7216
Y. Haruta et al. / Tetrahedron 64 (2008) 7211–7218
C30H42O5Si (MþH)þ: m/z 511.2874, found: 511.2910. Minor isomer:
product was chromatographed on a silica gel column (hexane/
AcOEt¼10:1) to give the title compound (1.08 g, 94%) as a colorless
oil, which was used for the next reaction without further purifi-
cation. A solution of the above compound (889 mg, 1.69 mmol) in
dry THF (10 mL) was added into a suspension of NaH (203 mg,
5.06 mmol) in dry THF (10 mL), and the mixture was stirred for
30 min at room temperature, followed by the addition of allyl
1H NMR (CDCl3):
d 7.70–7.57 (4H, m), 7.42–7.31 (6H, m), 4.45–4.42
(1H, m), 4.05–4.01 (1H, m), 3.58 (1H, d, J¼7.7 Hz), 3.58–3.52 (1H,
m), 3.02 (1H, d, J¼6.7 Hz), 1.88–1.70 (2H, m), 1.59–1.49 (2H, m),
1.47–1.41 (1H, m), 1.39 (3H, s), 1.38 (3H, d, J¼6.0 Hz), 1.28 (3H, s),
1.28 (3H, s), 1.24–1.08 (2H, m), 1.01 (9H, s), 0.88–0.85 (1H, m).
4.9. The MTPA Mosher ester of the major isomer of 28
bromide (584 mL, 6.75 mmol). After stirring for 1 h, the mixture was
diluted with diethyl ether (100 mL), washed successively with
saturated aqueous NaHCO3, water, and brine, dried over MgSO4,
and evaporated. The crude product was chromatographed on a sil-
R-(þ)- and S-(ꢁ)-MTPA-OH were converted to the correspond-
ing MTPA-Cl by the reaction with SOCl2 and NaCl, as described in
the literature. A solution of MTPA-Cl and 28 (22 mg, 0.043 mmol)
ica gel column (hexane/AcOEt¼7:1) to give the title compound
20
and (ꢁ)-MTPA-Cl (15.5 mg, 0.065 mmol) in dry pyridine (75
mL) and
(937 mg, 98%) as a colorless oil. [
a
]
D
ꢁ23.9 (c 0.31, CHCl3). 1H NMR
CCl4 (75 L) in the presence of DMAP (10.7 mg, 0.086 mmol) was
m
(CDCl3): d 7.72–7.63 (4H, m), 7.43–7.32 (6H, m), 5.84–5.74 (1H, m),
stirred for 15 h at room temperature. The mixture was diluted with
AcOEt (15 mL), washed successively with water (12 mL), 5% aque-
ous CuSO4 (10 mL), water (10 mL), and brine (10 mL), dried over
Na2SO4, and evaporated. The crude product was chromatographed
on a silica gel column (hexane/AcOEt¼13:1) to give the (S)-MTPA
5.17 (1H, d, J¼17.2 Hz), 5.08 (1H, d, J¼10.3 Hz), 4.03–3.98 (2H, m),
3.87–3.82 (1H, m), 3.67 (1H, d, J¼9.0 Hz), 3.62–3.57 (1H, m), 3.41
(3H, s), 3.18–3.09 (2H, m), 1.86–1.63 (3H, m), 1.60–1.42 (2H, m),
1.41–1.22 (3H, m), 1.38 (6H, s), 1.24 (3H, d, J¼6.0 Hz), 1.03 (9H, s),
1.08–0.87 (1H, m). 13C NMR (CDCl3):
d 135.9,134.6,129.6,127.6, 37.8,
ester (18 mg) as a colorless oil. 1H NMR (CDCl3):
d
7.61 (6H, d,
117.3, 116.9, 107.9, 85.9, 84.4, 81.2, 80.9, 75.9, 74.4, 73.7, 72.6, 61.4,
59.0, 40.7, 38.4, 36.1, 27.2, 24.8, 23.8, 19.5, 17.3. IR (neat): 1364, 1105,
1090 cmꢁ1. HR-ESIMS calcd for C34H50O5Si (MþNa)þ: m/z 589.3320,
found: 589.3305.
J¼7.1 Hz), 7.58–7.38 (5H, m), 7.34 (4H, t, J¼7.5 Hz), 5.17 (1H, d,
J¼2.8 Hz), 4.10 (1H, d, J¼8.4 Hz), 3.93 (1H, quint, J¼6.0 Hz), 3.60
(3H, s), 3.51–3.46 (2H, m), 1.89–1.82 (1H, m), 1.76 (1H, d, J¼11.6 Hz),
1.68–1.59 (2H, m), 1.40 (3H, d, J¼5.5 Hz), 1.39 (3H, s), 1.27 (3H, s),
1.25–1.10 (2H, m), 1.01 (9H, s), 0.90–0.88 (1H, m). (R)-MTPA ester:
4.12. (3R)-1-tert-Butyldiphenylsiloxy-3-[(1S,2RS,3S,4R)-1-
methoxy-2-allyloxy-3,4-isopropylenedioxypentyl]-
cyclohexanone (29)
1H NMR (CDCl3):
d
7.63 (4H, d, J¼6.6 Hz), 7.59–7.52 (2H, m), 7.42–
7.39 (5H, m), 7.34 (4H, t, J¼6.7 Hz), 5.20 (1H, d, J¼3.2 Hz), 4.08 (1H,
d, J¼8.2 Hz), 3.91 (1H, dq, J¼8.4, 6.0 Hz), 3.53–3.50 (2H, m), 3.52
(3H, s), 1.88–1.75 (3H, m), 1.66–1.63 (1H, m), 1.43–1.41 (1H, m), 1.38
(3H, s), 1.37 (3H, d, J¼5.8 Hz), 1.25 (3H, s), 1.26–1.21 (2H, m), 1.03
(9H, s), 0.99–0.93 (1H, m).
A mixture of the above compound (937 mg, 1.65 mmol) and
NH4F (3.06 g, 82.7 mmol) in dry methanol (20 mL) was heated
under reflux for 33 h. The mixture was cooled to room temperature,
diluted with water (100 mL), and extracted with diethyl ether
(150 mLꢂ2). The organic layers were washed with brine, dried over
MgSO4, and evaporated. The crude product was chromatographed
on a silica gel column (hexane/AcOEt¼1:1) to give the corre-
sponding hydroxyl compound (515 mg, 95%) as a colorless oil,
which was used for the next reaction without further purification. A
solution of the above compound (210 mg, 0.64 mmol) in dry CH2Cl2
(10 mL) was added into a suspension of PCC (374 mg, 1.73 mmol)
and Celite (1.0 g) in dry CH2Cl2 (10 mL) under argon atmosphere,
and the mixture was stirred for 2 h at room temperature. Celite
(1.0 g) and diethyl ether (20 mL) were added into the mixture, and
the whole was filtered through a Celite column. The filtrate was
evaporated to give a crude oil, which was chromatographed on
4.10. (3R)-1-tert-Butyldiphenylsiloxy-3-[(1S,3S,4R)-1-
methoxy-3,4-isopropylenedioxy-2-oxopentyl]cyclohexane
Proton sponge (11.3 g, 52.9 mmol) and (CH3)3O$BF4 (7.82 g,
52.9 mmol) were added into a solution of 28 (2.7 g, 5.29 mmol) in
dry CH2Cl2 (100 mL), and the mixture was stirred for 30 min at
room temperature. The mixture was quenched by the addition of
brine (250 mL) and extracted with diethyl ether (250 mLꢂ2). The
organic layers were washed successively with aqueous 10% HCl
(250 mL), water (250 mL), and brine (250 mL), dried over MgSO4,
and evaporated. The crude product was chromatographed on a sil-
ica gel column (hexane/AcOEt¼7:1) to produce the title compound
20
(2.58 g, 93%) as a colorless oil. [
a
]
ꢁ15.8 (c 1.71, CHCl3). 1H NMR
a silica gel column (hexane/AcOEt¼5:1) to give 29 (204 mg, 98%) as
D
20
(CDCl3):
d
7.66–7.61 (4H, m), 7.41–7.32 (6H, m), 4.04 (1H, d,
a colorless oil. [
a
]
D
þ11.9 (c 2.2, CHCl3). 1H NMR (CDCl3):
d 5.89–
J¼8.0 Hz), 3.93–3.88 (1H, m), 3.74 (1H, d, J¼4.1 Hz), 3.58–3.53 (1H,
m), 3.32 (3H, s), 1.81–1.77 (1H, m), 1.72–1.62 (2H, m), 1.55–1.53 (1H,
m), 1.46–1.38 (1H, m), 1.40 (3H, s), 1.36–1.20 (3H, m), 1.32 (3H, d,
J¼6.0 Hz), 1.29 (3H, s), 1.03 (9H, s), 0.91–0.86 (1H, m). 13C NMR
5.79 (1H, m), 5.24 (1H, dd, J¼1.5, 17.1 Hz), 5.14 (1H, dd, J¼1.4,
10.4 Hz), 4.12–4.05 (2H, m), 3.99–3.93 (1H, m), 3.68 (1H, dd, J¼1.7,
8.6 Hz), 3.43 (3H, s), 3.28 (1H, dd, J¼1.6, 8.7 Hz), 3.18 (1H, dd, J¼2.1,
8.8 Hz), 2.48–2.32 (3H, m), 2.30–2.16 (2H, m), 2.12–2.05 (1H, m),
1.85–1.82 (1H, m), 1.67–1.55 (2H, m), 1.39 (3H, s), 1.38 (3H, s), 1.29
(CDCl3): d 135.7, 134.6, 129.5, 127.4, 109.9, 88.2, 84.7, 74.2, 72.0, 59.0,
39.1, 37.9, 35.4, 28.3, 26.9, 26.2, 25.7, 19.0, 18.3. IR (neat): 1724, 1427,
(3H, d, J¼6.0 Hz). 13C NMR (CDCl3):
d 211.5, 45.8, 134.2, 117.1, 107.9,
1371, 1067 cmꢁ1
547.2850, found: 547.2856.
.
HR-ESIMS, Calcd for C31H44O5Si (MþNa)þ:
83.7, 81.9, 75.7, 73.5, 72.2, 60.9, 41.3, 39.9, 27.3, 26.8, 24.3, 17.2. IR
(neat): 1713, 1379, 1225, 1087 cmꢁ1. HR-ESIMS calcd for C18H30O5
(MþNa)þ: m/z 349.1985, found: 349.1986.
4.11. (3R)-1-tert-Butyldiphenylsiloxy-3-[(1S,2RS,3S,4R)-1-
methoxy-2-allyloxy-3,4-isopropylenedioxypentyl]cyclohexane
4.13. (3R)-1-tert-Butyldiphenylsiloxy-3-[(1S,2RS,3S,4R)-1-
methoxy-2-allyloxy-3,4-isopropylenedioxypentyl]-2-
phenylthiocyclohexanone
NaBH4 (124 mg, 3.28 mmol) was added portion-wise to a solu-
tion of the above compound (1.15 g, 2.19 mmol) and CeCl3$7H2O
(814 mg, 2.19 mmol) in methanol (25 mL) at 0 ꢀC under argon at-
mosphere, and the mixture was stirred for 3 h at room tempera-
ture. The reaction mixture was quenched by the addition of
saturated aqueous NH4Cl (200 mL) and extracted with AcOEt
(250 mLꢂ2). The organic layers were washed successively with
water and brine, dried over Na2SO4, and evaporated. The crude
The title compound was obtained (219 mg) in 81% yield from 29
(204 mg, 0.63 mmol) by a similar procedure as described in the
20
synthesis of 16. [
a
]
þ1.85 (c 0.65, CHCl3). 1H NMR (CDCl3):
d 7.42–
7.38 (2H, m), 7.31–7.21 (3H, m), 5.93–5.81 (1H, m), 5.26 (1H, d,
J¼17.2 Hz), 5.16 (1H, d, J¼10.4 Hz), 4.19–4.05 (2H, m), 4.01–3.96
(1H, m), 3.75–3.69 (1H, m), 3.49 (3H, s), 3.32–3.30 (1H, m), 3.25–