5284 J. Agric. Food Chem., Vol. 48, No. 11, 2000
Rafin et al.
with a Matrex silica gel 60 Å (70-230 mesh, Merck). Solvents
and reagents were obtained from a commercial source (Ald-
rich).
194.2 (2C, CS), 98.4 (C-1), 72.3 (C-2), 71.8 (C-4), 69.5 (C-5),
60.8 (C-3), 49.3-46.4 (4C, CH ), 40.5 (C-6), 12.3, 11.4 (4C,
2
CH
3
CH CH ). Anal. Calcd for C16H O S N (442.68): C, 43.41; H,
2
3
30 4 4 2
Syn th esis of Bis[1,3-S-(N,N-d ieth yld ith ioca r ba m oyl)]-
,3-d id eoxyglycer ol (1). The synthesis of 1 was realized as
6.83; S, 28.97; N, 6.33. Found: C, 43.65; H, 6.95; S, 29.30; N,
6.24.
1
described previously (Len et al., 1996).
Syn t h esis of 1-S-(N,N-Diet h yld it h ioca r b a m oyl)-DL-
glycer ol (4). The synthesis of 4 was realized as described
previously (Len et al., 1996).
Syn th esis of 3,6-Did eoxybis[3,6-S-(N,N-d ieth yld ith io-
ca r ba m oyl)]-1,2-O-isop r op ylid en e-r-D-glu cofu r a n ose (2).
3
-Deoxy-3-iodo-1,2:5,6-di-O-isopropylidene-R-D-allofuranose (7.0
Syn th esis of 2-O-Acetyl-1,3-d id eoxy-1,3-d i-S-(N,N-d i-
eth yld ith ioca r ba m oyl)glycer ol (5). 1 (10.0 g, 28.2 mmol)
was dissolved in acetic anhydride/triethylamine (3:2) (100 mL)
at room temperature for 2 h. After the addition of MeOH, the
solvent was removed under reduced pressure. The crude
product was purified on a silica gel column eluted with hexane/
g, 18.9 mmol) (Garegg et al., 1980) was reacted with 0.6 M
HCl in water/dioxane (7:93, 65 mL) at 30 °C during 30 min.
After the addition of sodium hydrogen carbonate (pH 7), the
mixture was stirred for 10 min and filtered, and the solvent
was removed under reduced pressure. The crude product was
purified on a silica gel column eluted with hexane/acetone (1:
1
acetone (98:2) to give 8.8 g (79% yield) of 5: H NMR δ 5.31
1
) to give 4.0 g (64% yield) of 3-deoxy-3-iodo-1,2-O-isopropyl-
2 3
(m, 1 H, H-2), 3.94 (dt, 4H, J 1′a,1′b ) 13.7 Hz, CH CH ), 3.83
2
2
idene-R-D-allofuranose: mp 110-111 °C; [R]
D
+113° (c 1.2,
(m, 2H, J 1a,1b ) J 3a,3b ) 14.3 Hz, J 1a,2 ) J 2,3a ) 4.7 Hz, H-1a,
1
CHCl
3
); H NMR δ 5.76 (d, 1H, J 1,2 ) 3.6 Hz, H-1), 4.57 (t,
H-3a), 3.69 (dt, 4H, J 1′′a,1′′b ) 13.6 Hz, CH
2
CH
3
), 3.53 (dd, 2H,
1
(
3
H, J 2,3 ) 4.2 Hz, H-2), 4.25 (dd, 1H, J 4,5 ) 2.9 Hz, H-4), 4.00
J
1b,2 ) J 2,3b ) 6.9 Hz, H-1b, H-3b), 1.21 (m, 12H, J 1′,2′ ) 6.8
13
m, 1H, J 5,6 ) 7.2 Hz, H-5), 3.88 (dd, 1H, J 3,4 ) 10.2 Hz, H-3),
Hz, J 1′′,2′′ ) 6.6 Hz, CH
2
CH
3
); C NMR δ 194.1 (2C, CS), 169.8
CH ), 39.7 (C-1,C-3), 21.0
.83 (dd, 1H, J 6,6′ ) 11.5 Hz, H-6), 3.68 (dd, 1H, J 5,6′ ) 3.9 Hz,
(CO), 70.6 (C-2), 49.8, 46.7 (CH
2
3
1
3
H-6′), 1.45, 1.27 [s, 6H, C(CH
3
)
2
]; C NMR δ 111.8 [C(CH
3
)
2
],
3 2 3
(CH ), 12.5,11.5 (4C, CH CH ).
1
(
03.0 (C-1), 83.5 (C-2), 81.5 (C-4), 71.5 (C-5), 63.4 (C-6), 26.5
2C, C(CH ), 18.7 (C-3).
p-Toluenesulfonyl chloride (4.0 g, 21.2 mmol) dissolved in
Syn th esis of 2-O-Bu ta n oyl-1,3-d id eoxy-1,3-d i-S-(N,N-
d ieth yld ith ioca r ba m oyl)glycer ol (6). Butanoyl chloride
(1.5 g, 14.1 mmol) was added dropwise in a stirring solution
of 1 (5.0 g, 14.1 mmol) and triethylamine (2.2 mL, 15.5 mmol)
in toluene (40 mL) at room temperature. After 4.5 h, the
mixture was filtered and the solvent was removed under
reduced pressure. The crude product was purified on a silica
gel column eluted with hexane/acetone (98:2) to give 3.8 g (64%
yield) of 6: 1H NMR δ 5.33 (m, 1 H, H-2), 3.96 (dt, 4H, J 1′a,1′b
3 2
)
toluene (27 mL) was slowly added to a stirred pyridine (27
mL) solution of 3-deoxy-3-iodo-1,2-O-isopropylidene-R-D-allo-
furanose (7.0 g, 21.2 mmol) at 0 °C. After 48 h at 4 °C, crushed
ice and aqueous HCl (9:1) (50 mL) were added to the mixture
and the two phases separated. The aqueous phase was
extracted with toluene (2 × 25 mL); the organic phases were
pooled, dried (Na
2
SO
4
), and concentrated. The crude product
) 13.5 Hz, CH
1a,2 ) J 2,3a ) 4.7 Hz, H-1a, H-3a), 3.70 (dt, 4H, J 1′′a,1′′b ) 13.9
Hz, CH CH ), 3.55 (dd, 2H, J 1b,2 ) J 2,3b ) 7.1 Hz, H-1b, H-3b),
2.23 (t, 2H, J R,â ) 7.4 Hz, H-R), 1.60 (m, 2H, J â,γ ) 7.4 Hz,
H-â), 1.22 (m, 12H, J 1′,2′ ) 6.7 Hz, J 1′′,2′′ ) 6.8 Hz, CH CH ),
0.89 (t, 3H, J γ,ω ) 7.4 Hz, H-γ); 13C NMR δ 194.3 (2C, CS),
172.4 (CO), 70.6 (C-2), 49.8, 46.7 (CH CH ), 40.0 (C-1,C-3), 38.2
(C-R), 18.3 (C-â), 13.6 (C-γ), 12.5, 11.5 (4C, CH CH ).
2 3
CH ), 3.84 (m, 2H, J 1a,1b ) J 3a,3b ) 14.1 Hz,
was purified on a silica gel column eluted with hexane/acetone
4:1) to give 8.6 g (84% yield) of 3-deoxy-3-iodo-1,2-O-isopro-
J
(
2
3
2
2
pylidene-6-O-tosyl-R-D-allofuranose: [R]
D
+233° (c 1.2, CHCl
3
);
1
H NMR δ 7.75-7.30 (4H, J o,m ) 8.3 Hz, tosyl), 5.71 (d, 1H,
2
3
J
1
J
1
1
1,2 ) 3.5 Hz, H-1), 4.53 (t, 1H, J 2,3 ) 4.0 Hz, H-2), 4.15 (dd,
H, H-4), 4.15 (m, 1H, H-5), 4.15 (dd, 1H, H-3), 4.15 (dd, 1H,
6,6′ ) 10.0 Hz, H-6), 3.68 (dd, 1H, J 5,6′ ) 4.0 Hz, H-6′), 1.48,
2
3
2
3
1
3
.30 [s, 6H, C(CH
3
)
2
]; C NMR δ 144.9 (Cipso), 132.6 (Cpara),
), 103.0 (C-1), 82.6
),
Syn t h esis of 2-O-Oct a n oyl-1,3-d id eoxy-1,3-d i-S-(N,N-
d ieth yld ith ioca r ba m oyl)glycer ol (7). Likewise, octanoyl
chloride (2.3 g, 14.1 mmol), 1 (5.0 g, 14.1 mmol), and triethyl-
amine (2.2 mL, 15.5 mmol) gave, after 5 h, 5.1 g (75% yield) of
29.9 (Cortho), 127.9 (Cmeta), 111.9 (C(CH
3 2
)
(
1
C-2), 81.5 (C-4), 69.4 (C-5), 70.7 (C-6), 26.6, 26.5 (2C, C(CH
8.1 (C-3).
N,N-Diethyldithiocarbamic acid lithium salt (1.9 g, 12.4
3 2
)
1
7: H NMR δ 5.32 (m, 1 H, H-2), 3.96 (dt, 4H, J 1′a,1′b ) 13.5
mmol) was added to a stirred solution of 3-deoxy-3-iodo-1,2-
O-isopropylidene-6-O-tosyl-R-D-allofuranose (1.5 g, 3.1 mmol)
in hexamethylphosphoramide/toluene (1:1) (5 mL). Upon
completion of the addition, the reaction mixture was stirred
at 110 °C for 24 h. The mixture was filtered and the solvent
removed by distillation under reduced pressure to yield a
viscous oil. This oily residue was treated with hexane/diethyl
ether (1:1), washed twice with water, and dried (Na
crude product was purified on a silica gel column eluted with
hexane/acetone (9:1) to give 0.9 g (60% yield) of 2: [R]
2 3
Hz, CH CH ), 3.84 (m, 2H, J 1a,1b ) J 3a,3b ) 14.2 Hz, J 1a,2 )
J
2,3a ) 4.7 Hz, H-1a, H-3a), 3.70 (dt, 4H, J 1′′a,1′′b ) 13.9 Hz,
CH CH ), 3.55 (dd, 2H, J 1b,2 ) J 2,3b ) 7.0 Hz, H-1b, H-3b), 2.24
(dd, 2H, J R,â ) 7.5 Hz, H-R), 1.23 (m, 12H, J 1′,2′ ) 6.7 Hz, J 1′′,2′′
) 6.8 Hz, CH CH ), 1.56-1.22 (m, 2H, H-â, H-ú), 0.82 (t, 3H,
ú,ω ) 5.3 Hz, H-ω); C NMR δ 194.3 (2C, CS), 172.6 (CO),
70.6 (C-2), 49.8, 46.7 (CH CH ), 40.0 (C-1,C-3), 34.3 (C-R), 31.6
(C-â), 29.0 (C-γ), 28.9 (C-δ), 24.9 (C-ꢀ), 22.5 (C-ú), 14.0 (C-ω),
12.5, 11.5 (4C, CH CH ).
2
3
2
3
1
3
J
2
3
2 4
SO ). The
2
3
2
2
D
+48°
Syn th esis of 1,3-Did eoxy-1,3-d i-S-(N,N-d ieth yld ith io-
ca r ba m oyl)-2-oxoglycer ol (8). A solution of 1,3-dichloropro-
panone (10.0 g, 78.6 mmol) and N,N-diethyldithiocarbamic acid
lithium salt (36.6 g, 236 mmol) in acetone (200 mL) was stirred
at reflux for 3 h. The solvent was removed under reduced
1
(
(
(
J
1
c 1.1, CHCl ); H NMR δ 5.71 (d, 1H, J 1,2 ) 3.9 Hz, H-1), 4.67
3
d, 1H, J 2,3 ) 0, H-2), 4.35 (dd, 1H, J 3,4 ) 3.6 Hz, H-4), 4.05
m, 1H, J 4,5 ) 8.8 Hz, H-5), 4.69 (d, 1H, H-3), 3.86 (dd, 1H,
6,6′ ) 14.4 Hz, H-6), 3.46 (dd, 1H, J 5,6′ ) 7.1 Hz, H-6′), 1.46,
.22 [s, 6H, C(CH
], 104.5 (C-1), 86.6 (C-2), 80.4 (C-4), 69.9 (C-5), 57.3
C-3), 50.0-47.1 (4C, CH CH ), 40.6 (C-6), 26.6,26.4 [2C,
], 12.5, 11.5 (4C, CH CH ). Anal. Calcd for C19
482.75): C, 47.27; H, 7.10; S, 26.57; N, 5.80. Found: C, 47.21;
13
3
)
2
]; C NMR δ 196.6, 192.6 (2C, CS), 111.2
pressure, and the crude product was extracted twice with CH
Cl /water (3:1) (50 mL). The organic phases were washed twice
with water and dried (Na SO ). The crude product was purified
2
-
[C(CH
3
)
2
2
(
2
3
2
4
C(CH
(
3
)
2
2
3
H
34
O
4
S
4
N
2
on a silica gel column eluted with hexane/acetone (9:1) to give
1
21.8 g (78% yield) of 8: mp 75-78 °C; H NMR δ 4.37 (s, 4H,
H, 7.02; S, 27.02; N, 5.82.
2
H-1a, H-1b, H-3a, H-3b), 3.93 (dt, 4H, J 1′a,1′b ) 13.5 Hz, CH -
Syn th esis 3,6-Did eoxybis[3,6-S-(N,N-d ieth yld ith ioca r -
ba m oyl)]-D-glu cop yr a n ose (3). 2 (2.0 g, 4.1 mmol) was
reacted with a 0.6 M HCl in water/dioxane (1:9) (200 mL) at
CH
) 6.7 Hz, CH
δ 198.4 (CO), 194.0 (2C, CS), 49.9 (C-3), 47.1 (C-1), 45.8 (4C,
CH CH ), 12.5, 11.4 (4C, CH CH ).
3
), 3.71 (dt, 4H, J 1′′a,1′′b ) 13.9 Hz, CH
2 3
CH ), 1.25 (t, 6H, J
1
3
2
CH ), 1.18 (t, 6H, J ) 6.7 Hz, CH
3
2 3
CH ); C NMR
6
0 °C for 2 h. After the addition of sodium hydrogen carbonate
2
3
2
3
(
pH 6), the mixture was stirred for 10 min and filtered, and
Syn th esis of Dieth yl N,N′-(1,3-Did eoxyglycer -1,3-d iyl)-
bis(d ith ioca r ba m a te) (9). A solution of 1,3-dichloro-1,3-
dideoxyglycerol (15.0 g, 116.3 mmol) and NaN (30.2 g, 465.2
3
mmol) in N,N-dimethylformamide (300 mL) was stirred at
reflux for 1 h. The solvent was removed under reduced
pressure, and a solution of diethyl ether/water (1:1) (200 mL)
was added. The aqueous phase was extracted with diethyl
the solvent was removed under reduced pressure. The crude
product was purified on a silica gel column eluted with hexane/
2
2
acetone (1:1) to give 0.9 g (50% yield) of 3: [R]
D
-38° (c 1.5,
OH); C NMR, R form δ 195.9, 194.3 (2C, CS), 91.7 (C-1),
1.2 (C-2), 70.9 (C-5), 70.7 (C-4), 57.3 (C-3), 49.3-46.4 (4C,
CH CH ), 40.5 (C-6), 12.3, 11.4 (4C, CH CH ); â form δ 195.2,
1
3
CH
7
3
2
3
2
3