Syntheses and reactions of 5-O-acetyl-1,2-anhydro-3-O-benzyl-α-D-ribofuranose and -β-D-lyxofuranose, 5-O-acetyl-1,2-anhydro-3,6-di-O-benzyl- and 1,2-anhydro-5,6-di-O-benzoyl-3-O-benzyl-β-D-mannofuranose, and 6-O-acetyl-1,2-anhydro-3,4-di-O-benzyl-α-D-glucopyranose and -β-D-talopyranose

Article abstract of DOI:10.1016/S0008-6215(00)00290-1

The title compounds 5-O-acetyl-1,2-anhydro-3-O-benzyl-α-D-ribofuranose and 5-O-acetyl-1,2-anhydro-3-O-benzyl-β-D-lyxofuranose, and 6-O-acetyl-1,2-anhydro-3,4-di-O-benzyl-α-D-glucopyranose and 6-O-acetyl-1,2-anhydro-3,4-di-O-benzyl-β-D-talopyranose, and 5-O-acetyl-1,2-anhydro-3,6-di-O-benzyl-β-D-mannofuranose and 1,2-anhydro-5,6-di-O-benzoyl-3-O-benzyl-β-D-mannofuranose have each been synthesized from the corresponding 2-O-tosylate and 1-free hydroxyl intermediates by base-initiated intramolecular S_N2 ring closure in almost quantitative yields. Acetyl and benzoyl groups were not affected in the ring closure reactions. Condensation of 6-O-acetyl-1,2-anhydro-3,4-di-O-benzyl-α-D-glucopyranose and 5-O-acetyl-1,2-anhydro-3,6-di-O-benzyl-β-D-mannofuranose with 1,2:3,4-di-O-isopropylidene-α-D-galactopyranose in the presence of ZnCl₂ as the catalyst afforded the 1,2-trans-linked 6-O-acetyl-3,4-di-O-benzyl-β-D-glucopyranosyl-(1 → 6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose and 5-O-acetyl-3,6-di-O-benzyl-α-D-mannofuranosyl-(1 → 6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose as the sole products in satisfactory yields, while condensation of 5-O-acetyl-1,2-anhydro-3-O-benzyl-β-D-lyxofuranose with 3-O-benzyl-1,2-O-isopropylidene-α-D-xylofuranose yielded the 1,2-trans-linked 5-O-acetyl-3-O-benzyl-α-D-lyxofuranosyl-(1 → 5)-3-O-benzyl-1,2-O-isopropylidene-α-D-xylofuranose as the sole product in a good yield. The 6-O-acetyl group in the glycosyl donor, 6-O-acetyl-1,2-anhydro-3,4-di-O-benzyl-α-D-glucopyranose, did not influence the stereoselectivity of the ring-opening-coupling reaction.

Full text of DOI:10.1016/S0008-6215(00)00290-1

www.elsevier.nl/locate/carres
Carbohydrate Research 330 (2001) 165–175
Syntheses and reactions of
5-O-acetyl-1,2-anhydro-3-O-benzyl-a-
-b- -lyxofuranose, 5-O-acetyl-1,2-anhydro-3,6-di-O-
benzyl- and 1,2-anhydro-5,6-di-O-benzoyl-3-O-benzyl-
-mannofuranose, and 6-O-acetyl-1,2-anhydro-3,4-
D-ribofuranose and
D
b-
D
di-O-benzyl-a-
D-glucopyranose and -b-D-talopyranose
Jun Ning, Fanzuo Kong *
Research Center for Eco-En6ironmental Sciences, Academia Sinica, PO Box 2871,
Beijing 100085, People’s Republic of China
Received 21 August 2000; accepted 24 October 2000
Abstract
The title compounds 5-O-acetyl-1,2-anhydro-3-O-benzyl-a-
-lyxofuranose, and 6-O-acetyl-1,2-anhydro-3,4-di-O-benzyl-a-
O-benzyl-b- -talopyranose, and 5-O-acetyl-1,2-anhydro-3,6-di-O-benzyl-b-
dro-5,6-di-O-benzoyl-3-O-benzyl-b- -mannofuranose have each been synthesized from the corresponding 2-O-tosylate
D
-ribofuranose and 5-O-acetyl-1,2-anhydro-3-O-benzyl-
-glucopyranose and 6-O-acetyl-1,2-anhydro-3,4-di-
-mannofuranose and 1,2-anhy-
b-D
D
D
D
D
and 1-free hydroxyl intermediates by base-initiated intramolecular SN2 ring closure in almost quantitative yields. Acetyl
and benzoyl groups were not affected in the ring closure reactions. Condensation of 6-O-acetyl-1,2-anhydro-3,4-di-O-
benzyl-a-
propylidene-a-
6-O-acetyl-3,4-di-O-benzyl-b-
tyl-3,6-di-O-benzyl-a- -mannofuranosyl-(1“6)-1,2:3,4-di-O-isopropylidene-a-
in satisfactory yields, while condensation of 5-O-acetyl-1,2-anhydro-3-O-benzyl-b-
O-isopropylidene-a- -xylofuranose yielded the 1,2-trans-linked 5-O-acetyl-3-O-benzyl-a-
benzyl-1,2-O-isopropylidene-a- -xylofuranose as the sole product in a good yield. The 6-O-acetyl group in the glycosyl
-glucopyranose, did not influence the stereoselectivity of the
D
-glucopyranose and 5-O-acetyl-1,2-anhydro-3,6-di-O-benzyl-b-
-galactopyranose in the presence of ZnCl2 as the catalyst afforded the 1,2-trans-linked
-glucopyranosyl-(1“6)-1,2:3,4-di-O-isopropylidene-a- -galactopyranose and 5-O-ace-
-galactopyranose as the sole products
-lyxofuranose with 3-O-benzyl-1,2-
-lyxofuranosyl-(1“5)-3-O-
D-mannofuranose with 1,2:3,4-di-O-iso-
D
D
D
D
D
D
D
D
D
donor, 6-O-acetyl-1,2-anhydro-3,4-di-O-benzyl-a-
D
ring-opening–coupling reaction. © 2001 Published by Elsevier Science Ltd. All rights reserved.
Keywords: Carbohydrate; 1,2-Anhydro sugars; Furanose; Pyranose
1. Introduction
tives have received considerable attention re-
cently because of their excellent reactivity and
stereoselectivity,1 and many natural and un-
usual oligosaccharides have been synthesized
by this method.1 Preparation of 1,2-anhydro
sugars was reported by Danishefsky’s group
using direct epoxidation of the glycals.1a–j
As useful intermediates for the syntheses of
oligosaccharides, 1,2-anhydro sugar deriva-
* Corresponding author. Tel.: +86-10-62563167; fax: +
86-10-62923563.
E-mail address: fzkong@mail.rcees.ac.cn (F. Kong).
0008-6215/01/$ - see front matter © 2001 Published by Elsevier Science Ltd. All rights reserved.
PII: S0008-6215(00)00290-1

166
J. Ning, F. Kong / Carbohydrate Research 330 (2001) 165–175
tions described above gave very high yields,
the intermediates involved in the procedure
could be subjected to the next reaction with-
out chromatographic separation. We were
gratified to find that ring closure of 5, 12, 19,
and 26 with t-BuOK or NaH in THF gave the
However, it would be difficult to prepare 1,2-
anhydro sugars having a cis arrangement of
the 3-hydroxy group and the epoxide ring by
this method, and large-scale preparation
would be inconvenient. Intramolecular SN2
ring closure reaction initiated by Schuerch’s
group is an effective approach.2 In a continu-
ing effort to synthesize 1,2-anhydro sugars by
this latter method, a variety of 1,2-anhydro
sugar benzyl ethers have been prepared in our
laboratory.1k–u However, in the stepwise syn-
theses of oligosaccharides, the preparation of
sugar derivatives with both persistent and
temporary groups is required.3 Benzyl and
allyl groups are usually used as persistent,
while esters are considered as temporary
blocking groups.3,4 In our previous communi-
cation, we reported a facile method for syn-
theses of 6-O-acetyl-1,2-anhydro-3,4-di-O-
5-O-acetyl-1,2-anhydro-3-O-benzyl-a-
furanose (6), 5-O-acetyl-1,2-anhydro-3-O-ben-
zyl-b- -lyxofuranose (13), 6-O-acetyl-1,2-
anhydro-3,4-di-O-benzyl-a- -glucopyranose
(20), and 6-O-acetyl-1,2-anhydro-3,4-di-O-
-talopyranose (27), respectively, in
D
-ribo-
D
D
benzyl-a-
D
almost quantitative yields. Acetyl groups were
not affected under the basic conditions. The
anhydro sugars 6, 13, 20, and 27 were iden-
1
tified from their H NMR spectra showing
upfield peaks from H-2 at l 3.57, 3.60, 3.06,
and 3.50 ppm, respectively, a salient feature of
the epoxide ring. Methanolysis of 6, 13, 20,
and 27 quantitatively gave the corresponding
1,2-trans methyl glycosides 7, 14, 21, and 28,
confirming the anhydro sugar structures. Con-
densation of 13 with 3-O-benzyl-1,2-O-iso-
benzyl-
D
-glycopyranoses and 5-O-acetyl-1,2-
anhydro-3-O-benzyl-glycofuranoses.5
We
present here the full account of this synthesis,
and also give two more examples, i.e., synthe-
sis of 5-O-acetyl-1,2-anhydro-3,6-di-O-benzyl-
and 1,2-anhydro-5,6-di-O-benzoyl-3-O-ben-
propylidene-a- -xylofuranose using ZnCl2 as
D
the catalyst in CH2Cl2 yielded an a-linked
disaccharide 29 (1,2-trans) as the sole product
in a high yield, while condensation of 20 with
zyl-b-
D
-mannofuranose starting from
D
-gluc-
ose by the intramolecular SN2 ring-closure
method.
1,2:3,4-di-O-isopropylidene-a- -galactopyran-
D
ose afforded a b-link disaccharide 30 (1,2-
trans) as the sole product in a satisfactory
yield. It is noted that the 6-O-acetyl group in
20 did not influence the stereoselectivity of the
ring-opening–coupling reaction, although it is
known that replacement of 6-O-benzyl with
6-O-acetyl alters the stereoselectivity of the
coupling reaction of benzylated galactopyran-
osyl phosphite from 1,2-trans to predominant
1,2-cis.9 Compounds 29 or 30 having a free
2-OH group and a potential 5-OH or 6-OH
group can be used for further selective func-
tionalization or glycosylation at the C-2 and
C-5, or C-6 positions.
2. Results and discussion
The syntheses of anhydro sugars 6, 13, 20,
and 27 are depicted in Scheme 1. Methanoly-
sis of 1, 8, 15, and 22 gave 2, 9, 16, and 23,
respectively, and subsequent tosylation af-
forded the corresponding methyl 2-sulfonate
glycosides 3, 10, 17, and 24. Selective acetoly-
sis of 3, 10, 17, and 24 using 7:1:0.6 (v/v)
HOAc–Ac2O–H2SO4 gave the corresponding
diacetates 4, 11, 18, and 25. Attempts for
selective removal of the 1-O-acetyl group of
the diacetates by known methods such as
Acetylation of 3110 with acetic anhydride in
pyridine afforded 5-O-acetyl-3,6-di-O-benzyl-
6
SnCl4 or N2H4·HOAc7 suffered from low
yields and tedious separation. However, in
these examples the 1-O-acetyl group of 4, 11,
18, and 25 was removed almost quantitatively
in anhydrous ether saturated with dry
ammonia8 to yield the key intermediates 5, 12,
19, and 26, respectively. Since all of the reac-
1,2-O-isopropylidene-a- -glucofuranose (32)
D
quantitatively (Scheme 2). Hydrolysis of 32 in
50% acetic acid under reflux gave 5-O-acetyl-
3,6-di-O-benzyl- -glucofuranose (33) in 92%
D
yield as a mixture of a and b anomers. Com-
pound 33 was treated with 5% aqueous

J. Ning, F. Kong / Carbohydrate Research 330 (2001) 165–175
167
NaOH, 1.5 equiv of TsCl, and tetra-
butylammonium hydrogensulfate (TBAHS) in
dichloromethane at room temperature to give
the key intermediate, 5-O-acetyl-3,6-di-O-ben-
be recovered. Ring closure of 34 with t-BuOK
or NaH in dry tetrahydrofuran gave the 5-O-
acetyl-1,2-anhydro-3,6-di-O-benzyl-b- -man-
D
nofuranose (35) quantitatively within 10 min,
and the acetyl group in 34 was not affected
under the alkaline conditions. Compound 35
was very sensitive to acidic and hydroxylic
zyl-2-O-(p-toluenesulfonyl)- -glucofuranose
D
(34) as a mixture of a and b isomers, in 71%
yield, from which the starting material could
Scheme 1. Reactions and conditions: (a) cat. H2SO4, MeOH, reflux, 3 h, 98% (2), 97% (9), 98% (16), 98% (23). (b) TsCl, pyridine,
50 °C, 20 h, 98% (3), 98% (10), 97% (17), 98% (24). (c) 7:1:0.6 HOAc–Ac2O–H2SO4, rt, 16 h, 97% (4), 96% (11), 96% (18), 96%
(25). (d) anhyd Et2O satd with dry ammonia, rt, 24 h, 97% (5), 97% (12), 96% (19), 97% (26). (e) t-BuOK (1.1 equiv), THF, rt,
20 min, 95% (6), 94% (13), 92% (20), 94% (27). (f) anhyd MeOH, rt, 1 h, 100% (7, 14, 21, 28). (g) 3-O-Benzyl-1,2-O-isopropyli-
dene-a-
D
-xylofuranose, CH2Cl2, ZnCl2, rt, 4 h, 81% (29). (h) 1,2:3,4-di-O-Isopropylidene-a-D-galactopyranose, CH2Cl2, ZnCl2, rt,
4 h, 83% (30).

168
J. Ning, F. Kong / Carbohydrate Research 330 (2001) 165–175
Scheme 2. Reactions and conditions: (a) pyridine, Ac2O, rt, 3 h, 100%. (b) 50% HOAc, reflux, 5 h, 92%. (c) TsCl, TBAHS, 5%
aq NaOH, CH2Cl2, rt, 15 h, 71%. (d) t-BuOK (1.1 equiv), THF, rt, 20 min, 96%. (e) Anhyd MeOH, rt, 1 h, 100%. (f)
1,2:3,4-di-O-Isopropylidene-a-D-galactopyranose, CH2Cl2, ZnCl2, rt, 4 h, 84%.
Scheme 3. Reactions and conditions: (a) TsCl, TBAHS, 5% aq NaOH, CH2Cl2, rt, 15 h, 69%. (b) t-BuOK (1.1 equiv), THF, rt,
20 min, 97%. (c) Anhyd MeOH, rt, 1 h, 100%.
solvent, and attempts to obtain an accurate
struction
of
some
specific
complex
elemental analysis of 35 were unsuccessful.
carbohydrates.
1
The H NMR spectrum of 35 showed an
upfield signal for H-2 at l 3.62 ppm, which is
a characteristic feature of the 1,2-epoxide ring
of carbohydrate compounds. The structure of
35 was further confirmed by methanolysis,
giving the methyl 5-O-acetyl-3,6-di-O-benzyl-
3. Experimental
General methods.—Melting points were de-
termined with a ‘Mel-Temp’ apparatus. Opti-
cal rotations were determined at 20 °C with a
Perkin–Elmer model 241-MC automatic po-
a-
also by its coupling reaction with 1,2:3,4-di-O-
-galactopyranose in the
D-mannofuranoside (36) quantitatively, and
1
larimeter. H NMR spectra were recorded
isopropylidene-a-
D
with an Varian XL-200 spectrometer for solu-
tions in CDCl3. Chemical shifts are given in
ppm downfield from internal Me4Si. TLC was
performed on silica gels G and HF, with
detection either by charring with 30% (v/v)
H2SO4 and MeOH or by UV light. Column
chromatography was conducted on columns
(16×240 mm, 18×300 mm) of silica gel
(100–200 mesh). Solutions were concentrated
at 60 °C under diminished pressure.
presence of ZnCl2 as the catalyst, giving the
1,2-trans-linked disaccharide 37 in 84% yield.
1,2-Anhydro-5,6-di-O-benzoyl-3-O-benzyl-
b- -mannofuranose (40) was prepared by a
D
procedure similar to that used for the synthe-
sis of compound 35 (see Scheme 3).
In conclusion, new procedures for the syn-
theses of 1,2-anhydro sugar derivatives with
both benzoyl and acetyl groups were success-
fully developed. The synthetic pathway pre-
sented here may open a way to the further
synthesis of other similar 1,2-anhydro sugars,
and it is expected that these sugar derivatives
will be valuable intermediates for the con-
Methyl 3,5-di-O-benzyl-
(2), methyl 3,5-di-O-benzyl-
(9),methyl3,4,6-tri-O-benzyl-h-
oside (16), and methyl 3,4,6-tri-O-benzyl-
galactopyranoside (23).—A solution of 11k (or
D
-arabinofuranoside
-xylofuranoside
-mannopyran-
D
D
D-

J. Ning, F. Kong / Carbohydrate Research 330 (2001) 165–175
169
8,1o 15,11 2212) (20 mmol) in anhydrous MeOH
(100 mL) containing two drops of H2SO4 was
stirred under reflux for 3 h, at the end of
which time TLC (2:1 petroleum ether–EtOAc)
indicated that the reaction was complete. Af-
ter rendering the solution basic with NaHCO3,
the mixture was concentrated to syrup, which
was subjected to column chromatography
with 2:1 petroleum ether–EtOAc as the eluent
to afford the known compounds 2,13 9,14 16,15
and 2316 in 98, 97, 98, and 98% yields,
respectively.
J4,5% 4.0, J5,5% 12.0 Hz, H-5%), 3.29 (s, 3 H,
OCH3), 2.41 (s, 3 H, PhCH3).
Data for 17: [h]D −10.2° (c 0.5, CHCl3); 1H
NMR: l 7.81 (d, 2 H, PhꢀH of Ts), 7.35–7.05
(m, 15 H, 3 PhꢀH), 4.88 (d, 1 H, J1,2 2.0 Hz,
H-1), 4.84 (t, 1 H, J1,2 2.0, J2,3 2.0 Hz, H-2),
4.78, 4.44 (2 d, 2 H, J 11.0 Hz, PhCH2), 4.62,
4.53 (2 d, 2 H, J 12.0 Hz, PhCH2), 4.41, 4.38
(2 d, 2 H, J 10.4 Hz, PhCH2), 3.93–3.68 (m, 5
H, H-3, 4, 5, 6, 6%), 3.33 (s, 3 H, OCH3), 2.35
(s, 3 H, PhCH3). Anal. Calcd for C35H38O8S:
C, 67.96; H, 6.15. Found: C, 67.81; H, 6.13.
Data for 24: mainly h, [h]D +27.2° (c 1.9,
Methyl 3,5-di-O-benzyl-2-O-(p-toluenesul-
1
CHCl3); H NMR: l 7.85 (d, 2 H, PhꢀH of
fonyl)-
O-benzyl-2-O-(p-toluenesulfonyl)-
oside (10), methyl 3,4,6-tri-O-benzyl-2-O-(p-
D
-arabinofuranoside (3), methyl 3,5-di-
Ts), 7.35–7.05 (m, 17 H, PhꢀH), 4.90 (d, 1 H,
J1,2 3.4 Hz, H-1), 4.84 (dd, 1 H, J1,2 3.4, J2,3
8.0 Hz, H-2), 4.74, 4.44 (2 d, 2 H, J 12.0 Hz,
PhCH2), 4.51 (s, 2 H, PhCH2), 4.46, 4.40 (2 d,
2 H, J 11.6 Hz, PhCH2), 3.94–3.84 (m, 3 H,
H-3, 4, 5), 3.52 (d, 2 H, J5,6 8.0 Hz, H-6, 6%),
3.35 (s, 3 H, OCH3), 2.35 (s, 3 H, PhCH3).
Anal. Calcd for C35H38O8S: C, 67.96; H, 6.15.
Found: C, 68.02; H, 6.12.
D-xylofuran-
toluenesulfonyl)-h- -mannopyranoside (17), and
D
methyl
sulfonyl)-
3,4,6-tri-O-benzyl-2-O-(p-toluene-
-galactopyranoside (24).—To a so-
D
lution of 2 (or 9, 16, 23) (15.0 mmol) in
pyridine (50 mL) was added TsCl (20.0
mmol). The mixture was stirred at 50 °C for
about 24 h. Then the reaction mixture was
poured onto ice-cold water and extracted with
CH2Cl2 (3×25 mL). The organic layer was
washed with N HCl (3×50 mL), dried over
Na2SO4, and concentrated to syrup. The
product was subjected to column chromatog-
raphy with 3:1 petroleum ether–EtOAc as the
eluent. Compounds 3 (98%), 10 (98%), 17
(97%), and 24 (98%) were obtained as syrups.
Data for 3: mainly a, [h]D +9.8° (c 1.9,
1,5-Di-O-acetyl-3-O-benzyl-2-O-(p-toluene-
sulfonyl)-h- -arabinofuranose (4), 1,5-di-O-
D
acetyl-3-O-benzyl-2-O-(p-toluenesulfonyl)-
xylofuranose (11), 1,6-di-O-acetyl-3,4-di-O-
benzyl-2-O-(p-toluenesulfonyl)-h- -manno-
pyranose (18), and 1,6-di-O-acetyl-3,4-di-O-
benzyl - 2 - O - (p - toluenesulfonyl) - - galacto-
D
-
D
D
pyranose (25).—A solution of compound 3 (or
10, 17, 24) (6.0 mmol) in AcOH (34 mL) and
Ac2O (5 mL) was cooled to 0 °C in an ice
bath, and H2SO4 (3 mL) was added dropwise
over 20 min. After the addition was complete,
the ice bath was removed, and the reaction
was allowed to continue for 16 h at ambient
temperature. The reaction solution was
poured into a solution of ice water (120 mL).
Stirring was continued for an additional 30
min, and the aq solution was extracted with
CH2Cl2 (3×25 mL). The combined CH2Cl2
extracts were carefully washed with 10% aq
NaHCO3 (3×70 mL), and the solvent was
removed in vacuo to a constant weight afford-
ing 4 (97%), (or 11, 96%; 18, 96%; 25, 96%).
Data for 4: mp 102–104 °C; [h]D +18.3° (c
1
CHCl3); H NMR: l 7.82 (d, 2 H, PhꢀH of
Ts), 7.36–7.12 (m, 12 H, PhꢀH), 4.83 (s, 1 H,
H-1), 4.82 (d, 1 H, J3,2 2.0 Hz, H-2), 4.54, 4.50
(2 d, 2 H, J 12.0 Hz, PhCH2), 4.45, 4.32 (2 d,
2 H, J 11.9 Hz, PhCH2), 4.13 (m, 1 H, H-4),
3.97 (dd, 1 H, J2,3 2.0, J4,3 7.1 Hz, H-3), 3.57
(dd, 1 H, J4,5 3.7, J5,5% 10.8 Hz, H-5), 3.53 (dd,
1 H, J4,5% 5.5, J5,5% 10.8 Hz, H-5%), 3.28 (s, 3 H,
OCH3), 2.45 (s, 3 H, PhCH3). Anal. Calcd for
C27H30O7S: C, 65.06; H, 6.02. Found: C,
65.20; H, 6.04.
Data for 10: mainly b, [h]D −16.1° (c 2.1,
1
CHCl3); H NMR: l 7.81 (d, 2 H, PhꢀH of
Ts), 7.37–7.10 (m, 12 H, PhꢀH), 4.78 (d, 1 H,
J1,2 2.4 Hz, H-1), 4.84 (dd, 1 H, J1,2 2.4, J2,3
4.0 Hz, H-2), 4.55, 4.50 (2 d, 2 H, J 12.0 Hz,
PhCH2), 4.43, 4.38 (2 d, 2 H, J 11.2 Hz,
PhCH2), 4.37–4.28 (m, 2 H, H-3, 4), 3.65 (dd,
1 H, J4,5 2.6, J5,5% 12.0 Hz, H-5), 3.55 (dd, 1 H,
1
1.3, CHCl3); H NMR: l 7.82 (d, 2 H, PhꢀH
of Ts), 7.42–7.25 (m, 7 H, PhꢀH), 6.02 (s, 1
H, H-1), 4.99 (d, 1 H, J2,3 3.0 Hz, H-2), 4.62,
4.48 (2 d, 2 H, J 12.0 Hz, PhCH2), 4.34–4.04
(m, 4 H, H-3, 4, 5, 5%), 2.48 (s, 3 H, PhCH3),

170
J. Ning, F. Kong / Carbohydrate Research 330 (2001) 165–175
1
Data for 5: [h]D +29.1° (c 1.4, CHCl3); H
NMR: l 7.82 (d, 2×0.2 H, PhꢀH of b
anomer), 7.80 (d, 2×0.8 H, PhꢀH of a
anomer), 7.41–7.18 (m, 7 H, PhꢀH), 5.36 (d,
0.2 H, J1,2 3.8 Hz, H-1 of b anomer), 5.34 (s,
0.8 H, H-1 of a anomer), 4.81 (d, J2,3 2.8 Hz,
H-2 of a anomer), 4.75 (dd, J1,2 3.8, J2,3 5.0
Hz, H-2 of b anomer), 4.55–4.32 (m, 2 H,
PhCH2), 4.23–3.93 (m, 4 H, H-3, 4, 5, 5%), 3.66
(bs, 1 H, OH), 2.46 (s, 3×0.8 H, PhCH3 of a
anomer), 2.43 (s, 3×0.2 H, PhCH3 of b
anomer), 2.03 (s, 3×0.2 H, COCH3 of b
anomer), 2.00 (s, 3×0.8 H, COCH3 of a
anomer). Anal. Calcd for C21H24O8S: C, 57.80;
H, 5.50. Found: C, 57.84; H, 5.48.
2.05, 2.01 (2 s, 6 H, 2 COCH3). Anal. Calcd
for C23H26O9S: C, 57.74; H, 5.44. Found: C,
57.82; H, 5.40.
Data for 11: 2:1 a, b mixture; [h]D −14.2°
1
(c 3.2, CHCl3); H NMR: l 7.80 (d, 2 H,
PhꢀH of Ts), 7.40–7.18 (m, 7 H, PhꢀH), 6.22
(d, 0.67 H, J1,2 4.4 Hz, H-1 of a anomer), 5.99
(s, 0.33 H, H-1 of b anomer), 5.01 (s, 0.33 H,
H-2 of b anomer), 4.95 (t, 0.67 H, J1,2 4.4, J2,3
4.4 Hz, H-2 of a anomer), 4.70–4.10 (m, 6 H,
H-3, 4, 5, 5%, PhCH2), 2.45 (s, 3×0.33 H,
PhCH3 of b anomer), 2.42 (s, 3×0.67 H,
PhCH3 of a anomer), 2.03–2.00 (m, 6 H, 2
COCH3). Anal. Calcd for C23H26O9S: C,
57.74; H, 5.44. Found: C, 57.74; H, 5.42.
Data for 18: only a isomer: mp 114–116 °C;
Data for 12: 1:3 a, b mixture: [h]D −24.1°
(c 0.9, CHCl3); H NMR: l 7.82 (d, 2×0.25
1
1
[h]D −6.4° (c 3.0, CHCl3); H NMR: l 7.85
(d, 2 H, PhꢀH of Ts), 7.35–7.20 (m, 10 H, 2
PhꢀH), 6.04 (d, 1 H, J1,2 2.2 Hz, H-1), 4.84 (t,
1 H, J2,1 2.2, J3,2 2.2 Hz, H-2), 4.86, 4.54 (2 d,
2 H, J 10.5 Hz, PhCH2), 4.61, 4.48 (2 d, 2 H,
J 11.3 Hz, PhCH2), 4.30 (dd, 1 H, J5,6 2.0, J6,6%
12.0 Hz, H-6), 4.21 (dd, 1 H, J5,6% 3.9, J6%,6 12.0
Hz, H-6%), 3.96–3.72 (m, 3 H, H-3, 4, 5), 2.40
(s, 3 H, PhCH3), 2.05, 2.02 (2 s, 6 H, 2
COCH3). Anal. Calcd for C31H34O9S: C,
63.92; H, 5.84. Found: C, 63.90; H, 5.86.
Data for 25: mainly a isomer: [h]D +32.1°
H, PhꢀH of Ts of a anomer), 7.80 (d, 2×0.75
H, PhꢀH of Ts of i anomer), 7.50–7.16 (m, 7
H, PhH), 5.46 (d, 0.25 H, J1,2 4.1 Hz, H-1 of
a anomer), 5.15 (s, 0.75 H, H-1 of b anomer),
4.80 (s, 0.75 H, H-2 of b anomer), 4.71 (t, 0.25
H, J2,1 4.1, J3,2 4.1 Hz, H-2 of a anomer),
4.63–4.12 (m, 6 H, H-3, 4, 5, 5%, PhCH2), 2.46
(s, 3×0.75 H, PhCH3 of b anomer), 2.42 (s,
3×0.25 H, PhCH3 of a anomer), 2.03(s, 3×
0.75 H, COCH3 of b anomer), 2.00 (s, 3×
0.25 H, COCH3 of a anomer). Anal. Calcd for
C21H24O8S: C, 57.80; H, 5.50. Found: C,
57.77; H, 5.53.
1
(c 1.2, CHCl3); H NMR: l 7.72 (d, 2 H,
PhꢀH of Ts), 7.40–7.10 (m, 12 H, PhꢀH), 6.26
(d, 1 H, J1,2 3.9 Hz, H-1), 4.98 (dd, 1 H, J1,2
3.9, J2,3 9.3 Hz, H-2), 4.82, 4.52 (2 d, 2 H, J
11.2 Hz, PhCH2), 4.62 (s, 2 H, PhCH2), 4.18–
3.86 (m, 5 H, H-3, 4, 5, 6, 6%), 2.38 (s, 3 H,
PhCH3), 2.10, 1.95 (2 s, 6 H, 2 COCH3). Anal.
Calcd for C31H34O9S: C, 63.92; H, 5.84.
Found: C, 63.88; H, 5.82.
Data for 19: Only a isomer: [h]D −16.5° (c
1
1.7, CHCl3); H NMR: l 7.83 (d, 2 H, PhꢀH
of Ts), 7.39–7.17 (m, 10 H, 2 PhCH2), 5.34 (d,
1 H, J2,1 2.0 Hz, H-1), 4.81 (t, 1 H, J1,2 =J3,2
2.0 Hz, H-2), 4.82, 4.53 (2 d, 2 H, J 12.0 Hz,
PhCH2), 4.39 (s, 2 H, PhCH2), 4.37 (dd, 1 H,
J2,3 2.0, J4,3 10.0 Hz, H-3), 4.14 (dd, 1 H, J5,6
6.0, J6%,6 12.0 Hz, H-6), 3.98 (dd, 1 H, J5,6% 2.4,
J6,6% 12.0 Hz, H-6%), 3.97 (m, 1 H, H-5), 3.72 (t,
1 H, J3,4 =J5,4 10.0 Hz, H-4), 2.90 (ds, 1 H,
OH), 2.38 (s, 3 H, PhCH3), 2.04 (s, 3 H,
COCH3). Anal. Calcd for C29H32O8S: C,
64.44; H, 5.92. Found: C, 64.50; H, 5.91.
Data for 26: Only a isomer: [h]D +43.1° (c
5-O-Acetyl-3-O-benzyl-2-O-(p-toluenesul-
fonyl)-
benzyl-2-O-(p-toluenesulfonyl)-
(12), 6-O-acetyl-3,4-di-O-benzyl-2-O-(p-tolu-
enesulfonyl)-h- -mannopyranose (19), and 6-O-
acetyl-3,4-di-O-benzyl-2-O-(p-toluenesulfonyl)-
h- -galactopyranose (26).—A solution of
D
-arabinofuranose (5), 5-O-acetyl-3-O-
D
-xylofuranose
D
D
1
compound 4 (or 11, 18, 25) (7.0 mmol) in
anhyd Et2O (100 mL) saturated with dry am-
monia was stirred for 24 h, at the end of
which time TLC (2:1 petroleum ether–EtOAc)
indicated that the reaction was complete. The
solution was concentrated to afford 5 (97%),
(or 12, 97%; 19, 96%; 26, 97%).
2.1, CHCl3); H NMR: l 7.75 (d, 2 H, PhꢀH
of Ts), 7.35–7.08 (m, 12 H, PhH), 5.49 (d, 1
H, J1,2 4.0 Hz, H-1), 4.84 (dd, 1 H, J1,2 4.0, J2,3
9.6 Hz, H-2), 4.79, 4.49 (2 d, 2 H, J 12.0 Hz,
PhCH2), 4.54 (s, 2 H, PhCH2), 4.20–4.04 (m,
3 H, H-5, 6, 6%), 3.98 (dd, 1 H, J2,3 9.6, J3,4 2.6
Hz, H-3), 3.84 (d, 1 H, J3,4 2.6 Hz, H-4), 2.37

J. Ning, F. Kong / Carbohydrate Research 330 (2001) 165–175
171
(s, 3 H, PhCH3), 1.99 (s, 3 H, COCH3). Anal.
Methyl
5-O-acetyl-3-O-benzyl-i-
D
-ribo-
Calcd for C29H32O8S: C, 64.44; H, 5.92.
Found: C, 64.39; H, 5.94.
furanoside (7), methyl 5-O-acetyl-3-O-benzyl-
h- -lyxofuranoside (14), methyl 6-O-acetyl-
3,4-di-O-benzyl-i- -glucopyranoside (21), and
methyl 6-O-acetyl-3,4-di-O-benzyl-h- -talo-
D
5-O-Acetyl-1,2-anhydro-3-O-benzyl-h-
bofuranose (6), 5-O-acetyl-1,2-anhydro-3-O-
benzyl-i- -lyxofuranose (13), 6-O-acetyl-
1,2-anhydro-3,4-di-O-benzyl-h- -glucopyranose
(20), and 6-O-acetyl-1,2-anhydro-3,4-di-O-
benzyl-i- -talopyranose (27).—To a solution
D-ri-
D
D
D
pyranoside (28).—Compound 6 (or 13, 20, 27)
(0.5 mmol) was dissolved in anhyd MeOH (5
mL) and kept for 1 h at rt. TLC (2:1
petroleum ether–EtOAc) indicated that the
reaction was complete. The solution was con-
centrated to quantitatively afford 7 (or 14, 21,
28).
D
D
of 5 (or 12, 19, 26) (2.0 mmol) in dry THF (6
mL) was added t-BuOK (2.2 mmol), and the
mixture was stirred at rt for 10 min, at the end
of which time TLC (2:1 petroleum ether–
EtOAc) indicated that the starting material
had disappeared. The mixture was concen-
trated to dryness, and the residue was repeat-
1
Data for 7: [h]D +13.9° (c 0.9, CHCl3); H
NMR: l 7.35 (s, 5 H, PhH), 4.88 (s, 1 H,
H-1), 4.61, 4.57 (ABdd, 2 H, J 11.4 Hz,
PhCH2), 4.30–4.00 (m, 5 H, H-2, 3, 4, 5, 5%),
3.35 (s, 3 H, OCH3), 2.05 (s, 3 H, COCH3).
Anal. Calcd for C15H20O6: C, 60.81; H, 6.76.
Found: C, 60.77; H, 6.72.
edly
extracted
with
3:1
petroleum
ether–EtOAc. Concentration of the combined
extracts yielded 6 (95%) (or 13, 94%; 20, 92%;
27, 94%).
Data for 14: [h]D +35.6° (c 0.6, CHCl3); 1H
NMR: l 7.40–7.30 (5 H, PhH), 4.90 (s, 1 H,
H-1), 4.65, 4.57 (2 d, 2 H, J 12.6 Hz, PhCH2),
4.48–4.30 (m, 3 H, H-3, 5, 5%), 4.19 (m, 1 H,
H-4), 4.07 (d, 1 H, J3,2 4.6 Hz, H-2), 3.36 (s, 3
H, OCH3), 2.04 (s, 3 H, COCH3). Anal. Calcd
for C15H20O6: C, 60.81; H, 6.76. Found: C,
60.84; H, 6.75.
1
Data for 6: [h]D +36.1° (c 1.1, CHCl3); H
NMR: l 7.38 (s, 5 H, PhH), 5.20 (d, 1 H, J1,2
1.7 Hz, H-1), 4.76, 4.66 (ABdd, 2 H, J 12.0
Hz, PhH), 4.30–3.90 (m, 4 H, H-3, 4, 5, 5%),
3.57 (t, 1 H, J1,2 =J2,3 1.7 Hz, H-2), 2.03 (s, 3
H, COCH3).
1
Data for 13: [h]D –8.6° (c 2.4, CHCl3); H
NMR: l 7.38–7.24 (5 H, PhH), 5.16 (d, 1 H,
J2,1 1.9 Hz, H-1), 4.72, 4.64 (2 d, 2 H, J 12.0
Hz, PhCH2), 4.58, 4.35 (m, 3 H, H-3, 5, 5%),
4.10 (m, 1 H, H-4), 3.60 (t, 1 H, J1,2=J3,2 1.9
Hz, H-2), 2.08 (s, 3 H, COCH3).
1
Data for 21: [h]D −31° (c 1.5, CHCl3); H
NMR: l 7.40–7.25 (m, 10 H, 2 PhH), 4.95,
4.85 (2 d, 2 H, J 12.0 Hz, PhCH2), 4.86, 4.57
(2 d, 2 H, J 10.2 Hz, PhCH2), 4.33 (dd, 1 H,
J5,6 1.0, J6%,6 12.8 Hz, H-6), 4.24 (dd, 1 H, J5,6%
2.1, J6,6% 12.8 Hz, H-6%), 4.17 (d, 1 H, J2,1 8.0
Hz, H-1), 3.66–3.48 (m, 4 H, H-2, 3, 4, 5),
3.55 (s, 3 H, OCH3), 2.50 (bs, 1 H, OH), 2.03
(s, 3 H, COCH3). Anal. Calcd for C23H28O7:
C, 66.35; H, 6.73. Found: C, 66.40; H, 6.75.
Data for 28: [h]D +14.3° (c 2.5, CHCl3); 1H
NMR: l 7.44–7.30 (m, 10 H, PhH), 4.99, 4.63
(2 d, 2 H, J 11.8 Hz, PhCH2), 4.83, 4.55 (2 d,
2 H, J 11.0 Hz, PhCH2), 4.82 (d, 1 H, J1,2 3.5
Hz, H-1), 4.22 (dd, 1 H, J5,6 7.4, J6,6% 12.0 Hz,
H-6), 4.14 (dd, 1 H, J5,6% 6.0, J6,6% 12.0 Hz,
H-6%), 4.0 (m, 1 H, H-5), 3.92–3.82 (m, 2 H,
H-3, 4), 3.73 (t, 1 H, J1,2=J2,3 =3.5 Hz, H-2),
3.35 (s, 3 H, OCH3), 2.00 (s, 3 H, COCH3).
Anal. Calcd for C23H28O7: C, 66.35; H, 6.73.
Found: C, 66.33; H, 6.71.
Data for 20: mp 93–94 °C; [h]D −10.2° (c
1
1.0, CHCl3); H NMR: l 7.42–7.23 (m, 10 H,
2 PhCH2), 4.95 (d, 1 H, J2,1 1.7 Hz, H-1), 4.80,
4.60 (2 d, 2 H, J 11.2 Hz, PhCH2), 4.79, 4.69
(2 d, 2 H, J 11.5 Hz, PhCH2), 4.33 (dd, 1 H,
J5,6 2.2, J6%,6 11.9 Hz, H-6), 4.24 (dd, 1 H, J5,6%
3.9, J6,6% 11.9 Hz, H-6%), 4.01 (dd, 1 H, J2,3 1.0,
J4,3 7.8 Hz, H-3), 3.81 (ddd, 1 H, J4,5 10.2, J6,5
2.2, J6%,5 3.9 Hz, H-5), 3.51 (dd, 1 H, J3,4 7.8,
J5,4 10.2 Hz, H-4), 3.06 (dd, 1 H, J1,2 1.7, J3,2
1.0 Hz, H-2), 2.03 (s, 3 H, COCH3).
Data for 27: mp 90–91 °C; [h]D +11.4° (c
1
1.9, CHCl3); H NMR: l 7.48–7.29 (m, 10 H,
PhH), 5.00 (d, 1 H, J1,2 4.0 Hz, H-1), 4.90,
4.67(2 d, 2 H, J 12.0 Hz, PhCH2), 4.86, 4.77 (2
d, 2 H, J 12.0 Hz, PhCH2), 4.24–4.00 (m, 3 H,
H-5, 6, 6%), 3.95 (dd, 1 H, J2,3 4.0, J3,4 5.1 Hz,
H-3), 3.77 (d, 1 H, J3,4 5.1 Hz, H-4), 3.50 (t, 1
H, J1,2 4.0, J2,3 4.0 Hz, H-2), 1.96 (s, 3 H,
COCH3).
5-O-Acetyl-3-O-benzyl-h-
(1“5) - 3 - O - benzyl - 1,2 - O - isopropylidene-
h- -xylofuranose (29).—To a solution of 1,2-
D
-lyxofuranosyl-
D

172
J. Ning, F. Kong / Carbohydrate Research 330 (2001) 165–175
J3,2 2.4 Hz, H-2), 4.25 (d, 1 H, J2%,1% 3.2 Hz,
H-1%), 4.22 (dd, 1 H, J3,4 7.9, J5,4 1.8 Hz, H-4),
4.07 (dd, 1 H, J1%,2% 3.2, J3%,2% 11.0 Hz, H-2%),
4.01 (m, 1 H, H-5), 3.74 (dd, 1 H, J2%,3% 11.0,
J4%,3% 8.1 Hz, H-3%), 3.65 (m, 1 H, H-5%), 3.60
(dd, 1 H, J3%,4%=8.1, J5%,4%=10.5 Hz, H-4%),
3.52 (d, 2 H, J5,6 4.8 Hz, H-6a,6b), 2.02 (s, 3
H, COCH3), 1.52, 1.50, 1.48, 1.47 (4 s, 12 H,
4 CCH3). Anal. Calcd for C34H44O12: C, 63.35;
H, 6.83. Found: C, 65.53; H, 6.32.
O-isopropylidene-3-O-benzyl-a- -xylofuran-
D
ose (196 mg, 0.70 mmol) in anhyd CH2Cl2 (5
,
mL) was added 4-A molecular sieves (1 g) and
ZnCl2 (0.6 g). The mixture was stirred for 10
min at rt, and a solution of 13 (145.2 mg, 0.55
mmol) in CH2Cl2 (5 mL) was added. The
mixture was stirred at rt for 12 h, at the end of
which time TLC (2:1 petroleum ether–EtOAc)
indicated that 13 had disappeared. The sus-
pension was filtered to remove solid material,
and the filtrate was washed with water (3×50
mL), dried over Na2SO4, and concentrated to
a syrup. The crude product was purified by
column chromatography using 1:2 petroleum
ether–EtOAc as the eluent. Compound 29
was obtained as a syrup (253 mg, 81%):
5-O-Acetyl-3,6-di-O-benzyl-1,2-O-isopropyl-
idene-h- -glucofuranose (32).—Acetylation of
D
31 (8.6 g, 21.5 mmol) with Ac2O (15 mL) in
C5H5N (20 mL) at rt for 4 h gave compound
32 in a quantitative yield as a syrup: [h]D
1
−26° (c 5.3, CHCl3); H NMR: l 7.40–7.20
1
(m, 10 H, 2 PhH), 5.92 (d, 1 H, J1,2 4.0 Hz,
H-1), 5.33 (m, 1 H, H-5), 4.65–4.41 (m, 6 H,
H-2, 4, 2 PhCH2), 3.97 (d, 1 H, J3,4 3.2 Hz,
H-3), 3.85 (dd, 1 H, J5,6 2.0, J6,6% 12.0 Hz,
H-6), 3.72 (dd, 1 H, J5,6% 6.0, J6,6% 12.0 Hz,
H-6%), 1.96 (s, 3 H, COCH3), 1.50, 1.34 (2 s, 6
H, 2 CCH3). Anal. Calcd for C25H30O7: C,
67.83; H, 6.82. Found: C, 67.87; H, 6.79.
[h]D+1.2° (c 1.4, CHCl3); H NMR: l 7.40–
7.30 (m, 10 H, PhH), 5.91 (d, 1 H, J2,1 3.8 Hz,
H-1), 4.98 (s, 1 H, H-1%), 4.68–4.45 (m, 5 H,
H-2, 2 PhCH2), 4.38–4.26 (m, 4 H, H-3%, 4,
5a, 5b), 4.17 (m, 1 H, H-4%), 4.06 (d, 1 H, J3%,2%
4.3 Hz, H-2%), 3.94–3.68 (m, 3 H, H-3, 5%a,
5%b), 2.64 (bs, 1 H, OH), 2.05 (s, 3 H,
COCH3), 1.52, 1.31 (2 s, 6 H, 2 CCH3). Anal.
Calcd for C31H36O10: C, 65.49; H, 6.34.
Found: C, 65.63; H, 6.32.
5-O-Acetyl-3,6-di-O-benzyl- -glucofuranose
D
(33).—A solution of 32 (5.2 g, 11.7 mmol) in
50% AcOH (60 mL) was refluxed with stirring
for 5 h, at the end of which time TLC (1:1
petroleum ether–EtOAc) indicated that the
reaction was complete. The mixture was con-
centrated to a syrup. The crude product was
purified by column chromatography with 1:1
petroleum ether–EtOAc as the eluent. Com-
pound 33 was obtained as a syrupy anomeric
mixture (4.4 g, 92%, a:b 1:1): [h]D −36° (c
6-O-Acetyl-3,4-di-O-benzyl-i-
osyl - (1“6) - 1,2:3,4 - di - O - isopropylidene-
h- -galactopyranose (30).—To a solution of
1,2:3,4-di-O-isopropylidene-a- -galactopyran-
D-glucopyran-
D
D
ose (182 mg, 0.70 mmol) in anhyd CH2Cl2 (7
,
mL) was added 4-A molecular sieves (1 g) and
ZnCl2 (0.5 g). The mixture was stirred for 10
min at rt, and a solution of 20 (234 mg, 0.61
mmol) in CH2Cl2 (3 mL) was added. The
mixture was stirred at rt for 12 h, at the end of
which time TLC (2:1 petroleum ether–EtOAc)
indicated that 20 had disappeared. The sus-
pension was filtered, and the filtrate was
washed with water (3×50 mL), dried over
Na2SO4, and concentrated to a syrup. The
crude product was purified by column chro-
matography with 1:2 petroleum ether–EtOAc
as the eluent. Compound 30 was obtained as a
syrup (326 mg, 83%): [h]D +1.6° (c 2.5,
1
6.5, CHCl3); H NMR: l 7.40–7.20 (m, 10 H,
2 PhH), 5.41 (d, 0.5 H, J1,2 3.8 Hz, H-1 of a
anomer), 5.28 (m, 1 H, H-5), 5.14 (s, 0.5 H,
H-1 of b anomer), 4.63–4.38 (m, 4 H, 2
PhCH2), 4.19–3.67 (5 H, H-2, 3, 4, 6, 6%), 1.96
(s, 3 H, COCH3). Anal. Calcd for C22H26O7:
C, 65.67; H, 6.48. Found: C, 65.84; H, 6.53.
5-O-Acetyl-3,6-di-O-benzyl-2-O-(p-toluene-
sulfonyl)- -glucofuranose (34).—To a solution
D
of compound 33 (3.4 g, 6.1 mmol) in CH2Cl2
(40 mL) was added TsCl (1.75 g, 9.2 mmol),
TBAHS (150 mg, 0.44 mmol) and 5% aq
NaOH (15.0 mL). The solution was stirred at
rt for 15 h, and then diluted with CH2Cl2 and
washed with cold water. The organic phase
was dried over Na2SO4, then evaporated un-
1
CHCl3); H NMR: l 7.40–7.20 (m, 10 H, 2
PhH), 5.50 (d, 1 H, J2,1 5.0 Hz, H-1), 5.06,
4.80 (2 d, 2 H, J 11.2 Hz, PhCH2), 4.87, 4.55
(2 d, 2 H, J 10.8 Hz, PhCH2), 4.61 (dd, 1 H,
J2,3 2.4, J4,3 7.9 Hz, H-3), 4.35, 4.31 (2 d, 2 H,
J 7.5 Hz, H-6%a, 6%b), 4.33 (dd, 1 H, J1,2 5.0,

J. Ning, F. Kong / Carbohydrate Research 330 (2001) 165–175
173
2 H, J 11.8 Hz, PhCH2), 4.40–4.25 (m, 2 H,
H-3, 4), 4.05 (dd, 1 H, J1,2 1.0, J2,3 4.8 Hz,
H-2), 3.84 (2 d, 1 H, J5,6 4.0, J6,6% 11.0 Hz,
H-6), 3.72 (2 d, 1 H, J5,6% 5.2, J6,6% 11.0 Hz,
H-6%), 3.31 (s, 3 H, OCH3), 2.02 (s, 3 H,
COCH3). Anal. Calcd for C23H28O7: C, 66.35;
H, 6.73. Found: C, 66.50; H, 6.77.
der diminished pressure to give 34 (2.4 g, 71%)
as an a,b mixture in the ratio of 1:6, along
with recovered starting material 3 (0.6 g).
1
Data for 34: [h]D −18° (c 7.3, CHCl3); H
NMR: l 7.80 (d, 2 H, PhꢀH of Ts), 7.39–7.19
(m, 12 H, PhH), 5.43 (d, 0.14 H, J1,2 4.2 Hz,
H-1 of a anomer), 5.28 (m, 1 H, H-5), 5.08 (s,
0.86 H, H-1 of b anomer), 4.77 (s, 0.86 H, H-2
of b anomer), 4.68 (dd, 0.14 H, J1,2 4.2, J2,3 3.6
Hz, H-2 of a anomer), 4.62–4.40 (5 H, 2
PhCH2, H-4), 4.20 (m, 1 H, H-3), 3.82–3.64 (2
H, H-6, 6%), 2.44 (s, 3×0.86 H, PhCH3 of b
anomer), 2.42 (s, 3×0.14 H, PhCH3 of a
anomer), 1.87 (s, 3×0.14 H, COCH3 of a
anomer), 1.86 (s, 3×0.86 H, COCH3 of b
anomer). Anal. Calcd for C29H32O9S: C, 62.59;
H, 5.76. Found: C, 62.41; H, 5.81.
5-O-Acetyl-3,6-di-O-benzyl-h-
osyl - (1“6) - 1,2:3,4 - di - O - isopropylidene - h-
-galactopyranose (37).—To a solution of
1,2:3,4-di-O-isopropylidene-a- -galactopyran-
D-mannofuran-
D
D
ose (130 mg, 0.50 mmol) in anhyd CH2Cl2 (4
,
mL) was added 4-A molecular sieves (1 g) and
ZnCl2 (0.5 g). The mixture was stirred for 10
min at rt, and a solution of 35 (156 mg, 0.41
mmol) in CH2Cl2 (3 mL) was added. The
mixture was stirred at rt for 12 h, at the end of
which time TLC (2:1 petroleum ether–EtOAc)
indicated that 35 had disappeared. The sus-
pension was filtered to remove solid material,
and the filtrate was washed with water (3×50
mL), dried over Na2SO4, and concentrated to
a syrup. The crude product was purified by
column chromatography with 1:2 petroleum
ether–EtOAc as the eluent. Compound 37
was obtained as a syrup (213 mg, 84%): [h]D
5-O-Acetyl-1,2-anhydro-3,6-di-O-benzyl-i-
-mannofuranose (35).—To a solution of 34
D
(560 mg, 1.01 mmol) in dry THF (6 mL) was
added t-BuOK (124 mg, 1.11 mmol), and the
mixture was stirred at rt for 10 min, at the end
of which time TLC (2:1 petroleum ether–
EtOAc) indicated that the starting material
had disappeared. The mixture was concen-
trated to dryness, and the residue was repeat-
1
+1.2° (c 2.7, CHCl3); H NMR: l 7.40–7.20
edly
extracted
with
3:1
petroleum
(m, 10 H, 2 PhH), 5.51 (d, 1 H, J1,2 4.9 Hz,
H-1), 5.37 (m, 1 H, H-5%), 4.99 (d, 1 H, J1%,2%
1.2 Hz, H-1%), 4.59–4.51 (m, 5 H, H-3, 2
PhCH2), 4.44–4.28 (m, 3 H, H-2, 3%, 4%), 4.21
(dd, 1 H, J3,4 7.6, J4,5 2.1 Hz, H-4), 4.13 (dd, 1
H, J1%,2% 1.2, J2%,3% 5.0 Hz, H-2), 3.96 (m, 1 H,
H-5), 3.82 (dd, 1 H, J5%,6%a 3.9, J6%a,6%b 11.2 Hz,
H-6%a), 3.76–3.64 (m, 3 H, H-6%b, 6a, 6b), 2.55
(bs, 1 H, OH), 2.03 (s, 3 H, COCH3), 1.55,
1.46, 1.35, and 1.34 (4 s, 12 H, 4 CCH3). Anal.
Calcd for C32H44O12: C, 62.01; H, 7.06.
Found: C, 61.94; H, 7.10.
ether–EtOAc. Concentration of the combined
extracts yielded 35 as a syrup (372 mg, 96%):
1
[h]D +23.7° (c 2.9, CHCl3); H NMR: l
7.42–7.20 (m, 10 H, 2 PhH), 5.38 (ddd, 1 H,
J4,5 6.6, J5,6 2.4, J5,6% 5.6 Hz, H-5), 5.13 (d, 1 H,
J1,2 2.0 Hz, H-1), 4.70, 4.62 (ABq, 2 H, J 11.7
Hz, PhCH2), 4.63 (dd, 1 H, J3,4 8.1, J4,5 6.6
Hz, H-4), 4.53, 4.48 (ABq, 2 H, J 11.2 Hz,
PhCH2), 4.40 (dd, 1 H, J2,3 2.0, J3,4 8.1 Hz,
H-3), 3.84 (dd, 1 H, J5,6 2.4, J6,6% 11.5 Hz,
H-6), 3.73 (dd, 1 H, J5,6% 5.6, J6,6% 11.5 Hz,
H-6%), 3.62 (t, 1 H, J1,2=J2,3=2.0 Hz, H-2),
2.03 (s, 3 H, COCH3).
5,6-Di-O-benzoyl-3-O-benzyl-2-O-(p-tolu-
enesulfonyl)- -glucofuranose (39).—To a solu-
D
Methyl
5-O-acetyl-3,6-di-O-benzyl-h- -
D
tion of 5,6-di-O-benzoyl-3-O-benzyl- -gluco-
D
furanose (38)17 (2.1 g, 4.39 mmol) in CH2Cl2
(40 mL) was added TsCl (1.17 g, 6.14 mmol),
TBAHS (75 mg, 0.22 mmol) and 5% aq
NaOH (12.0 mL). The solution was stirred at
rt for 15 h, and then diluted with CH2Cl2 and
washed with cold water. The organic phase
was dried over Na2SO4, then evaporated un-
der diminished pressure to give 39 (1.9 g, 69%)
as an a,b mixture in the ratio of 1:3, along
with recovered starting material 38 (0.2 g).
mannofuranoside (36).—Compound 35 (120
mg, 0.31 mmol) was dissolved in anhyd
MeOH (5 mL) and kept for 1 h at rt. TLC
(2:1 petroleum ether–EtOAc) indicated that
the reaction was complete. The solution was
concentrated to afford 36 quantitatively as a
1
syrup: [h]D +37.2° (c 1.8, CHCl3); H NMR:
l 7.38–7.24 (m, 10 H, 2 PhH), 5.38 (m, 1 H,
H-5), 4.82 (d, 1 H, J1,2 1.0 Hz, H-1), 4.57, 4.54
(ABq, 2 H, J 12 Hz, PhCH2), 4.53, 4.49 (ABq,

174
J. Ning, F. Kong / Carbohydrate Research 330 (2001) 165–175
1
J2,3=J3,4 =5.6 Hz, H-3), 4.10 (dd, 1 H, J1,2
Data for 39: [h]D −18° (c 7.3, CHCl3); H
0.9, J2,3 5.6 Hz, H-2), 3.33 (s, 3 H, OCH3).
Anal. Calcd or C28H28O8: C, 68.29; H, 5.69.
Found: C, 68.15; H, 5.61.
NMR: l 7.80 (d, 2 H, PhꢀH of Ts), 8.01–7.11
(m, 15 H, 3 PhH), 5.75 (m, 0.75 H, H-5 of b
anomer), 5.67 (m, 0.25 H, H-5 of a anomer),
5.52 (d, 0.25 H, J1,2 3.7 Hz, H-1 of a anomer),
5.12 (s, 0.75 H, H-1 of b anomer), 4.91 (dd,
0.75 H, J5,6 2.4, J6,6% 12.4 Hz, H-6 of b
anomer), 4.86 (dd, 0.25 H, J5,6 2.8, J6,6% 11.9
Hz, H-6 of a anomer), 4.80 (s, 0.75 H, H-2 of
b anomer), 4.72 (dd, 0.25 H, J1,2 3.7, J2,3 2.3
Hz, H-2 of a anomer), 4.63–4.56 (m, 2 H,
H-4, 6%), 4.54, 4.39 (2 d, 2 H, J 12.4 Hz,
PhCH2), 4.30 (dd, 0.25 H, J2,3 2.3, J3,4 4.0 Hz,
H-3 of a anomer), 4.25 (d, 0.75 H, J3,4 4.0 Hz,
H-3 of b anomer), 2.47 (s, 3×0.75 H, PhCH3
of b anomer), 2.45 (s, 3×0.25 H, PhCH3 of a
anomer). Anal. Calcd for C34H32O10S: C,
64.55; H, 5.06. Found: C, 64.61; H, 5.10.
1,2-Anhydro-5,6-di-O-benzoyl-3-O-benzyl-i-
Acknowledgements
This project was supported by Chinese
Academy of Sciences (KJ 952J1510 and KIP-
RCEES9904) and The National Natural Sci-
ence Foundation of China (59973026 and
29905004).
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