mmol), and AIBN (10 mg, 20 mol %) in dry and degassed toluene
(4.8 mL) was refluxed for 1 h. The solution was cooled, and water
was added. The organic phase was separated, washed, and dried
on magnesium sulfate. The solvent was evaporated under
vacuum, and the crude was chromatographed on silica gel, first
neutralized with a 5% v/v NEt3 solution in petroleum ether, to
136.9, 140.9, 141.9, 146.7; MS m/z 448 [M+] (9), 386 (1), 99 (100);
IR (KBr) cm-1 759, 694. Anal. Calcd for C29H36O4: C, 77.64; H,
8.09. Found: C, 77.48; H, 8.16.
11-(Vin ylm eth yliden e)-3,3,17,17-(eth ylen edioxy)an dr ost-
5-en e (5b). A solution of 2b (100 mg, 0.19 mmol) in dry toluene
(2 mL) was refluxed overnight. The organic phase was washed
with water and dried on magnesium sulfate. The solvent was
evaporated under vacuum, and the crude was chromatographed
with a mixture petroleum ether/ethyl acetate 9/1 to afford 5b
(33 mg, 42% yield): mp 110 °C; 1H NMR (CDCl3) δ 0.91 (3H, s),
1.08 (3H, s), 1.18-1.37 (3H, m), 1.51 (1H, dt, J ) 13.8, 3.9 Hz),
1.66-2.03 (13H, m), 2.13 (1H, dd, J ) 13.8, 3.3 Hz), 2.25 (1H,
dt, J ) 13.2, 3.6 Hz), 2.48 (1H, bd, J ) 13.8 Hz), 2.84 (2H, m),
3.90-4.01 (8H, m), 5.01 (1H, bd, J trans ) 17.4 Hz), 5.02 (1H, bd,
J cis ) 10.2 Hz), 5.51 (1H, bd, J ) 5.7 Hz), 5.76 (2H, m); 13C NMR
(CDCl3) δ 17.5, 17.7, 21.9, 30.9, 31.3, 33.9, 35.0, 37.5, 41.0, 42.6,
42.7, 46.5, 47.3, 55.9, 64.3, 64.3, 64.4, 65.3, 108.9, 115.9, 118.7,
123.6, 133.5, 137.4, 137.5, 141.7; MS (ICP/NH3) m/z 430 [M +
NH4] (100). Anal. Calcd for C26H36O4: C, 75.69; H, 8.80. Found:
C, 75.53; H, 8.97.
11-Meth yl-3,3,17,17-(eth ylen ed ioxy)a n d r ost-5,11(12)-d i-
en e (4c) a n d 11-Meth ylid en e-3,3,17,17-(eth ylen ed ioxy)-
a n d r ost-5-en e (5c). A solution of 2c (613 mg, 1.25 mmol) in
dry mesitylene was refluxed for 2 h. The organic phase was
washed and dried on magnesium sulfate. The solvent was
evaporated under vacuum, and the crude was chromatographed
with a mixture petroleum ether/ethyl acetate 9/1 to afford 4c
(173 mg, 36% yield) [mp 80 °C; 1H NMR (CDCl3) δ 0.92 (3H, s),
1.07 (3H, s), 1.30 (2H, m), 1.48 (1H, dt, J ) 13.8, 3.9 Hz), 1.66
(2H, m), 1.81 (3H, s), 1.75-1.97 (10H, m), 2.14 (1H, dd, J ) 13.7,
3.0 Hz), 2.31 (1H, dt, J ) 13.1, 3.6 Hz), 2.52 (1H, dq, J ) 13.7,
2.1 Hz), 3.87-4.01 (8H, m), 5.51 (1H, bd, J ) 6.0 Hz), 5.70 (1H,
s); 13C NMR (CDCl3) δ 17.6, 18.0, 22.1, 27.6, 30.9, 31.3, 33.7,
34.9, 37.4, 40.5, 42.6, 46.7, 47.1, 56.7, 64.2, 64.3, 64.4, 65.2, 109.0,
118.7, 123.4, 133.3, 135.0, 141.7; MS (m/z) 386 [M]+ (5), 99 (100).
Anal. Calcd for C24H34O4: C, 74.58; H, 8.87. Found: C, 74.55;
H, 8.96] and 5c (69 mg, 14% yield) [mp 234 °C; 1H NMR (CDCl3)
δ 0.77 ( 3H, s), 1.23 (1H, m), 1.29 (3H, s), 1.38 (1H, dt, J ) 14.1,
3.9 Hz), 1.55-1.98 (11H, m), 2.14 (1H, dt, J ) 14.1, 3.0 Hz),
2.38 (1H, bd, J ) 12.0 Hz), 2.47 (1H, dt, J ) 13.8, 3.7 Hz), 2.61
(1H, dq, J ) 14.4, 2.9 Hz), 3.83-3.99 (8H, m), 4.98 (2H, bd, J )
8.4), 5.30 (1H, bs); 13C NMR (CDCl3) δ 14.4, 18.7, 23.1, 31.1,
32.0, 33.5, 34.5, 34.9, 37.4, 41.9, 45.6, 46.6, 51.1, 54.1, 64.2, 64.4,
64.5, 65.2, 109.1, 113.5, 119.0, 120.7, 141.6, 145.0; MS (m/z) 387
[M + H]+ (100). Anal. Calcd for C24H34O4: C, 74.58; H, 8.87.
Found: C, 74.54; H, 8.95.]
1
afford R-3b (34 mg, 21% yield) [mp 132 °C; H NMR (CDCl3) δ
0.84 (3H, s), 1.06 (1H, t, J ) 10.2 Hz), 1.15 (3H, s), 1.19-1.29
(1H, m), 1.35-1.47 (5H, m), 1.61-1.71 (3H, m), 1.74-1.97 (5H,
m), 2.03-2.22 (3H, m), 2.42 (1H, dm, J ) 14.7 Hz), 2.58 (1H,
dq, J ) 14.0, 2.6 Hz), 3.81-3.98 (8H, m), 4.97 (1H, bd, J trans
)
15.9 Hz), 4.98 (1H, bd, J cis ) 11.5 Hz), 5.43 (1H, bd, J ) 5.6
Hz), 5.73-5.82 (1H, m); 13C NMR (CDCl3) δ 14.8, 17.7, 23.4, 31.3,
31.6, 32.7, 34.2, 37.9, 38.3, 39.9, 41.5, 42.7, 45.3, 49.4, 52.2, 64.3,
64.4, 64.6, 65.2, 109.0, 116.1, 119.7, 122.8, 137.0, 140.7; m/z 414
[M+] (1), 99 (100). Anal. Calcd for C26H38O4 C, 75.32; H, 9.24.
Found: C, 74.97; H, 9.44], S-3b (50 mg, 31% yield) [mp 132 °C;
1H NMR (CDCl3) δ 0.95 (3H, s), 1.15 (3H, s), 1.19-1.30 (1H, m),
1.35-1.42 (1H, m), 1.46-1.55 (3H, m), 1.63-1.78 (7H, m), 1.85
(1H, dt, J ) 13.1, 3.6 Hz), 1.97-2.03 (1H, m), 2.09-2.25 (4H,
m), 2.48-2.52 (1H, m), 2.56 (1H, dq, J ) 14.0, 2.6 Hz), 3.81-
3.98 (8H, m), 4.96-5.02 (2H, m), 5.16-5.17 (1H, m), 5.68-5.78
(1H, m); 13C NMR (CDCl3) δ 16.0, 21.6, 22.9, 29.4, 30.9, 31.8,
32.2, 34.2, 34.7, 36.9, 37.2, 40.8, 45.6, 52.4, 53.4, 64.2, 64.5, 64.6,
65.1, 109.0, 115.6, 119.8, 120.9, 139.7, 141.7; MS m/z 414 [M+]
(1), 99 (100); HRMS calcd for C26H37O4 (M+ - H) 413.2692, found
413.2690], and 6 (49 mg, 27% yield) [mp 132 °C; 1H NMR (CDCl3)
δ 0.86 (3H, s), 0.96 (3H, d, J ) 6.7 Hz), 1.19-1.31 (1H, m), 1.37
(3H, s), 1.36-1.45 (1H, m), 1.50-1.60 (3H, m), 1.65-1.86 (7H,
m), 1.96-2.03 (2H, m), 2.09 (1H, dd, J ) 14.5, 3.2 Hz), 2.16 (1H,
d, J ) 13.6 Hz), 2.57 (1H, dd, J ) 14.5, 2.9 Hz), 2.58 (1H, t, J )
12.5 Hz), 2.74 (1H, dt, J ) 12.2, 3.5 Hz), 2.95 (1H, sep), 3.83
(3H, s), 3.86-3.98 (8H, m), 5.29-5.31 (1H, m); 13C NMR (CDCl3)
δ 13.0, 13.7, 20.7, 23.9, 31.1, 34.0, 36.6, 37.9, 41.7, 41.9, 44.3,
45.2, 48.0, 49.7, 53.0, 53.3, 64.2, 64.3, 64.4, 65.0, 89.0, 102.9,
108.9, 119.8, 121.4, 142.9, 172.7; MS (ICP/NH3) m/z 536 [M +
NH4]+ (7.5), 519 [M + H]+ (100), 501 [M - H2O + NH4]+ (70);
IR (KBr) cm-1 1744 (CdO). Anal. Calcd for C29H42O8: C, 67.16;
H, 8.16. Found: C, 66.78; H, 8.30].
11-P h en yl-3,3,17,17-(eth ylen ed ioxy)a n d r osta -5,11(12)-d i-
en e (4a ). A solution of 2a (604 mg, 1.09 mmol) in dry toluene
(30 mL) was refluxed overnight. The organic phase was washed
with water and dried on magnesium sulfate. The solvent was
evaporated under vacuum, and the crude was chromatographed
with a mixture petroleum ether/ethyl acetate 85/15 to afford 4a
1
(374 mg, 76% yield): mp 211 °C; H NMR (CDCl3) δ 0.77 (1H,
dt, J ) 13.3), 1.00 (1H, dt, J ) 13.7), 1.06 (6H, s), 1.23-1.52
(4H, m), 1.74 (1H, m), 1.82-2.12 (8H, m), 2.41 (1H, dq, J ) 13.7),
2.60 (1H, m), 3.75-3.95 (8H, m), 5.52 (1H, bs), 5.80 (1H, d, J )
1.5 Hz), 7.13-7.29 (5H, m); 13C NMR (CDCl3) δ 17.6, 18.5, 21.9,
31.9, 33.6, 35.0, 38.2, 41.4, 42.3, 46.4, 47.5, 55.6, 64.0, 64.1, 64.3,
65.2, 77.2, 109.0, 118.5, 123.4, 125.9, 126.9, 127.6, 128.1, 128.4,
Su p p or tin g In for m a tion Ava ila ble: Characterization
data for all new compounds. This material is available free of
J O0401016
J . Org. Chem, Vol. 69, No. 9, 2004 3219