10194
M. Ono et al. / Tetrahedron 60 (2004) 10187–10195
(0.707 g, 9% yield from (4R)-17)) of (4R)-8 from n-hexane/
AcOEtZ7:1 elute and (4R)-4 (1.737 g, total; 3.241 g
(47% overall yield from (4R)-17)) as a homogeneous oil
from n-hexane/AcOEtZ2:1 elute, respectively. (4R)-4:
[a]2D4ZC2.00 (cZ0.51, CHCl3) corresponding to 93% ee
by means of HPLC analysis), The NMR data of (4R)-4 were
identical with those of the reported (G)-4.5 Acetate of (4R)-
8: [a]2D6ZC8.98 (cZ0.50, CHCl3) corresponding to 93%
ee by means of HPLC analysis): IR (neat): 1740 cmK1; 1H
NMR: d 2.02 (3H, s), 3.72 (3H, s), 3.82 (3H, s), 4.23 (1H, br,
q, JZ7.0 Hz), 4.33 (1H, dd, JZ11.0, 5.0 Hz), 4.40 (1H, dd,
JZ11.0, 9.0 Hz), 5.87 (1H, dd, JZ16.0, 2.0 Hz), 6.88 (1H,
dd, JZ8.0, 2.0 Hz), 6.92 (1H, dt, JZ8.0, 2.0 Hz), 7.11 (1H,
dd, JZ8.0, 2.0 Hz), 7.16 (1H, dd, JZ16.0, 7.0 Hz), 7.25
(1H, dt, JZ8.0, 2.0 Hz). FAB MS m/z: 279 (MC1)C; Anal.
Found: C, 64.60; H, 6.50. Calcd for C15H18O5: C, 64.74; H,
6.52%.
stirred for 30 min. The generated precipitate was filtered
with the aid of celite and the filtrate was condensed. The
residue was diluted with ether and treated with 10% aqueous
HCl. The organic layer was dried over MgSO4 and
evaporated to give a residue, which was chromatographed
on silica gel (30 g, n-hexane/AcOEtZ1:1) to afford
diastereomeric lactone (2S,3R,4S)-25 (0.010 g, 2%) and
the desired (2R,3S,4S)-25 (0.463 g, 78%) in elution order.
Crystallization of (2R,3S,4S)-25 from CHCl3 gave a color-
less crystal. (2R,3S,4S)-25: mp 81–82 8C, [a]2D4ZK72.2
(cZ0.41, MeOH) corresponding to O99% ee by means of
1
HPLC analysis): IR (KBr): 3298, 1756 cmK1; H NMR: d
2.82 (1H, dd, JZ8, 15 Hz), 3.13 (1H, dd, JZ3, 15 Hz), 3.74
(3H, s), 3.88 (1H, t, JZ9 Hz), 4.25 (1H, dt, JZ3, 8 Hz),
4.30 (1H, d, JZ9 Hz), 6.84 (2H, d, JZ9 Hz), 7.17 (2H, d,
JZ9 Hz). Anal. Calcd for C12H14O5: C, 60.50; H, 5.92.
Found: C, 50.90; H, 5.90. MS (FAB) m/z: 239 (MCC1).
(2S,3R,4S)-25: [a]2D2ZK86.0 (cZ0.11, MeOH) corre-
sponding to 93% ee by means of HPLC analysis): IR
4.1.12. Methyl (4S)-4-hydroxy-5-(40-methoxyphenyl)-
2(E)-pentenoate 5. (1) To a solution of (4R)-4 (2.01 g,
8.51 mmol) in CH2Cl2 (40 mL) were added triphenyl
phosphine (Ph3P; 4.46 g, 17 mmol) and carbon tetrabromide
(CBr4; 8.46 g, 25.5 mmol) at 0 8C and the whole mixture
was stirred for 1.5 h at room temperature. The reaction
mixture was evaporated to afford a residue, which was
chromatographed on silica gel (80 g, n-hexane/AcOEtZ
30:1) to provide (4R)-13 (2.342 g, 92%) as a colorless oil.
(4R)-13: [a]2D7ZC3.00 (cZ0.50, CHCl3) corresponding to
93% ee by means of HPLC analysis), The NMR data of
(4R)-13 were identical with those of the reported (G)-13.
(2) To a solution of (4R)-13 (1.43 g, 4.8 mmol) in
1
(KBr): 3429, 1758 cmK1; H NMR: d 2.90 (1H, dd, JZ8,
15 Hz), 3.08 (1H, dd, JZ5, 15 Hz), 3.76 (3H, s), 4.03 (1H,
d, JZ5 Hz), 4.19 (1H, t, JZ5 Hz), 4.72 (1H, dt, JZ5,
8 Hz), 6.84 (2H, d, JZ9 Hz), 7.20 (2H, d, JZ9 Hz). Anal.
Calcd for C12H14O5: C, 60.50; H, 5.92. Found: C, 60.37; H,
5.91. MS (FAB) m/z: 239 (MCC1). (2) To a solution of
(2R,3S,4S)-25 (0.101 g, 0.42 mmol) and N,N-diisopropyl-
ethylamine (1.32 g, 9.29 mmol) in MeCN (1 mL) was added
chloromethylmethyl ether (CH3OCH2Cl; 0.68 g,
8.45 mmol) at 0 8C and the whole mixture was stirred for
24 h at room temperature. The reaction mixture was diluted
with brine and ether at 0 8C, the organic layer was dried over
MgSO4. Evaporation of the organic solvent gave a residue,
which was chromatographed on silica gel (10 g, n-hexane/
AcOEtZ8:1) to afford (2R,3S,4S)-26 (0.107 g, 78%) as a
colorless oil. (2R,3S,4S)-26: [a]2D4ZK18.7 (cZ0.49,
CHCl3) corresponding to O99% ee by means of HPLC
analysis): IR (neat): 1790 cmK1; 1H NMR: d 2.94 (1H, dd,
JZ7, 14 Hz), 3.15 (1H, dd, JZ4, 14 Hz), 3.40 (3H, s), 3.44
(3H, s), 3.79 (3H, s), 4.07 (1H, t, JZ7 Hz), 4.42 (1H, dt, JZ
4, 7 Hz), 4.47 (1H, d, JZ7 Hz), 4.65 (1H, d, JZ7 Hz), 4.73
(1H, d, JZ7 Hz), 4.79 (1H, d, JZ7 Hz), 5.02 (1H, d, JZ
7 Hz), 6.85 (2H, d, JZ8 Hz), 7.18 (2H, d, JZ8 Hz). Anal.
Calcd for C16H22O7: C, 58.89; H, 6.80. Found: C, 58.96; H,
6.97. MS (FAB) m/z: 326 (MC). (3) To a solution of
(2R,3S,4S)-26 (0.076 g, 0.23 mmol) in benzene (5 mL) was
added 1 M diisobutylaluminum hydride (Dibal-H) in
toluene solution (1.41 mL, 1.41 mmol) at 0 8C and the
whole mixture was stirred for 1 h at 0 8C. The reaction
mixture was diluted with brine and extracted with ether. The
organic layer was dried over MgSO4 and evaporated to
give a residue, which was chromatographed on silica gel
(10 g, n-hexane/AcOEtZ1:1) to afford (4S)-7 (0.062 g,
81%) as a colorless oil. (4S)-7: [a]2D4ZK39.3 (cZ0.51,
MeOH) corresponding to O99% ee by means of HPLC
analysis): IR (neat): 3439 cmK1; 1H NMR: d 2.62 (1H, dd,
JZ10, 14 Hz), 2.92 (1H, d, JZ5 Hz), 3.00 (1H, dd, JZ3,
14 Hz), 3.21 (1H, t, JZ6 Hz), 3.41 (3H, s), 3.46 (3H, s),
3.65 (1H, dd, JZ4, 7 Hz), 3.74–3.78 (2H, m), 3.79 (3H, s),
3.91–3.97 (2H, m), 4.71–4.77 (4H, m), 6.85 (2H, d, JZ
9 Hz), 7.18 (2H, d, JZ9 Hz). Anal. Calcd for C16H26O7: C,
58.17; H, 7.93. Found: C, 57.75; H, 8.06. MS (FAB) m/z:
369 (MCCK).
˚
nitromethane (20 mL) were added molecular sieves (4 A;
2.0 g) and silver nitrate (AgNO3; 1.62 g, 9.54 mmol) and the
whole mixture covered with aluminum foil was stirred for
24 h at room temperature. The reaction mixture was worked
up in the same way as the previous (G)-15 to give (4S)-15
(1.22 g, 91%). (4S)-15: [a]2D7ZC15.9 (cZ0.51, CHCl3)
corresponding to 93% ee by means of HPLC analysis), The
NMR data of (4S)-15 were identical with those of the
reported (G)-15. (3) To a mixture of Zn-dust (1.14 g) and
CH3COONH4 (1.14 g) in MeOH (5 mL) was added a
solution of (4S)-15 (1.140 g, 4.06 mmol) in MeOH (7 mL)
and the whole mixture was stirred for 1 h at 0 8C. The
generated precipitate was filtered off with the aid of celite
and the filtrate was diluted with water and ether. The organic
layer was dried over MgSO4 and evaporated to give a
residue, which was chromatographed on silica gel (40 g,
n-hexane/AcOEtZ5:1) to afford (4S)-5 (0.833 g, 87%) as a
colorless oil. (4S)-5: [a]2D6ZC1.00 (cZ0.50, CHCl3)
corresponding to 93% ee by means of HPLC analysis),
The NMR data of (4S)-5 were identical with those of the
previous (G)-5.
4.1.13. (2S,3S,4S)-4-Hydroxy-2,3-dimethoxymethyl-5-
(40-methoxyphenyl)-pentanol 7. (1) To a solution of 50%
aqueous N-methylmorpholine N-oxide (0.58 mL,
2.49 mmol) and 2% aqueous osmium tetraoxide (OsO4;
3.16 mL, 10 mol%) in acetone (5 mL) was added a solution
of (4S)-5 (0.588 g, 2.49 mmol) in acetone (5 mL) at 0 8C
and the whole mixture was stirred for 2 h at the same
temperature. The reaction mixture was diluted with 10%
aqueous Na2SO3 (5 mL) at 0 8C and the whole mixture was