 8.47.
AcOEt 1:1); IR (neat) 3448, 1736, 1683, 1604 cmK1; H
NMR (300 MHz, CDCl3): d 0.75 (t, JZ7.5 Hz, 3H), 1.14
(sext, JZ7.5 Hz, 2H), 1.30–1.41 (m, 2H), 1.65 (br s, 1H),
2.01 (q, JZ7.5 Hz, 2H), 2.28 (t, JZ7.8 Hz, 2H), 2.38 (t, JZ
7.2 Hz, 2H), 2.65 (s, 3H), 2.69 (t, JZ7.5 Hz, 2H), 3.68 (s,
3H), 4.29 (s, 2H), 7.05 (d, JZ1.8 Hz, 1H), 7.20 (d, JZ
1.8 Hz, 1H), 7.30 (d, JZ8.1 Hz, 2H), 8.01 (d, JZ8.1 Hz,
2H); 13C NMR (75 MHz, CDCl3): d 13.86, 22.55, 26.48,
26.69, 33.05, 33.57 (2 C), 35.01, 51.58, 63.40, 125.20,
128.13, 128.44, 129.87, 135.70, 136.81, 138.27, 140.70,
141.25, 144.53, 173.76, 197.66; MS (EI): m/z (%): 382 (5)
[MC], 364 (81) [MCKH2O], 333 (10) [MCKH2O–OCH3],
321 (100) [MCKH2O–CH2CH2CH3], 291 (72) [MCK
H2O–CH2CO2CH3]; EA calcd (%) for C24H30O4 (382.49):
C, 75.36; H, 7.91; found: C, 75.28; H, 7.99.
4.1.9. Compound 9aaai. Yield 51%; oil (Rf 0.35, hexane/
1
AcOEt 3:1); IR (neat) 3363 cmK1; H NMR (300 MHz,
CDCl3): d 0.93 (t, JZ7.5 Hz, 3H), 0.97 (t, JZ7.5 Hz, 3H),
1.39 (sept, JZ7.5 Hz, 4H), 1.54–1.69 (m, 4H), 1.81 (br s,
1H), 2.62 (t, JZ7.5 Hz, 2H), 2.69 (t, JZ7.5 Hz, 2H), 3.89
(s, 3H), 4.74 (s, 2H), 6.66 (d, JZ16.5 Hz, 1H), 6.86 (ddd,
JZ8.1, 2.7, 0.6 Hz, 1H), 7.02–7.06 (m, 2H), 7.12 (d, JZ
4.1.13. Compound 9aaea. Yield 68%; oil (Rf 0.4, hexane/
1
AcOEt 1:1); IR (neat) 3444, 1682, 1604 cmK1; H NMR
(300 MHz, CDCl3): d 0.75 (t, JZ7.5 Hz, 3H), 1.15 (sext,
JZ7.2 Hz, 2H), 1.31–1.41 (m, 2H), 1.49–1.88 (m, 11H),
2.28 (t, JZ7.8 Hz, 2H), 2.65 (s, 3H), 2.68 (t, JZ7.2 Hz,