give the title compound (1.88 g, crude) as an amber oil: 4.44 (dt,
2JHF = 47.3, 3JHH = 6.1, 2H), 3.39 (m, 2H), 1.93 (m, 2H), 1.6-1.8
(m, 2H), 1.3-1.6 (m, 8 H). 13C-NMR (75 MHz, CDCl3): 84.08 (d,
J = 163.3), 64.43, 30.32 (d, J = 19.3), 29.05, 28.86, 28.25, 25.08
(d, J = 5.2), 22.22. 19F NMR (282.4 MHz, CDCl3): -218.40.
dH2O (10 ml). The combined organic phases were washed with sat.
NaCl (10 ml), dried (Na2SO4) and concentrated in vacuo to yield
the title compound (2.97 g, 8.8 mmol, 85%) as a pale oil. TLC
1
(EtOAc–hexane 15 : 85): Rf 0.67; H-NMR (300 MHz, CDCl3):
3.60 (t, J = 6.6, 2 H), 3.42 (t, J = 6.8, 2 H), 1.86 (m, 2 H), 1.47-
1.59 (m, 2 H), 1.32 (m, 10H), 0.89 (s, 9 H), 0.05 (s, 6 H). 13C-NMR
(75 MHz, CDCl3): 63.29, 34.03, 32.86, 29.42, 29.33, 29.72, 28.17,
31.60, 25.77, 18.90, -5.24.
1,2:5,6-Di-O-isopropylidene-a-D-glucofuranosyl
(+)-(R)-8-
fluorooctanesulfinate. To diacetone-D-glucose (0.77 g, 2.9 mmol)
◦
in dry THF (12 ml) under N2 gas at -78 C was added pyridine
(0.29 ml, 3.5 mmol) followed by 8-fluorooctanesulfinyl chloride
(3.52 mmol). The mixture was stirred for 3 h (-78 ◦C). The
reaction was quenched dropwise with water (5 ml) then dissolved
in DCM (50 ml). The resulting mixture was washed with 5%
HCl (50 ml), 2% NaHCO3 (50 ml), and sat. NaCl (50 ml), then
dried over Na2SO4 and concentrated by roto-evaporation. The
title compound was obtained by flash chromatography (40%
Et2O–hexanes), to obtain a thick, pale oil (0.79 g, 1.8 mmol, 62%,
dr R : S: 91 : 9). [a]D21 = +1.39 deg cm3 g-1 dm-1(c 1.10, acetone).
TLC (EtOAc–hexane 1 : 1): Rf 0.70. IR (film): 2987, 2935, 2859,
1457, 1374, 1256, 1217, 1165, 1136, 1076, 1023, 955, 887, 837,
754, 730, 687 cm-1. 1H-NMR (300 MHz, CDCl3): 5.91 (d, J = 3.5,
tert-Butyl-[10-(8-fluoro-octane-1-(S)-sulfinyl)-decyloxy]-dime-
thylsilane. Freshly ground magnesium turnings (0.14 g,
5.9 mmol) were covered with dry THF (1.5 ml) under N2 gas. To
this mixture, was added (9-bromo-nonyloxy)-tert-butyldimethyl-
silane (1.49 g, 4.4 mmol) in dry THF (7 ml). The resulting mixture
was refluxed for 7 h and then cooled to room temperature.
In another vessel, the (R)-DAG sulfinate ester prepared above
(0.33 g, 0.77 mmol) was dissolved in toluene (16 ml) and cooled to
0 ◦C. To this solution was added a portion of the Grignard reagent
(4.5 ml, 2.6 mmol) and the reaction mixture was stirred for 30 min
at 0 ◦C, allowed to warm to room temperature and stirred for
24 h. The solution was quenched with sat. NH4Cl (10 ml) and then
extracted with DCM (2 ¥ 10 ml). The combined organic phases
were dried over Na2SO4 and concentrated by roto-evaporation.
The title compound was obtained by flash chromatography (60%
EtOAc–hexanes) to obtain a white solid (0.27 g, 0.61 mmol, 80%).
TLC (EtOAc–hexane 75 : 25): Rf 0.30. IR (KBr): 3434, 2927, 2854,
1636, 1471, 1388, 1361, 1256, 1103, 1017, 934, 837, 776, 726,
1H), 4.78 (d, J = 3.5, 1H), 4.71 (d, J = 1.2, 1H), 4.43 (dt, 2JHF
=
47.3, 3JHH = 6.1, 2H), 3.96-4.17 (m, 4H), 2.81 (2dt, J = 7.8, 13.4,
2H), 1.70 (m, 2H), 1.28-1.47 (m, 10H), 1.50 (s, 3H), 1.41 (s, 3H),
1.32 (s, 3H), 1.30 (s, 3H). 13C-NMR (75 MHz, CDCl3): 112.40,
109.42, 105.35, 84.07 (d, J = 163.1), 83.84, 83.05, 80.93, 72.14,
67.70, 57.86, 30.33 (d, J = 19.3), 29.09, 28.93, 28.66, 26.86, 26.74,
26.19, 25.29, 25.10 (d, J = 5.3), 21.03. 19F NMR (282.4 MHz,
CDCl3): -218.36 EI-MS: m/z 423 (27 [M - 15]+), 365 (3), 249 (7),
185 (19), 170 (14, [FC8H16SO]+), 127 (28, [C6H7O3]+), 101 (100,
[C5H9O2]+), 85 (13), 59 (20), 43 (39, [C2H3O]+); HR-EI-MS m/z
423.1851 ([M–CH3]+, C19H32O7FS requires 423.1853).
1
2
663 cm-1. H-NMR (300 MHz, CDCl3): 4.42 (dt, JHF = 47.3,
3JHH = 6.1, 2H), 3.58 (t, J = 6.6, 2H), 2.64 (m, 4H), 1.68-1.84
(m, 4H), 1.58-1.84 (m, 2H), 1.22-1.54 (m, 20H), 0.88 (s, 9H), 0.03
(s, 6H). 13C-NMR (75 MHz, CDCl3): 84.09 (d, J = 163.2), 63.26,
52.47, 52.38, 52.38, 32.82, 30.32 (d, J = 19.2), 29.33, 29.30, 29.15,
29.08, 28.94, 28.87, 28.76, 25.97, 25.97, 25.97, 25.74, 25.07 (d,
J = 5.3), 22.60, 22.58, 18.36, -5.27, -5.27. 19F NMR (282.4 MHz,
CDCl3): -218.36. EI-MS: m/z 419 (2 [M - OH]+), 379 (100, [M–t-
Bu]+), 359 (3), 199 (3), 101 (7), 89 (3), 75 (24), 69 (16), 55 (16), 41
(10).
1,2:5,6-Di-O-isopropylidene-a-D-glucofuranosyl (-)-(S)-8-fluoro-
octanesulfinate. Obtained as for 1,2:5,6-di-O-isopropylidene-a-
D-glucofuranosyl-(+)-(R)-8-fluorooctanesulfinate, except for the
solvent (toluene) and the base (i-Pr2NEt). (30% yield, dr R : S:
17 : 83). [a]2D1 = -36.2 deg cm3 g-1 dm-1 (c 1.20, acetone). TLC
(EtOAc–hexane 1 : 1): Rf 0.67. IR (film): 2988, 2934, 2859, 1714,
tert-Butyl-[10-(8-fluoro-octane-1-(R)-sulfinyl)-decyloxy]-dime-
thylsilane. Obtained as for tert-butyl-[10-(8-fluoro-octane-1-(S)-
sulfinyl)-decyloxy]-dimethylsilane, using (S)-DAG sulfinate ester
(69% yield). Structural data identical for that of tert-butyl-[10-(8-
fluoro-octane-1-(S)-sulfinyl)-decyloxy]-dimethylsilane.
1
1457, 1373, 1256, 1220, 1165, 1135, 1075, 1022, 830. H-NMR
(300 MHz, CDCl3): 5.91 (d, J = 3.6, 1H), 4.74 (d, J = 2.3, 1H),
4.60 (d, J = 3.7, 1H), 4.43 (dt, 2JHF = 47.3, 3JHH = 6.1, 2H), 3.98-
4.32 (m, 4H), 2.78 (m, 2H), 1.60-1.79 (m, 2H), 1.30-1.48 (m, 10H),
1.51 (s, 3H), 1.43 (s, 3H), 1.34 (s, 3H), 1.31 (s, 3H). 13C-NMR
(75 MHz, CDCl3): 112.46, 109.24, 104.97, 84.08 (d, J = 163.1),
83.61, 80.38, 79.21, 72.40, 66.71, 57.37, 30.32 (d, J = 19.5), 29.06,
28.92, 28.64, 26.74, 26.71, 26.27, 25.19, 25.10 (d, J = 5.3), 21.26.
19F NMR (282.4 MHz, CDCl3): -218.37 EI-MS: m/z 423 (31 [M -
15]+), 367 (4). 365 (3), 249 (3), 185 (17), 127 (30, [C6H7O3]+), 101
(100, [C5H9O2]+), 85 (12), 59 (19), 43 (44, [C2H3O]+); HR-EI-MS
m/z 423.1858 ([M–CH3]+, C19H32O7FS requires 423.1853).
10-(8-Fluoro-octane-1-(S)-sulfinyl)-decan-1-ol. To a solution
of (S)-OTBS-sulfoxide (18 mg, 0.041 mmol) in MeOH (1.4 ml) at
0 ◦C was added (1S)-(+)-10-camphorsulfonic acid (2 mg, 9 mmol)
with stirring. The resulting solution was stirred for 45 min. The
reaction was quenched with sat. NaHCO3 (3.5 ml) and extracted
with DCM (3 ¥ 2 ml). The extracts were dried (Na2SO4) and
dried under a gentle flow of N2 to obtain the title compound as
a white solid (11 mg, 0.033 mmol, 81%). TLC (EtOAc–hexane
75 : 25): Rf 0.03. IR (KBr): 3437, 2923, 2850, 1636, 1468, 1417,
1063, 1018, 932, 879, 727 cm-1. 1H-NMR (300 MHz, CDCl3): 4.43
(9-Bromo-nonyloxy)-tert-butyldimethylsilane.
9-Bromo-1-
nonanol (2.33 g, 10.4 mmol), tert-butyldimethylsilyl chloride
(1.85 g, 12.3 mmol) and imidazole (1.85 g, 27.1 mmol) were
combined and DMF (2.6 ml) was added. The mixture was stirred
at room temperature under N2 overnight. The resulting cloudy
yellow mixture was diluted with ether (10 ml) and washed with
sat. NaCl (10 ml). The organic phase was evaporated in vacuo and
the resulting oil was partitioned between hexanes (3 ¥ 10 ml) and
2
3
(dt, JHF = 47.3, JHH = 6.1, 2H), 3.63 (t, J = 6.5, 2H), 2.65 (m,
4H), 1.28-1.84 (m, 26H). 13C-NMR (75 MHz, CDCl3): 84.14 (d,
J = 163.0), 62.95, 52.44, 52.39, 52.39, 32.73, 30.33 (d, J = 19.3),
29.25, 29.25, 29.09, 29.09, 28.95, 28.82, 28.76, 25.67, 25.08 (d, J =
5.2), 22.59, 22.59. 19F NMR (282.4 MHz, CDCl3): -218.34. EI-MS
(pk intensity, fragment): m/z 305 (72 [M - OH]+), 157 (27), 143
This journal is
The Royal Society of Chemistry 2010
Org. Biomol. Chem., 2010, 8, 1322–1328 | 1327
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