3952 J . Org. Chem., Vol. 62, No. 12, 1997
Calvo-Flores et al.
3-O-Acetyl-1,2-O-isopr opyliden e-r-D-glu cofu r an ose 5,6-
Cyclic Su lfite (8a ). Column chromatography (ether) of the
crude product gave 8a (82%). The mixture of the two stere-
oisomers could be resolved by column chromatography (ether-
hexane, 1:1) using an analytical sample. The first stereoiso-
mer was a solid that showed the following physical data: mp
120-121 °C; [R]D +62° (c 1, chloroform); IR (KBr) 1731, 1384,
Hz), 4.96 (ddd, 0.5 H, J ) 6.4, 4.5 Hz), 4.81-4.60 (m, 3 H),
4.49 (dd, 0.5 H, J ) 4.6, 8.9 Hz), 4.26 (dd, 0.5 H, J ) 9.1, 4.6
Hz), 4.03 (dd, 0.5 H, J ) 9.2, 6.2 Hz), 3.70 (dd, 0.5 H, J ) 9.1,
4.8 Hz), 3.45 (dd, 0.5 H, J ) 9.2, 4.7 Hz), 1.57, 1.56, 1.36, 1.35
(4s, 6 H); 13C NMR (CDCl3) δ 113.8, 113.7, 104.2, 81.7, 80.5,
80.4, 79.3, 77.3, 76.6, 68.9, 68.5, 62.9, 62.5, 26.6, 26.5, 26.4,
26.4; MS m/z 292 (M+ + 1).
2-Aceta m id o-2-d eoxy-3,4-O-isop r op ylid en e-a ld eh yd o-
D-glu cose Dim eth yl Aceta l 5,6-Cyclic Su lfite (14a ). Col-
umn chromatography (ethyl acetate) of the crude product gave
14a (95%) as a syrup: IR (neat) 3298, 1662, 1541, 1455, 1373,
1213, 1124, 1089 cm-1; 1H NMR (CDCl3) δ 5.86 (d, 0.5 H, J )
8.7 Hz), 5.80 (d, 0.5 H, J ) 8.5 Hz), 4.87 (ddd, 0.5 H, J ) 7.3,
6.4, 4.1 Hz), 4.72 (dd, 0.5 H, J ) 8.8, 6.4 Hz), 4.69 (t, 0.5 H, J
) 9.2 Hz), 4.63 (dd, 0.5 H, J ) 9.1, 6.6 Hz), 4.52 (dd, 0.5 H, J
) 8.9, 4.2 Hz), 4.51 (dt, 0.5 H, J ) 9.1, 6.6 Hz), 4.45-4.25 (m,
2.5 H), 4.18 (dd, 0.5 H, J ) 8.0, 1.1 Hz), 4.02 (t, 0.5 H, J ) 7.1
Hz), 3.62 (t, 0.5 H, J ) 7.7 Hz), 3.37, 3.37, 3.33, 3.29 (4s, 6 H),
1.99, 1.99 (2s, 3H), 1.37, 1.34 (2s, 6 H); 13C NMR (CDCl3) δ
170.1, 169.9, 110.3, 110.2, 103.2, 102.9, 82.3, 80.4, 77.5, 77.5,
77.3, 75.9, 69.2, 55.5, 55.1, 53.8, 52.9, 49.5, 49.2, 27.0, 27.0,
26.9, 23.3; MS m/z 354 (M+ + 1), 322; MS (calcd mass for
C13H23NO8S + H 354.1222) obsd m/z 354.1225.
1
1265, 1242, 1185 cm-1; H NMR (CDCl3) δ 6.01 (d, 1 H, J )
3.8 Hz), 5.00 (d, 1 H, J ) 2.3 Hz), 4.71 (d, 1 H, J ) 3.8 Hz),
4.56 (dd, 1 H, J ) 13.3, 7.7 Hz), 4.44-4.36 (m, 3 H), 2.10 (s, 3
H), 1.51, 1.35 (2s, 6 H); 13C NMR (CDCl3) δ 169.7, 113.1, 105.2,
83.4, 74.1, 73.2, 69.2, 63.7, 26.8, 26.4, 20.8; MS m/z 309 (M+
+
1), 293, 251, 245, 187. Anal. Calcd for C11H16O8S: C, 42.85;
H, 5.23; S, 10.40. Found: C, 42.81; H, 5.26; S, 10.08. The
second stereoisomer eluted was a solid that showed the
following physical data: mp 110-111 °C; [R]D -67° (c 1,
1
chloroform); IR (KBr) 1749, 1376, 1265, 1209, 1166 cm-1; H
NMR (CDCl3) δ 5.89 (d, 1 H, J ) 3.6 Hz), 5.29 (d, 1 H, J ) 3.2
Hz), 5.03 (ddd, 1 H, J ) 8.0, 6.4, 4.1 Hz), 4.77 (dd, 1 H, J )
8.9, 6.4 Hz), 4.61 (dd, 1 H. J ) 8.9, 4.1 Hz), 4.52 (d, 1 H, J )
3.6 Hz), 4.22 (dd, 1 H, J ) 8.0, 3.2 Hz), 2.12 (s, 3 H), 1.50,
1.30 (2s, 6 H); 13C NMR (CDCl3) δ 169.2, 112.9, 105.3, 83.4,
77.8, 76.2, 75.5, 69.1, 26.8, 26.2, 20.9; MS m/z 309 (M+ + 1),
293, 251, 245,187. Anal. Calcd for C11H16O8S: C, 42.85; H,
5.23; S, 10.40. Found: C, 42.61; H, 5.36; S, 10.00.
2,3-O-Isop r op ylid en e-a ld eh yd o-D-xylose Dim eth yl Ac-
eta l 4,5-Cyclic Su lfite (14b). Column chromatography (ethyl
acetate) of the crude product gave 14b (81%) as a syrup: IR
1,2-O-Isopr opyliden e-3-O-m eth yl-r-D-glu cofu r an ose 5,6-
Cyclic Su lfite (8c). Column chromatography (ether-hexane
1:1) of the crude product gave 8c (mixture of stereoisomers)
(neat) 1027, 999 cm-1
;
1H NMR (CDCl3) (selected signals) δ
5.06 (ddd, ∼0.5 H, J ) 6.9, 5.0, 2.5 Hz), 4.72 (dd, ∼0.5 H, J )
8.3, 6.9 Hz), 4.42 (d, 0.5 H, J ) 5.5 Hz), 3.47, 3.46, 3.45, 3.44
(4 s, 6 H), 1.46, 1.44, 1.43, 1.40 (4 s, 6 H);
1
(85%) as a syrup: IR (neat) 1295, 1213, 1165, 1124 cm-1; H
NMR (CDCl3) δ 5.87 (d, 1 H, J ) 3.5 Hz), 5.12 (dt, 0.5 H, J )
6.6, 4.8 Hz), 4.73-4.56 (m, 3 H), 4.52 (dd, 0.5 H, J ) 8.8, 4.8
Hz), 4.43 (dd, 0.5 H, J ) 8.0, 3.2 Hz), 4.21 (dd, 0.5 H, J ) 6.6,
3.3 Hz), 3.86 (d, 0.5 H, J ) 3.2 Hz), 3.79 (d, 0.5 H, J ) 3.3 Hz),
3.45, 3.43 (2s, 3 H), 1.48, 1.31 (2s, 6 H); 13C NMR (CDCl3) δ
112.4, 105.6, 105.5, 83.6, 83.4, 81.8, 81.6, 81.2, 79.0, 78.0, 76.7,
70.4, 68.8, 58.3, 26.9, 26.3; MS m/z 281 (M+ + 1), 265, 217.
3-O-Ben zyl-1,2-O-isopr opyliden e-r-D-glu cofu r an ose 5,6-
Cyclic Su lfite (8d ). Column chromatography (1:1 ether-
hexane) of the crude product gave 8d (mixture of stereoiso-
mers) (89%) as a syrup: IR (neat) 1455, 1378, 1212, 1164, 1076
13C NMR (CDCl3) δ
111.8, 111.4, 104.8, 104.6, 83.2, 79.2, 77.2, 76.8, 76.2, 75.5, 69.1,
67.4, 56.5, 56.3, 54.4, 54.3, 27.1, 26.8, 26.6.
3-O-Acetyl-1,2-O-isop r op ylid en e-â-D-a ltr ofu r a n ose 5,6-
Cyclic Su lfite (59). Column chromatography (ether-hexane
5:1) of the crude product gave 59 (100%) as a syrup: IR (neat)
1
1749, 1217, 1029 cm-1; H NMR (CDCl3) δ 5.93 (d, 1 H, J )
3.8 Hz), 5.42, 5.33 (2 s, 1 H), 5.15 (ddd, 0.5 H, J ) 10.0, 6.2,
3.7 Hz), 4.81-4.55 (m, 3 H), 4.41 (d, ∼0.5 H, J ) 9.6 Hz), 4.13-
4.00 (m, 0.5 H), 3.94 (d, 0.5 H, J ) 10.0 Hz), 2.11, 2.10 (2 s, 3
H), 1.55, 1.52, 1.31 (3 s, 6 H); 13C NMR (CDCl3) δ 169.5, 112.9,
112.7, 106.3, 86.8, 84.4, 84.3, 80.3, 78.4, 77.3, 77.1, 70.6, 69.2,
26.7, 25.5, 20.8; MS (calcd mass for C11H16O8S + H 309.0644)
obsd m/z 309.0657.
1
cm-1; H NMR (CDCl3) δ 7.34 (m, 5 H), 5.91 (d, 1 H, J ) 3.6
Hz), 5.90 (d, 1 H, J ) 3.4 Hz), 5.16 (dt, 0.5 H, J ) 6.6, 4.9 Hz),
4.80-4.45 (m, 6 H), 4.25 (dd, 0.5 H, J ) 6.6, 3.3 Hz), 4.13 (d,
0.5 H, J ) 3.2 Hz), 4.04 (d, 0.5 H, J ) 3.4 Hz), 1.49, 1.48, 1.31
(3 s, 6 H); 13C NMR (CDCl3) δ 137.2, 136.9, 128.8, 128.7, 128.4,
128.2, 128.0, 127.9, 112.5, 112.4, 105.7, 105.6, 82.6, 82.3, 81.7,
81.4, 81.3, 79.2, 78.1, 76.9, 72.8, 72.7, 70.5, 69.0, 27.0, 26.9,
26.3, 26.3; MS m/z 357 (M+ + 1), 341, 281, 181, 91.
3-O-Ben zyl-2-d eoxy-L-er yth r o-a ld eh yd o-p en tose Dim -
eth yl Aceta l 4,5-Cyclic Su lfite (67). Column chromatog-
raphy (ether-hexane 5:1) of the crude product gave 67 (98%)
as a syrup: IR (neat) 1210, 1125, 1028 cm-1; 1H NMR (CDCl3)
δ 7.34 (m, 5 H), 4.98 (ddd, 0.5 H, J ) 10.5, 6.9, 4.4 Hz), 4.72-
4.47 (m, 5 H), 4.43 (dd, 0.5 H, J ) 8.3, 5.9 Hz), 3.99 (dt, 0.5 H,
J ) 7.3, 4.7 Hz), 3.81 (m, 0.5 H), 3.32, 3.31, 3.28 (3 s, 6 H),
3-Deoxy-1,2-O-isopr opyliden e-r-D-r iboh exofu r an ose 5,6-
Cyclic Su lfite (8e). Column chromatography (ether) of the
crude product gave 8e (85%). The mixture of the two stere-
oisomers could be resolved by column chromatography (ether:
hexane 1:3) using an analytical sample. The first stereoisomer
was a solid that showed the following physical data: mp 66-
1.98-1.80 (m, 2 H);
13C NMR (CDCl3) δ 128.6, 128.3, 128.1,
128.0, 101.5, 101.4, 84.5, 81.6, 75.2, 74.3, 73.6, 73.5, 68.5, 68.2,
53.3, 53.2, 52.8, 35.4, 35.2; MS m/z 285 (M+ + 1 - CH3OH).
Gen er a l P r oced u r e for F or m a tion of Cyclic Su lfa tes
3, 9a ,c-f, 15a ,b, 24, 28, 36, 60, a n d 68. To a solution of the
cyclic sulfites 2, 8a ,c-f, 14a ,b, 59, and 67 (5 mmol) in a
mixture of MeCN (20 mL)/CCl4 (20 mL) was added NaIO4 (1.5
equiv) followed by a catalytic amount of RuCl3‚3H2O and water
(20 mL). The resulting mixture was stirred for 15-60 min at
rt until TLC showed complete disappearance of the starting
material. The mixture was diluted with ether (50 mL/mmol).
The organic layer was washed with water (2 × 100 mL) and
brine (100 mL). The organic solution was dried (Na2SO4) and
filtered. The filtrate was evaporated under reduced pressure
to give the corresponding cyclic sulfate, which was purified
by column chromatography. Compounds 24, 28, and 36 were
obtained from the corresponding diols 23, 27, and 35, respec-
tively, following the general procedures described above for
the synthesis of cyclic sulfites and cyclic sulfates without the
purification of the intermediate cyclic sulfite.
67 °C; [R]D -53° (c 1, chloroform); IR (KBr) 1205, 1024 cm-1
;
1H NMR (CDCl3) δ 5.82 (d, 1 H, J ) 3.6 Hz), 4.79 (pseudo-t, 1
H, J ) 4.2 Hz), 4.66-4.40 (m, 4 H), 2.36 (d, 1 H, J ) 13.6, 4.1
Hz), 1.86 (ddd, 1 H, J ) 13.6, 10.0, 4.8 Hz), 1.51, 1.32 (2s, 6
H); 13C NMR (CDCl3) δ 112.0, 105.8, 83.5, 80.5, 78.2, 69.8, 36.3,
26.9, 26.2; MS m/z 251 (M+ + 1), 235. Anal. Calcd for
C9H14O6S: C, 43.25; H, 5.60; S, 12.80. Found: C, 43.21; H,
5.46; S, 12.42. The second stereoisomer eluted was a solid that
showed the following physical data: mp 45-46 °C; [R]D -64°
(c 1, chloroform); IR (KBr) 1380, 1323, 1258, 1205 cm-1 1H
;
NMR (CDCl3) δ 5.79 (d, 1 H, J ) 3.5 Hz), 4.85-4.71 (m, 3 H),
4.40 (dd, 1 H, J ) 8.6, 4.4 Hz), 4.15 (ddd, 1 H, J ) 10.5, 6.8,
4.5 Hz), 2.26 (dd, 1 H, J ) 13.6, 4.5 Hz), 1.66 (ddd, 1 H, J )
13.6, 10.5, 4.7 Hz), 1.49, 1.30 (2s, 6 H); 13C NMR (CDCl3) δ
111.9, 105.8, 80.9, 80.3, 76.9, 69.3, 36.2, 26.8, 26.1; MS m/z
251 (M+ + 1), 235. Anal. Calcd for C9H14O6S: C, 43.25; H,
5.60; S, 12.80. Found: C, 43.21; H, 5.46; S, 12.52.
(2R)-1-O-Ben zylglycer ol 2,3-Cyclic Su lfa te (3). Column
chromatography (ether-hexane 1:1) of the crude product gave
3 (50%) as a syrup: [R]D +2.4° (c 4, chloroform); IR (neat) 1386,
1211, 1108, 1058, 984 cm-1; 1H NMR (CDCl3) δ 7.40-7.30 (m,
5 H), 5.04 (tt, 1 H, J ) 6.6, 4.9 Hz), 4.69 (dd, 1 H, J ) 8.8, 6.6
Hz), 4.62-4.56 (m, 3 H), 3.76 (d, 2 H, J ) 4.9 Hz); 13C NMR
3-Azid o-3-d e oxy-1,2-O-isop r op ylid e n e -r-D-a llofu r a -
n ose 5,6-Cyclic Su lfite (8f). Column chromatography (ether-
hexane 1:1) of the crude product gave 8f (98%) as a syrup: IR
(neat) 2114, 1377, 1254, 1218, 1163, 1110 cm-1 1H NMR
;
(CDCl3) δ 5.80 (d, 0.5 H, J ) 3.6 Hz), 5.79 (d, 0.5 H, J ) 3.4