924 J. Chin. Chem. Soc., Vol. 50, No. 4, 2003
Hong et al.
(10 mL) was added LiAlH4 (30 mg, 0.78 mmol) at 0 °C. The
suspension was stirred for 1 h and graduately warmed up to
ambient temperature. The reaction was quenched by slow ad-
dition of H2O (10 mL). The solution was diluted with EtOAc
(100 mL), washed with brine (50 mL ´ 2), dried over MgSO4,
concentrated in vacuo and the residue was purified by flash
column chromatography with 10% EtOAc-hexane (Rf = 0.42
in 20% EtOAc-hexane) to give alcohol 10 (37 mg, 89%
yield). A similar procedure was applied to (-)-9-anti (80 mg,
(C 0.17, CHCl3), IR (neat): 3100-3500, 2925, 2728, 1572,
1408, 746, 663 cm-1; 1H NMR (CDCl3, * denonate minor iso-
mer) d 7.30-7.10 (m, 5H), 5.51 (br.s, 1H), 5.40* (br.s, 1H),
4.30-4.05 (m, 1H), 2.50-2.25 (m, 5H), 2.10-1.45 (m, 11H),
0.99* (d, J = 7.0 Hz, 3H), 1.01 (d, J = 7.0 Hz, 3H); 13C NMR
(CDCl3) d 140.81, 140.06, 133.52, 130.45, 129.05, 128.99,
127.56, 127.24, 127.14, 122.25, 121.12, 116.92, 116.84,
41.77, 39.28, 39.06, 238.70, 38.29, 25.38, 25.25, 25.19,
23.69, 23.03, 22.99, 22.81, 22.73, some C not evident be-
cause of tautomeric exchange; MS (m/z, relative intensity):
342 (M+, 6), 326 (5), 246 (18), 231 (30), 217 (52), 149 (25),
108 (100); exact mass calculated for C21H26O2S (M+):
342.1655; found 342.1654.
27
0.21 mmol) and gave alcohol 10 (28 mg, 88% yield). [a]D
-3.1 (C 0.19, CHCl3), IR (neat): 3100-3600, 2927, 1660,
1
1450, 1052 cm-1; H NMR (CDCl3) d 5.41 (br.s, 1H), 3.60-
3.45 (m, 2H), 2.20-2.10 (m, 1H), 2.00-1.72 (m, 4H), 1.62-
1.20 (m, 6H), 0.96 (d, J = 6.8 Hz, 3H); 13C NMR (CDCl3) d
141.68 (C), 120.74 (C), 61.63 (CH2), 38.36 (CH), 37.56
(CH2), 25.15 (CH2), 24.58 (CH2), 22.96 (CH2), 22.73 (CH2),
19.67 (CH3); MS (m/z, relative intensity): 154 (M+, 20), 123
(20), 110 (98), 81 (100); exact mass calculated for C10H18O
(M+): 154.1358; found 154.1355.
Preparation of acetate 13
To a solution of 12 (50 mg, 0.15 mmol) in benzene (10
mL) was added Ph3SnH (56 mg, 0.16 mmol), AIBN (7 mg,
0.04 mmol), subsequently. The solution was heated to reflux
for 1 h and cool down to room temperature, concentrated in
vacuo and the residue was purified by flash column chroma-
tography with 30% EtOAc-hexane (Rf = 0.37 in 60% EtOAc-
hexane) to give thiolether 12.5 as a yellow oil (27 mg, 73%
yield). [a]D27 -3 (C 0.09, CHCl3), IR (neat): 3100-3600, 2929,
Preparation of aldehyde 11
To a solution of 10 (100 mg, 0.65 mmol) in CH2Cl2 (100
mL) was added PCC (210 mg, 0.97 mmol) at room tempera-
ture. The suspension was stirred for 2 h and was diluted with
EtOAc (100 mL). The solution was washed with brine (50
mL ´ 2), dried over MgSO4, concentrated in vacuo and the
residue was purified by flash column chromatography with
5% EtOAc-hexane (Rf = 0.70 in 10% EtOAc-hexane) to give
1
2862, 1731, 1595, 1393, 1275, 1228, 756 cm-1; H NMR
(CDCl3) d 5.39 (br.s, 1H), 2.55-2.38 (m, 3H), 2.10-1.75 (m,
6H), 1.65-1.10 (m, 8H), 1.00-0.80 (m, 1H), 0.95 (d, J = 9.6
Hz, 3H); 13C NMR (CDCl3) d 196.88 (C), 196.85 (C), 142.15
(C), 120.71 (CH), 118.65 (C), 41.33 (CH), 32.71 (CH2),
30.45 (CH2), 29.70 (CH2), 25.28 (CH2), 24.67 (CH2), 23.10
(CH2), 22.86 (CH2), 19.67 (CH3), 19.19 (CH2); MS (m/z, rela-
tive intensity): 235 (M++1, 22), 234 (M+, 28), 233 (37), 216
(65), 125 (100); exact mass calculated for C15H22O2 (M+):
234.1620; found 234.1619.
24
aaldehyde 11 (83 mg, 84% yield). [a]D -11.3 (C 0.03,
1
CHCl3), IR (neat): 2925, 1458, 1217, 758 cm-1; H NMR
(CDCl3) d 9.66 (t, J = 2.2 Hz, 1H), 5.44 (br.s, 1H), 2.68-2.55
(m, 1H), 2.52-2.40 (m, 1H), 2.35-2.22 (m, 1H), 2.00-1.80 (m,
3H), 1.65-1.35 (m, 5H), 1.04 (d, J = 6.7 Hz, 3H); 13C NMR
(CDCl3) d 202.99 (CH), 140.19 (C), 121.27 (CH), 48.86
(CH2), 35.97 (CH), 25.72 (CH2), 25.12 (CH2), 22.90 (CH2),
22.56 (CH2), 19.58 (CH3); MS (m/z, relative intensity): 153
(M++1, 3), 151 (M+-1, 12), 136 (29), 121 (32), 109 (48), 81
(100); exact mass calculated for C10H16O (M+): 152.1201;
found 152.1209.
To a solution of thiolether 12.5 (30 mg, 0.13 mmol) in
Ac2O (10 mL) was added NaOAc (3.72 mg, 0.045 mmol) and
the reaction solution was stirred at 25 °C for 2 h. The solution
was concentrated in vacuo and the residue was diluted with
Et2O (100 mL). The organic solution was washed with satu-
rated aqueous NaHCO3 solution (50 mL ´ 2), brine (50 mL ´
2), dried over MgSO4, concentrated in vacuo and the residue
was purified by flash column chromatography with 10%
EtOAc-hexane (Rf = 0.85 in 20% EtOAc-hexane) to give ace-
tate 3 as a yellow oil (25 mg, 71% yield). [a]D26 -6.6 (C 0.08,
CHCl3); IR (neat): 2928, 1706, 1646, 1441, 1180, 734, 697
cm-1; 1H NMR (CDCl3) d 5.36 (br.s, 1H), 2.78 (d, J = 4.9 Hz,
2H), 2.50-2.40 (m, 2H), 2.24 (s, 3H), 2.05-1.75 (m, 4H),
1.70-1.15 (m, 8H), 1.05-0.80 (m, 1H), 0.94 (d, J = 7 Hz, 3H);
13C NMR (CDCl3) d 205.83 (C), 175.66 (C), 166.76 (C),
141.13 (C), 130.61 (C), 120.79 (CH), 41.33 (CH), 34.51
Preparation of thiolether 12
To a solution of 11 (800 mg, 5.26 mmol) in CH2Cl2 (40
mL) was added 1,3-cyclopentadione (612 mg, 6.2 mmol),
benzenethiol (5.76 g, 52 mmol), silica gel (12 g), sequentially
and stirred for 24 h at 25 °C. The reaction mixture was fil-
tered through filter paper, concentrated in vacuo and the resi-
due was purified by flash column chromatography with 40%
EtOAc-hexane (Rf = 0.27 in 50% EtOAc-hexane) to give
thiolether 12 as a yellow oil (1.31 g, 73% yield). [a]D26 -1.6