8502 J . Org. Chem., Vol. 66, No. 25, 2001
Takekawa and Shishido
brine, and dried over MgSO4. Removal of the solvent and
14.3 (q), 21.0 (q), 33.4 (t), 41.3 (d), 60.8 (t), 66.4 (t), 116.4 (t),
123.9 (d), 130.5 (d), 136.0 (d), 170.7 (s), 171.2 (s); MS (EI) m/z
43 (base peak), 181 (M+ - 45); HRMS Calcd for C10H13O3
column chromatography (silica gel, hexane/AcOEt ) 95/5) gave
46 (374 mg, 66% from the olefin 31) as a colorless oil: [R]30
D
) +9.9° (c ) 2.19, CHCl3); IR (neat) cm-1 1740, 1714, 1646,
1239, 1084; 1H NMR (400 MHz, CDCl3) δ 1.04 (9H, s), 1.28
(3H, t, J ) 6.8 Hz), 1.45-1.54 (3H, m), 2.02 (3H, s), 3.72 (1H,
dd, J ) 2.9, 11.4 Hz), 3.81 (1H, dd, J ) 5.0, 11.4 Hz), 4.11-
4.17 (4H, m), 5.80 (1H, d, J ) 15.5 Hz), 6.47 (1H, dd, J ) 9.1,
15.5 Hz), 7.37-7.45 (6H, m), 7.65 (4H, t, J ) 6.8 Hz); 13C NMR
(75 MHz, CDCl3) δ 14.2 (q), 19.1 (s), 20.9 (q), 25.1 (d), 25.1 (d),
26.7 (q), 28.4 (d), 60.0 (t), 61.9 (t), 63.1 (t), 119.2 (d), 127.7 (d),
127.7 (d), 129.7 (d), 133.2 (s), 133.3 (s), 135.4 (d), 135.5 (d),
150.4 (d), 166.4 (s), 170.8 (s); MS (EI) m/z 241 (base peak),
480 (M+); HRMS Calcd for C28H36O5Si (M+): 480.2332, found:
480.2349.
(M+): 181.0865, found: 181.0873. 49:[R]30 ) +0.3° (c ) 0.18,
D
CHCl3); IR (neat) cm-1 1743, 1719, 1232, 1177, 1042, 986, 921;
1H NMR (400 MHz, CDCl3) δ 1.28 (3H, t, J ) 7.1 Hz), 2.05
(3H, s), 2.27 (1H, m), 2.39 (1H, m), 2.57 (1H, m), 4.00 (1H, dd,
J ) 6.6, 11.0 Hz), 4.06 (1H, dd, J ) 6.3, 11.0 Hz), 4.18 (2H, q,
J ) 7.1 Hz), 5.12 (1H, d, J ) 17.3 Hz), 5.14 (1H, d, J ) 10.5
Hz), 5.66 (1H, ddd, J ) 7.8, 10.5, 17.1 Hz), 5.84 (1H, d, J )
15.6 Hz), 6.89 (1H, ddd, J ) 7.3, 7.6, 15.6 Hz); 13C NMR (100
MHz, CDCl3) δ 14.4 (q), 21.0 (q), 34.1 (t), 42.0 (d), 60.3 (t), 66.4
(t), 117.2 (t), 123.1 (d), 137.0 (d), 145.6 (d), 166.0 (s), 170.7 (s);
MS (EI) m/z 43 (base peak), 181 (M+ - 45); HRMS Calcd for
C10H13O3 (M+): 181.0865, found: 181.0826.
(2′S,3′R,3S)-Eth yl 3-(2′-Acetoxym eth yl-3′-iod om eth yl)-
cyclop r op yl)a cr yla te (47). To the solution of 46 (200 mg,
0.42 mmol) was added tetra-n-butylammonium fluoride (0.54
mL, 1.0 M solution in THF) at 0 °C. After being stirred at 0
°C for 45 min then at room temperature for 30 min, the
mixture was quenched with H2O and extracted with CH2Cl2.
Organic layer was washed with brine and dried over MgSO4.
Removal of the solvent and column chromatography (silica gel,
hexane/AcOEt ) 65/35) gave the alcohol (96.4 mg, 96%) as a
colorless oil: [R]29D ) -0.53° (c ) 0.76, CHCl3); IR (neat) cm-1
3445, 1739, 1714, 1644, 1238, 1145, 1082, 1033; 1H NMR (300
MHz, CDCl3 + D2O) δ 1.28 (3H, t, J ) 7.2 Hz), 1.49 (1H, m),
1.60 (2H, m), 2.09 (3H, s), 3.54 (1H, dd, J ) 8.3, 11.9 Hz), 3.90
(1H, dd, J ) 4.8, 11.9 Hz), 4.02 (1H, dd, J ) 8.3, 11.9 Hz),
4.18 (2H, q, J ) 7.2 Hz), 4.41 (1H, dd, J ) 5.7, 11.9 Hz), 5.87
(1H, d, J ) 15.6 Hz), 6.50 (1H, dd, J ) 9.5, 15.4 Hz); 13C NMR
(75 MHz, CDCl3) δ 14.1 (q), 20.8 (q), 24.6 (d), 24.9 (d), 28.6
(d), 60.1 (t), 60.6 (t), 62.7 (t), 119.5 (d), 149.7 (s), 149.8 (d),
166.3 (s), 171.0 (s); MS (EI) m/z 43 (base peak), 242(M+);
HRMS Calcd for C12H18O5 (M+): 242.1155, found: 242.1187.
Iodination of the alcohol (39 mg, 0.16 mmol) as described for
14a gave the iodide 47 (52 mg, 92%) as a colorless oil, after
purification by column chromatography (silica gel, hexane/
(2S )-2-Vin yl-3-(3,4-(m e t h yle n e d ioxy)p h e n yl)-1-p r o-
p a n ol ((S)-51). Hydrolysis of the acetate 20 (48 mg, 0.19
mmol) with KOH in aqueous ethanol gave (S)-51 (39 mg, 97%)
as a colorless oil after column chromatography (hexane/AcOEt
) 80/20): [R]29D ) +2.2° (c ) 2.73, CHCl3) (>99% ee: DAICEL,
CHIRALCEL OB (0.46 × 25 cm), 1% iPrOH/hexane (v/v), flow
rate; 1.0 mL/min; retention time; 44 min for (+)-isomer and
51 min for (-)-isomer. Eluent detection was monitored by UV
absorbance at 254 nm); IR (neat) cm-1 3376, 1504, 1488, 1246,
1039; 1H NMR (400 MHz, CDCl3) δ 2.49 (1H, m), 2.58 (1H,
dd, J ) 6.8, 13.7 Hz), 2.67 (1H, dd, J ) 7.3, 13.7 Hz), 3.47
(1H, dd, J ) 7.3, 10.5 Hz), 3.59 (1H, dd, J ) 5.0, 10.5 Hz),
5.09 (1H, d, J ) 17.8 Hz), 5.14 (1H, dd, J ) 10.5 Hz), 5.69
(1H, ddd, J ) 8.2, 10.5, 17.8 Hz), 6.61 (1H, d, J ) 7.7 Hz),
6.66 (1H, s), 6.71 (1H, d, J ) 7.7 Hz); 13C NMR (100 MHz,
CDCl3) δ 37.0 (t), 48.2 (d), 64.7 (t), 100.8 (t), 108.0 (d), 109.5
(d), 117.4 (t), 121.9 (d), 133.4 (s), 139.1 (d), 145.8 (s), 147.5 (s);
MS (EI) m/z 135 (base peak), 206 (M+); HRMS Calcd for
C
12H14O3 (M+): 206.0943, found: 206.0949.
(3S)-3-ter t-Bu tyld im eth ylsiloxym eth yl-4-(3,4-(Meth yl-
en ed ioxy)p h en yl)-1-p r op en e ((S)-52). Imidazole (24 mg,
0.35 mmol), tert-butyldimethylsilyl chloride (39 mg, 0.26
mmol), and 4-(dimethylamino)pyridine (cat.) were added to a
solution of the alcohol (36 mg, 0.17 mmol) in dry DMF (0.8
mL). After being stirred for 1 h at room temperature, the
mixture was quenched with H2O and extracted with AcOEt.
Organic layer was washed with brine and dried over MgSO4.
Removal of the solvent and column chromatography (silica gel,
hex/AcOEt ) 97/3) gave the silyl ether (S)-52 (53 mg, 95%) as
AcOEt ) 90/10): [R]30 ) -2.6° (c ) 1.48, CHCl3); IR (neat)
D
cm-1 1739, 1714, 1646, 1234, 1144, 1031; 1H NMR (300 MHz,
CDCl3) δ 1.28 (3H, t, J ) 7.2 Hz), 1.52 (1H, m), 1.79 (2H, m),
2.09 (3H, s), 3.17 (1H, dd, J ) 8.3, 10.3 Hz), 3.38 (1H, dd, J )
7.3, 10.3 Hz), 4.11-4.26 (4H, m), 5.89 (1H, d, J ) 15.6 Hz),
6.47 (1H, dd, J ) 9.5, 15.4 Hz); 13C NMR (75 MHz, CDCl3) δ
2.9 (t), 14.2 (q), 20.9 (q), 29.1 (d), 30.5 (d), 31.1 (d), 60.2 (t),
61.4 (t), 120.1 (d), 148.4 (d), 166.1 (s), 170.7 (s); MS (EI) m/z
43(base peak), 352(M+); HRMS Calcd for C12H17IO4(M+):
352.0171, found:352.0154.
a colorless oil: [R]28 ) +3.75° (c ) 1.07, CHCl3); IR (neat)
D
cm-1 1504, 1488, 1041; 1H NMR (400 MHz, CDCl3) δ 0.04 (6H,
s), 0.91 (9H, s), 2.40 (1H, m), 2.49 (1H, dd, J ) 8.2, 13.7 Hz),
2.81 (1H, dd, J ) 5.9, 13.7 Hz), 3.49 (1H, dd, J ) 6.4, 10.0
Hz), 3.54 (1H, dd, J ) 5.5, 10.0 Hz), 4.96 (1H, d, J ) 18.2 Hz),
5.00 (1H, d, J ) 10.0 Hz), 5.69 (1H, ddd, J ) 7.7, 10.0, 18.2
Hz), 5.92 (2H, s), 6.61 (1H, d, J ) 7.7 Hz), 6.67 (1H, s), 6.71
(1H, d, J ) 7.7 Hz); 13C NMR (100 MHz, CDCl3) δ -5.4 (q),
-5.3 (q), 18.3 (s), 25.9 (q), 37.0 (t), 48.1 (d), 65.3 (t), 100.7 (t),
107.9 (d), 109.7 (d), 115.7 (t), 122.1 (d), 134.2 (s), 139.5 (d),
145.5 (s), 147.3 (s); MS (EI) m/z 320 (base peak, M+); HRMS
Calcd for C18H28O3Si (M+): 320.1808, found: 320.1836.
(3S)-3-ter t-Bu tyld im eth ylsiloxym eth yl-4-(3,4-(m eth yl-
en ed ioxy)p h en yl)-1-bu ta n ol ((S)-53). 9-Borabicyclo[3.3.1]-
nonane (0.7 mL, 0.5 M in THF) was added at 0 °C to a solution
of the olefin (S)-52 (56 mg, 0.17 mmol) in THF (1 mL). After
being stirred at room temperature for 2 h, H2O (0.5 mL), 3 N
NaOH solution (0.2 mL), and 30% H2O2 solution (0.3 mL) were
added to the mixture, and stirring was continued at room
temperature for 2 h. The reaction mixture was extracted with
AcOEt, washed with brine, and dried over MgSO4. Removal
of the solvent and column chromatography (silica gel, hex/
AcOEt ) 95/5) gave the alcohol (S)-53 (58 mg, 98%) as a
(E)-(3R)-Eth yl 5-Acetoxym eth ylh epta-3,6-dien oate ((E)-
48), (Z)-(3R)-Eth yl 5-Acetoxym eth ylh ep ta -3,6-d ien oa te
((Z)-48), a n d (E)-(2S)-Eth yl 5-Acetoxym eth ylh ep ta -2,6-
d ien oa te (49). Radical reaction of iodide 47 (50 mg, 0.14
mmol) gave the 5:1:1 mixture of (E)-48, (Z)-48, and 49 (26 mg,
80%) as a colorless oil. Separation was done by HPLC (Hibar
RT 250-25 LiChrosorb Si 60 (7µm), hexane/AcOEt ) 95/5 (v/
v), flow rate; 10 mL/min (v/v), retention time; 77 min for (Z)-
48, 86 min for (E)-48 and 98 min for 49. Eluent detection was
monitored by UV absorbance at 215 nm). (E)-48: [R]30
)
D
-0.06° (c ) 1.02, CHCl3); IR (neat) cm-1 1739, 1730, 1640,
1238, 1175, 1035, 923; 1H NMR (400 MHz, CDCl3) δ 1.26 (3H,
t, J ) 7.1 Hz), 2.04 (3H, s), 3.06 (2H, d, J ) 6.8 Hz), 3.12 (1H,
m), 4.06 (2H, d, J ) 6.8 Hz), 4.14 (2H, q, J ) 7.1 Hz), 5.11
(1H, dm, J ) 16.4 Hz), 5.12 (1H, dm, J ) 10.3 Hz), 5.50 (1H,
dd, J ) 7.3, 15.6 Hz), 5.66 (1H, dt, J ) 7.3, 15.6 Hz), 5.74 (1H,
m); 13C NMR (100 MHz, CDCl3) δ 14.3 (q), 21.0 (q), 38.2 (t),
45.8 (d), 60.7 (t), 66.3 (t), 116.7 (s), 124.4 (d), 132.1 (d), 136.6
(d), 170.7 (s), 171.3 (s); MS (EI) m/z 43 (base peak), 181 (M+
-
45); HRMS Calcd for C10H13O3(M+): 181.0865, found: 181.0869.
colorless oil: [R]28 ) -11° (c ) 2.64, CHCl3); IR (neat) cm-1
D
(Z)-48: [R]30 ) +0.9° (c ) 0.16, CHCl3); IR (neat) cm-1 1740,
3365, 1041; 1H NMR (400 MHz, CDCl3 + D2O) δ 0.03 (3H, s),
0.04 (3H, s), 0.90 (9H, s), 1.56 (1H, m), 1.67 (1H, m), 1.88 (1H,
m). 2.44 (1H, dd, J ) 7.3, 13.7), 2.57 (1H, dd, J ) 7.7, 13.7
Hz), 3.47 (1H, dd, J ) 6.8, 10.0 Hz), 3.59 (1H, dd, J ) 4.1,
10.5 Hz), 3.62 (1H, m), 3.67 (1H, m), 5.93 (2H, s), 6.60 (1H, d,
J ) 8.2 Hz), 6.66 (1H, s), 6.72 (1H, d, J ) 8.2 Hz); 13C NMR
(75 MHz, CDCl3) δ -5.6 (q), 18.2 (s), 25.8 (q), 35.4 (t), 37.7 (t),
D
1638, 1240, 1176, 1036; 1H NMR (400 MHz, CDCl3) δ 1.26 (3H,
dt, J ) 0.7, 7.1 Hz), 2.04 (3H, s), 3.11 (2H, dm, J ) 7.1 Hz),
3.38 (1H, m), 4.01, (1H, dd, J ) 7.3, 10.5 Hz), 4.05 (1H, dd, J
) 6.6, 10.5 Hz), 4.15 (2H, dq, J ) 0.7, 7.1 Hz), 5.11 (1H, dm,
J ) 9.0 Hz), 5.12 (1H, dm, J ) 17.3 Hz), 5.45 (1H, dd, J ) 9.5,
10.7 Hz), 5.68-5.80 (2H, m); 13C NMR (100 MHz, CDCl3) δ