â-Hydroxy-γ-lactones
J . Org. Chem., Vol. 66, No. 4, 2001 1427
(m, 3H), 1.87 (dd, J ) 6.7, 1.5 Hz, 1H), 2.69 (br s, 2H), 2.87
(dd, J ) 6.8, 3.7 Hz, 1H), 3.70 (ddd, J ) 2.9, 1.8, 1.8 Hz, 1H),
4.13 (dd, J ) 4.2, 2.2 Hz, 1H), 4.35 (s, 1H), 7.35-7.44 (m, 6H),
7.66-7.68 (m, 4H); 13C NMR (CDCl3) δ 14.0 (q), 19.4 (s), 22.6
(t), 26.1 (t), 26.9 (q), 29.5 (t), 32.0 (t), 38.1 (t), 44.5 (t), 54.2 (d),
74.4 (d), 75.7 (d), 84.1 (d), 127.6 (d), 127.7 (d), 129.7 (d), 129.8
(d), 133.5 (s), 134.4 (s), 135.5 (d), 135.8 (d), 135.9 (d); IR (CHCl3)
ν˜max (cm-1) 3684, 3019, 2400, 1522, 1230, 928; MS (m/z relative
intensity) 381 (M - Bu-t)+ (18), 311 (63), 199 (100). Anal. Calcd
for C27H38O3Si: C, 73.92; H, 8.73. Found: C, 73.94; H, 8.93.
P r ep a r a tion of (1R)-1-[(4S,5S,2R)-4-(ter t-Bu tyl-d ip h en -
yl-silan yloxy)-5-pen tyl-tetr ah ydr o-fu r an -2-yl]-dec-9-en -1-ol
(4). To a mixture of CuI (cat.) in dry THF (2.5 mL) under argon
atmosphere was added n-C8H15BrMg (0.38 mL, 1 M in THF,
0.38 mmol) at -30 °C. The mixture was stirred for 10 min,
and the epoxide 17 (110 mg, 0.25 mmol) was added slowly.
TLC showed almost instant conversion. The reaction was
quenched with a saturated aqueous solution of NH4Cl. The
layers were partitioned, and the aqueous phase was extracted
with Et2O. The combined organic layers were dried, filtered,
and concentrated to yield a crude oil that was used in the next
reaction without purification.
4.2, 4.2 Hz, 1H), 4.34 (dd, J ) 8.8, 4.3 Hz, 1H), 7.35-7.46 (m,
6H), 7.65-7.67 (m, 4H); 13C NMR (CDCl3) δ 14.0 (q), 19.3 (s),
22.6 (t), 26.1 (t), 27.0 (q), 29.8 (t), 32.0 (t), 38.0 (t), 43.9 (t),
54.4 (d), 73.8 (d), 78.6 (d), 83.6 (d), 127.6 (d), 129.8 (d), 133.5
(s), 134.4 (s), 135.9 (d); IR (CHCl3) (cm-1) 3650, 3300, 2900,
1590, 1350, 1100; MS (m/z relative intensity) 381 (M - Bu-t)+
(18), 311 (11), 199 (100); HRMS calcd for C23H29O3Si (M - Bu-
t) 381.18860, found 381.18719.
P r ep a r a tion of (1S)-1-[(4S,5S,2S)-4-(ter t-Bu tyl-d ip h en -
yl-silan yloxy)-5-pen tyl-tetr ah ydr o-fu r an -2-yl]-dec-9-en -1-ol
(5). Obtained from 21 (147 mg, 0.33 mmol) as described above
for 4 from 17, affording 5 (81 mg, 78% yield) as a white solid:
mp 35-37 °C; [R]25 ) +20.5 (c 0.4, CHCl3); 1H NMR (CDCl3)
D
δ 0.88 (dd, J ) 6.4, 6.4 Hz, 3H), 1.24-1.33 (m, 18 H), 1.50-
1.65 (m, 4H), 1.83 (dd, J ) 14.1, 3.4 Hz, 1H), 2.02 (dd, J )
13.0, 6.6 Hz, 2H), 2.36 (ddd, J ) 14.0, 10.0, 5.5 Hz, 1H), 3.46
(ddd, J ) 8.0, 5.0, 2.5 Hz, 1H), 3.61 (ddd, J ) 7.0, 7.0, 2.7 Hz,
1H), 3.93 (dd, J ) 9.8, 5.4 Hz, 1H), 4.03 (dd, J ) 5.4, 2.7 Hz,
1H), 4.92 (d, J ) 10.0 Hz, 1H), 4.98 (d, J ) 17.0 Hz, 1H), 5.80
(dddd, J ) 17.0, 10.0, 7.0, 7.0 Hz, 1H); 13C NMR (CDCl3) δ
14.0 (q), 22.6 (t), 26.0 (t), 28.7 (t), 28.9 (t), 29.0 (t), 29.4 (t),
29.5 (t), 29.7(t), 32.0 (t), 33.7 (t), 34.3 (t), 38.7 (t), 71.5 (d), 73.9
To a stirred mixture of the crude in THF (2.5 mL) was added
tetra-n-butylammonium fluoride (0.36 mL, 1 M in THF, 0.36
mmol). The mixture was stirred until TLC showed no remain-
ing silyl ether. The residue was diluted with Et2O (5 mL), and
H2O (5 mL) was added. The resulting mixture was extracted
with Et2O. The combined organic layers were dried, filtered,
and concentrated. Silica gel flash chromatography of the
(d), 79.1 (d), 84.3 (d), 114.1 (t), 139.1 (d); IR (CHCl3) ν˜max (cm-1
)
3684, 2930, 2400, 1520, 1230, 1045; MS (m/z relative intensity)
297 (M - CH3)+ (4), 187 (4), 157 (100). Anal. Calcd for
C
19H36O3: C, 73.03; H, 11.61. Found: C, 73.08; H, 11.53.
P r epar ation of Meth yl (2E)(5R,6R)-8-Ben zyloxy-5-(ter t-
bu tyl-d ip h en yl-sila n yloxy)-6-h yd r oxy-oct-2-en oa te (33).
The procedure used above to obtain 25 from 24 was applied
to 13 on a 5.82 g (12.26 mmol) scale, yielding 33 (5.98 g, 89%
yield) as a colorless oil: [R]25D ) -16.65 (c 2.7, CHCl3); 1H NMR
(CDCl3) δ 1.06 (s, 9H), 1.24 (dd, J ) 7.0, 7.0 Hz, 3H), 1.77 (ddd,
J ) 5.8, 5.8, 5.8 Hz, 2H), 2.25 (ddd, J ) 14.0, 7.1, 6.4 Hz, 1H),
2.53 (ddd, J ) 14.0, 7.1, 6.4 Hz, 1H), 2.49 (ddd, J ) 9.1, 5.8,
5.8 Hz, 1H), 3.60-3.71 (m, 2H), 3.77 (ddd, J ) 6.4, 6.4, 3.8
Hz, 1H), 4.13 (ddd, J ) 7.0, 7.0, 7.0 Hz, 2H), 4.46 (s, 2H), 5.66
(d, J ) 15.4 Hz, 1H), 6.77 (ddd, J ) 15.4, 7.1, 7.1 Hz, 1H),
7.25-7.45 (m, 11H), 7.64-7.67 (m, 4H); 13C NMR (CDCl3) δ
14.2 (q), 19.4 (s), 27.1 (q), 32.6 (t), 35.7 (t), 60.0 (t), 68.5 (t),
72.0 (d), 73.2 (t), 75.0 (d), 123.6 (d), 127.6 (d), 127.7 (d), 128.4
(d), 129.8 (d), 129.9 (d), 132.9 (s), 133.5 (s), 135.9 (d), 138.1
(s), 145.0 (d), 166.2 (s); IR (film) ν˜max (cm-1) 3450, 2900, 1710,
1100; MS m/ z (relative intensity) 489 (M - Bu-t)+ (0.3), 275
(12), 207 (14), 91 (100). Anal. Calcd for C33H42O5Si: C, 72.49;
H, 7.74. Found: C, 72.49; H, 7.99.
P r ep a r a tion of (2E)(5R,6R)-8-Ben zyloxy-5-(ter t-bu tyl-
d ip h en yl-sila n yloxy)-oct-2-en e-1,6-d iol (34). The procedure
used above to obtain 19 from 25 was applied to 33 on a 5.98
g (10.93 mmol) scale, yielding 34 (4.53 g, 82% yield) as an oil:
[R]25D ) -8.28 (c 0.25, CHCl3); 1H NMR (CDCl3) δ 1.05 (s, 9H),
1.77 (ddd, J ) 6.0, 6.0, 6.0 Hz, 2H), 2.11 (ddd, J ) 13.0, 6.5,
6.5 Hz, 1H), 2.37 (ddd, J ) 13.0, 6.5, 6.5 Hz, 1H), 2.55 (br s,
1H), 3.52 (ddd, J ) 9.0, 6.0, 6.0 Hz, 1H), 3.63 (ddd, J ) 9.0,
6.0, 6.0 Hz, 1H), 3.67-3.72 (m, 2H), 3.88 (d, J ) 4.7 Hz, 2H),
4.46 (s, 2H), 5.29-5.49 (m, 2H), 7.18-7.45 (m, 11H), 7.60-
7.68 (m, 4H);13C NMR (CDCl3) δ 19.5 (s), 27.1 (q), 33.0 (t), 35.9
(t), 63.5 (t), 68.3 (t), 71.5 (d), 73.1 (t), 75.8 (d), 127.5 (d), 127.6
(d), 127.7 (d), 128.4 (d), 128.6 (d), 129.7 (d), 129.9 (d), 131.8
(d), 133.4 (s), 133.9 (s), 135.9 (s), 135.9 (d), 138.2 (s); MS m/ z
(relative intensity) 447 (M - Bu-t)+ (5), 309 (19), 154 (70), 91
(100); IR (film) ν˜max (cm-1) 3350, 3050, 1415, 1100. Anal. Calcd
for C31H40O4Si: C, 73.77; H, 7.99. Found: C, 73.73; H, 8.16.
P r epar ation of (2S)-1-[(2R,4R,5R)-5-(2-Ben zyloxy-eth yl)-
4-(ter t-b u t yl-d ip h en yl-sila n yloxy)-t et r a h yd r o-fu r a n -2-
yl]-eth a n e-1,2-d iol (32). The procedure used above to obtain
26 from 19 was applied to 34 on a 1.4 g (2.77 mmol) scale,
yielding 32 (1.15 g, 80% yield) as a colorless oil: [R]25D ) +18.8
(c 1.84, CHCl3); 1H NMR (CDCl3) δ 1.10 (s, 9H), 1.77-1.88 (m,
1H), 1.90 (dd, J ) 9.0, 6.0 Hz, 2H), 1.95-2.02 (m, 1H), 2.44
(br s, 1H), 3.19 (br s, 1H), 3.50-3.61 (m, 4H), 3.75 (ddd, J )
9.5, 4.0, 4.0 Hz, 1H), 3.80-3.88 (m, 2H), 4.37 (ddd, J ) 4.7,
4.7, 4.7 Hz, 1H), 4.46 (br s, 2H), 7.25-7.47 (m, 11H), 7.61-
7.70 (m, 4H); 13C NMR (CDCl3) δ 19.3 (s), 27.1 (q), 30.2 (t),
35.6 (t), 63.8 (t), 67.7 (t), 72.8 (d), 72.9 (t), 74.0 (d), 78.4 (d),
79.7 (d), 127.6 (d), 127.7 (d), 127.8 (d), 128.3 (d), 129.9 (d), 133.2
residue afforded 4 (61 mg, 78% yield) as a white solid: mp
1
50-52 °C; [R]25 ) +15.2 (c 0.8, CHCl3); H NMR (CDCl3) δ
D
0.70 (dd, J ) 7.2, 7.2 Hz, 3H), 1.25-1.36 (m, 18H), 1.48-1.63
(m, 4H), 1.81 (ddd, J ) 13.3, 9.0, 4.3 Hz, 1H), 2.01 (dd, J )
13.0, 6.7 Hz, 2H), 2.33 (br s, 1H), 3.36 (d, J ) 5.6 Hz, 1H),
3.74 (ddd, J ) 7.0, 7.0, 2.5 Hz, 1H), 4.02 (dd, J ) 15.4, 6.7 Hz,
1H), 4.23 (s, 1H), 4.92 (d, J ) 10.0 Hz, 1H), 4.97 (d, J ) 17.0
Hz, 1H), 5.80 (dddd, J ) 17.0, 10.0, 7.0, 7.0 Hz, 1H); 13C NMR
(CDCl3) δ 14.0 (q), 22.5 (t), 25.6 (t), 25.9 (t), 28.8 (t), 28.9 (t),
29.0 (t), 29.4 (t), 29.6 (t), 31.9 (t), 33.1 (t), 33.7 (t), 37.9 (t),
73.4 (d), 74.1 (d), 80.2 (d), 82.5 (d), 114.1 (t), 139.2 (d); IR
(CHCl3) ν˜max (cm-1) 3684, 3620, 2930, 2400, 1522, 1046; MS
(m/z relative intensity) 312 (M)+ (2), 199 (3), 157 (100). Anal.
Calcd for C19H36O3: C, 73.03; H, 11.61. Found: C, 73.08; H,
12.10.
P r ep a r a tion of (2R)-2-[(4S,5S,2S)-4-(ter t-Bu tyl-d ip h en -
yl-sila n yloxy)-5-p en t yl-t et r a h yd r o-fu r a n -2-yl]-2-m et h -
a n esu lfon yloxy-eth yl Ben zoa te (30). The procedure used
above for the preparation of 28 from 26 was applied to 27 on
a 1.49 g (3.26 mmol) scale, giving 30 (1.56 g, 75% yield) as a
colorless oil: [R]25 ) +16.84 (c 1.8, CHCl3); 1H NMR (CDCl3)
D
δ 0.87 (dd, J ) 6.6, 6.6 Hz, 3H), 1.10 (s, 9H), 1.16-1.23 (m,
5H), 1.31-1.45 (m, 2H), 1.61-1.63 (m, 1H), 2.06 (d, J ) 6.7
Hz, 1H), 2.08 (dd, J ) 7.5, 2.4 Hz, 1H), 3.07 (s, 3H), 3.50 (dd,
J ) 8.6, 4.3 Hz, 1H), 3.94 (ddd, J ) 7.5, 7.5, 4.9 Hz, 1H), 4.34
(ddd, J ) 9.9, 9.9, 4.3 Hz, 1H), 4.45 (dd, J ) 12.4, 6.7 Hz, 1H),
4.68 (dd, J ) 12.4, 3.0 Hz, 1H), 5.12 (ddd, J ) 6.6, 4.5, 2.2 Hz,
1H), 7.35-7.46 (m, 8H), 7.57-7.70 (m, 5H), 8.03-8.06 (m, 2H);
13C NMR (CDCl3) δ 14.0 (q), 19.2 (s), 22.5 (t), 26.1 (t), 27.1 (q),
29.5 (t), 31.8 (t), 37.2 (t), 38.9 (q), 63.6 (t), 73.7 (d), 75.5 (d),
80.6 (d), 83.9 (d), 127.7 (d), 128.5 (d), 129.6 (d), 129.8 (d), 133.2
(d), 133.3 (d), 133.7 (s), 135.7 (d), 136.0 (d), 166.1 (s); IR (CHCl3)
ν˜max (cm-1) 3683, 3019, 2400, 1722, 1230, 929; MS (m/z relative
intensity) 581 (M - Bu-t)+ (100), 303 (33), 277 (79), 165 (90);
HRMS calcd for C31H37O7SiS (M - Bu-t)+ 581.20292, found
581.20341.
P r ep a r a tion of ter t-Bu tyl-[5-(2S)-oxir a n -2-yl)-(2S,3S,-
5S)-2-p en tyl-tetr a h yd r o-fu r a n -3-yloxy]-d ip h en yl-sila n e
(21). The procedure used above for the preparation of 17 from
28 was applied to 30 on a 1.53 g (2.4 mmol) scale, affording
21 (840 mg, 80% yield) as a colorless oil: [R]25 ) +4.83 (c
D
0.6, CHCl3); 1H NMR (CDCl3) δ 0.87 (dd, J ) 6.4, 6.4 Hz, 3H),
1.08 (s, 9H), 1.25 (br s, 4H), 1.44 (br s, 1H), 1.49-1.61 (m, 2H),
1.65-1.80 (m, 2H), 1.99 (ddd, J ) 13.4, 6.7, 6.7 Hz, 1H), 2.49
(br s, 1H), 2.72 (dd, J ) 4.4, 4.4 Hz, 1H), 3.14 (dd, J ) 3.0, 3.0
Hz, 1H), 3.43 (dd, J ) 14.2, 6.9 Hz, 1H), 3.58 (ddd, J ) 8.3,