1054 J . Org. Chem., Vol. 63, No. 4, 1998
Hanessian and Grillo
4.5 Hz, 1H), 3.64 (dd, J ) 10.7, 4.5 Hz, 1H), 2.08-1.88 (m,
4H), 1.07 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 172.8, 153.4,
135.5, 133.5, 129.6, 127.6, 122.5, 84.7, 80.7, 77.8, 66.1, 27.5,
On allowing the solution to warm to rt, a slurry formed which
was filtered under reduce pressure and washed repeatedly
with hot EtOAc. The filtrates were concentrated under
reduced pressure and passed through a short silica plug
(hexane:EtOAc 4:1). Removal of the eluant under reduced
pressure gave the lactol (1.79 g, 94%) as a colorless oil. To a
solution of lactol (1.79 g, 4.2 mmol) in CH2Cl2 (42 mL) was
added a catalytic amount of PhCO2H followed by Ph3PdCHCO2-
Me (1.82 g, 5.46 mmol) in one portion. The reaction mixture
was stirred for 12 h at rt, the solvent was evaporated, and the
residue was purified by column chromatography (hexane:
EtOAc 5:1) to give 9 (1.52 g, 85%) as a colorless oil: [R]D +1.34
t
26.8, 20.9, 19.2; EIMS (m/z) 421 (M - 1), 365, (M - Bu);
HRMS calcd for C25H29O4Si (M - 1) 421.18350, found 421.18450.
5: 1H NMR (400 MHz, CDCl3) δ 7.70-7.65 (m, 4H), 7.42-
7.37 (m, 7H), 6.10 (dd, J ) 5.7, 2.0 Hz, 1H), 5.05 (m, 1H), 4.20
(m, 1H), 4.06 (m, 1H), 3.65 (m, 2H), 2.10-1.70 (m, 4H), 1.04
(s, 9H).
(2S ,2′S ,5′S )-5-(5′-(((t er t -B u t y l-d ip h e n y l-s ily la n y l)-
oxy)m eth yl)tetr a h yd r o[2,2′]bifu r a n yl-5-on e (6). A mix-
ture of 2 (6.18 g, 14.64 mmol) and Pd/C (0.5 g, 5%) in EtOAc
(30 mL) was stirred under 1 atm of pressure of hydrogen for
5 h. Filtration of the mixture through Celite followed by
solvent removal under reduced pressure gave the desired
product 6 (6.20 g, quantitative) as a colorless oil, which
crystallized on standing: mp 76-77 °C; [R]D +4.0 (c 0.075,
1
(c 0.87, CHCl3); IR (CHCl3) 3600-3400, 1728 cm-1; H NMR
(400 MHz, CDCl3) δ 7.72-7.69 (m, 10H), 7.0 (dt, J ) 15.6, 7.1,
6.7 Hz, 1H), 5.87 (d, J ) 15.6 Hz, 1H), 4.15 (m, 1H), 3.85 (m,
1H), 3.71 (s, 3H), 3.67 (dd, J ) 4.6, 2.0 Hz, 2H), 2.57 (brs, OH),
2.45 (m, 1H), 2.28 (m, 1H), 1.55 (m, 2H), 1.08 (s, 9H); 13C NMR
(100 MHz, CDCl3) δ 166.9, 148.9, 135.5, 133.5, 129.5, 127.5,
121.1, 82.2, 79.8, 71.1, 66.4, 51.2, 31.0, 28.6, 27.9, 26.8, 26.7,
19.1; EIMS (m/z) 483 (M + 1), 460, 425, 405, 306, 153, (100.0);
HRMS calcd for C28H39O5Si (M + 1) 483.2566, found 483.25510.
1
CHCl3); IR (CHCl3) 1775 cm-1; H NMR (400 MHz, CDCl3) δ
7.71-7.67 (m, 4H), 7.45-7.36 (m, 6H), 4.47 (m, 1H), 4.13 (m,
1H), 4.05 (m, 1H), 3.68 (dd, J ) 10.7, 4.4 Hz, 1H), 3.64 (dd, J
) 6.5, 4.4 Hz, 1H), 2.69 (m, 1H), 2.43 (m, 1H), 2.24 (m, 2H),
2.07-1.82 (m, 4H), 1.05 (s, 9H); 13C NMR (100 MHz, CDCl3) δ
177.6, 135.5, 135.6, 129.5, 127.5, 127.6, 81.0, 80.9, 80.4, 66.2,
28.0, 27.8, 27.7, 26.7, 24.6, 19.1; EIMS (m/z) 423 (M - 1), 367;
HRMS calcd for C25H31O4Si (M - 1) 423.19916, found 423.19740.
(2R ,2′S ,5′S )-5′-(((t er t -B u t y ld ip h e n y ls ila n y l)o x y )-
m eth yl)tetr a h yd r o[2,2′]bifu r a n yl-5-on e (8). A mixture of
3 and 4 (4.56:1 ratio, 6.60 g, 15.64 mmol) and Pd/C (0.5 g, 5%)
in EtOAc (30 mL) was stirred under 1 atm of pressure of
hydrogen for 5 h. Filtration of the mixture through Celite
followed by solvent removal under reduced pressure gave a
mixture of 8 and its 4S,5R-erythro isomer 7 (6.63 g, quantita-
tive). Column chromatography (10% EtOAc:hexane) gave the
pure trans-erythro compound 8 (5.0 g, 92%) as a colorless oil
and the cis-4S,5R-erythro compound 7 (1.04 g) as a colorless
(2′S,5′S,6R)-6-((Ben zyloxy)m eth oxy)-6-[5′-(((ter t-bu tyl-
d ip h e n ylsila n yl)oxy)m e t h yl)t e t r a h yd r ofu r a n -2′-yl]-
h exa n oic Acid Meth yl Ester (10). A mixture of 10% Pd/C
(0.12 g) and 9 (1.52 g, 3.15 mmol) in EtOAc (3 mL) was stirred
for 5 h at rt. The mixture was filtered through Celite, washed
with EtOAc, and concentrated to afford the product (1.5 g,
quantitative) as a colorless oil: [R]D +33.3 (c 1.68, CHCl3); IR
1
(CHCl3) 1740 cm-1; H NMR (400 MHz, CDCl3) δ 7.70-7.67
(m, 4H), 7.38-7.31 (m, 6H), 4.1 (m, 1H), 3.85 (m, 1H), 3.64
(m, 2H), 3.60 (m, 1H), 3.60 (s, 3H), 2.70 (brs OH), 2.28 (t, J )
7.4 Hz, 2H), 1.98-1.41 (m, 10H), 1.05 (s, 9H); 13C NMR (100
MHz, CDCl3) δ 174.0, 135.5, 133.5, 129.5, 127.5, 85.2, 79.8,
71.1, 66.4, 51.2, 34.0, 33.0, 27.9, 26.8, 26.7, 19.1; EIMS (m/z)
485 (M + 1), 467, 135 (100.0); HRMS calcd for C28H41O5Si (M
+ 1) 485.27234, found 485.27370.
oil: For 8: [R]D -3.9 (c 0.28, CHCl3); IR (CHCl3) 1780 cm-1
;
1H NMR (400 MHz, CDCl3) δ 7.76-7.70 (m, 4H), 7.43-7.36
(m, 6H), 4.41 (m, 4H), 4.14 (m, 1H), 3.68 (dd, J ) 10.7, 4.5 Hz,
1H), 3.64 (dd, J ) 10.7, 4.5 Hz, 1H), 2.53 (m, 2H), 2.30 (m,
1H), 2.20-1.80 (m, 3H), 1.73 (m, 1H), 1.06 (s, 9H); 13C MNR
(100 MHz, CDCl3) δ 177.0, 135.5, 133.4, 129.5, 127.5, 81.6,
80.2, 80.1, 66.2, 28.2, 28.0, 27.5, 26.7, 23.8, 19.1; EIMS (m/z)
BOMCl (4.39 mL, 31.5 mmol) was added to a solution of
the above product (1.7 g, 3.51 mmol) and DIPEA (5.5 mL, 31.5
mmol) in CH2Cl2 (35 mL) at 0 °C. The mixture was stirred
for 48 h at 0 °C, quenched with saturated aqueous NH4Cl, and
extracted with CH2Cl2. The organic layer was washed several
times with water and brine and then dried (Na2SO4). Filtra-
tion and evaporation of the solvent afforded the crude mixture
which was chromatographed on a silica gel column (hexane:
EtOAc 6:1) to give 10 (1.37 g, 65%) as a colorless oil: [R]D
t
423 (M - 1), 367 (M - Bu), for 347. For 7: 1H NMR (400
MHz, CDCl3) δ 7.71-7.67 (m, 4H), 7.45-7.36 (m, 6H), 4.48
(m, 1H), 4.11 (m, 1H), 4.05 (m, 1H), 3.68 (dd, J ) 10.7, 4.4 Hz,
1H), 3.64 (dd, J ) 6.5, 4.4 Hz, 1H), 2.70-2.52 (m, 1H), 2.50
(m, 2H), 2.49-2.35 (m, 1H), 1.85 (m, 4H), 1.05 (s, 9H).
In tr a m olecu la r Mitsu n obu Rea ction (8 fr om 6). To a
stirring solution of 6 (100 mg, 0.235 mmol) in THF:H2O (10:1,
11 mL) was added LiOH (13 mg, 0.54 mmol) in one portion at
0 °C. Stirring was continued for 1 h until TLC analysis
indicated the absence of the starting material. Prewashed
Amberlite IR-120 resin (H+) was added to the aqueous phase
until pH ∼4 was attained. The mixture was filtered, and the
aqueous phase was repeatedly extracted with CH2Cl2. The
combined organic phases were dried (Na2SO4), and the solvent
was removed under reduced pressure. The residue was further
dried over P2O5 under reduced pressure for 1 h to afford the
crude ω-hydroxy acid intermediate as a viscous oil (95.5 mg,
0.216 mmol). A solution of Ph3P (170 mg, 0.648 mmol) in THF
(1 mL) was added to a solution of this intermediate in THF
(11.7 mL) at 0 °C followed by the dropwise addition of DEAD
(0.1 mL, 2.97 mmol), and the yellow solution was stirred for a
further 30 min. Evaporation of the solvent followed by column
chromatography (hexane:EtOAc 9:1) gave a 13:1 inseparable
mixture of 8 and 6 (80 mg, 86%).
1
+10.68 (c 0.51, CHCl3); IR (CHCl3) 1740 cm-1; H NMR (400
MHz, CDCl3) δ 7.80-7.76 (m, 4H), 7.48-7.31 (m, 6H), 4.94
(d, J ) 6.88 Hz, 1H), 4.84 (d, J ) 6.88 Hz, 1H), 4.71 (d, J )
11.8 Hz, 1H), 4.66 (d, J ) 11.8 Hz, 1H), 4.14 (m, 1H), 4.06 (m,
1H), 3.70 (m, 1H), 3.69 (m, 2H), 3.68 (s, 3H), 2.33 (t, J ) 7.3
Hz, 2H), 2.15-1.85 (m, 4H), 1.84-1.31 (m, 6H), 1.10 (s, 9H);
13C NMR (100 MHz, CDCl3) δ 174.0, 137.9, 135.6, 133.6, 129.5,
128.3, 127.7, 127.6, 94.6, 81.4, 79.6, 78.7, 69.5, 66.5, 51.4, 33.9,
31.4, 28.2, 26.8, 25.2, 25.1, 19.2; HRMS calcd for C36H49O6-
SiNa 627.31177, found 627.31400.
(1′′S ,2′S ,5′S ,6R )-6-((B e n zy lo x y )m e t h o x y )-6-[5′-(1′′-
h yd r oxyt r id ecyl)t et r a h yd r ofu r a n -2′-yl]h exa n oic Acid
Meth yl Ester (11) a n d Isom er (12). To a solution of 10 (0.87
g, 1.45 mmol) in THF (29 mL) at 0 °C was added a solution of
n-Bu4NF (5.8 mL, 1.0M, 5.8 mmol) in THF, and the mixture
was stirred for 3 h at rt, then quenched with saturated aqueous
NH4Cl, and diluted with ether and the organic layer was
washed with water and brine and dried (Na2SO4). Filtration
and evaporation of the solvent followed by column chroma-
tography gave the expected alcohol (0.5 g, quantitative) as a
colorless oil: [R]D +19 (c 0.105, CHCl3); IR (CHCl3) 3695-3460,
(2′S ,5′S ,6R )-6-[5′-(((t er t -Bu t yld ip h e n ylsila n yl)oxy)-
m eth yl)tetr ah ydr ofu r an -2′-yl]-6-h ydr oxyh ex-2-en oic Acid
Meth yl Ester (9). A solution of DIBAL-H (4.18 mL, 1.5 M,
6.2 mmol) in toluene was added dropwise to a stirring solution
of 8 (1.9 g, 4.48 mmol) in toluene (22 mL) at -78 °C. The
solution was stirred at -78 °C for 1 h. Methanol (6 mL) was
added dropwise at -78 °C, and the solution was stirred for 20
min before being allowed to warm to 0 °C. Ethyl acetate (10
mL) was added followed by the addition of water (2 drops).
1
1735 cm-1; H NMR (400 MHz, CDCl3) δ 7.33-7.26 (m, 5H),
4.87 (d, J ) 6.88 Hz, 1H), 4.6 (m, 2H), 4.04 (m, 1H), 3.99 (m,
1H), 3.73 (m, 1H), 3.62 (s, 3H), 3.61 (m, 1H), 3.50 (m, 1H),
2.27 (t, J ) 7.4 Hz, 2H), 1.95-1.88 (m, 3H), 1.68-1.30 (m, 7H);
13C NMR (100 MHz, CDCl3) δ 173.9, 137.8, 128.2, 127.6, 127.5,
94.5, 81.2, 79.7, 78.4, 69.5, 64.7, 51.3, 33.8, 31.1, 27.5, 26.6,
25.0, 24.9; EIMS (m/z) 367 (M + 1), 338, 259 (100.0); HRMS
calcd for C20H31O6 (M +1 ) 367.21280, found 367.21207.