A facile method for the preparation of sugar orthoesters promoted by anhydrous sodium bicarbonate

Article abstract of DOI:10.1139/V09-146

A facile and eco-friendly method for the preparation of sugar orthoesters by using anhydrous sodium bicarbonate is described. Various sugar orthoesers, including sugar sugar orthoesters, were synthesized in good-to-excellent yields by the reaction of a pr

Full text of DOI:10.1139/V09-146

1733
A facile method for the preparation of sugar
orthoesters promoted by anhydrous sodium
bicarbonate
Shanqiao Wei, Jinzhong Zhao, and Huawu Shao
Abstract: A facile and eco-friendly method for the preparation of sugar orthoesters by using anhydrous sodium bicarbon-
ate is described. Various sugar orthoesers, including sugar–sugar orthoesters, were synthesized in good-to-excellent yields
by the reaction of a protected glycosyl bromide with an alcohol or sugar.
Key words: sugar orthoesters, anhydrous sodium bicarbonate, protected glycosyl bromide.
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Resume : On a developpe une methode facile et ecologique de preparation d’orthoesters de sucres utilisant le bicarbonate
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de sodium anhydre. On a realise la synthese de divers orthoesters de sucres, y compris des orthoesters de sucre-sucre, avec
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des rendements allant de bons a excellents en procedant a la reaction d’un bromure de glycosyle protege avec un alcool
ou un sucre.
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Mots-cles : orthoesters de sucres, bicarbonate de sodium anhydre, bromure de glycosyle protege.
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[Traduit par la Redaction]
ing anhydrous sodium bicarbonate instead of an organic
base is reported.15,16
Introduction
Sugar 1,2-orthoesters are some of the most important in-
termediates in organic synthesis,1,2 especially in the oligo-
saccharide synthesis.3–7 Sugar 1,2-orthoesters are classic
glycosyl donors and can be efficiently converted to the cor-
responding 1,2-trans-glycosides by the action of protonic or
Lewis acids, such as TMSOTf,8 BF3ꢀEt2O,9a and TfOH.9b
Sugar 1,2-orthoesters are also extremely practical for the se-
lective protection of a pyranose ring while the other acetyl
groups on the 3, 4, and 6 positions are converted to benzyl
groups, and so forth. At present, there are several methods
in the literature for the preparation of carbohydrate 1,2-or-
thoesters.10,11 The well-known method involves the treat-
ment of peracetylated or perbenzoylated glycosyl bromides
with alcohols in the presence of a quaternary ammonium
salt12 or silver triflate5,13 and an organic base, usually syn-
collidine or 2,6-lutidine.14 It is necessary to utilize two kinds
of reagents, quaternary ammonium salt and bulky amine
compound, for the reaction to occur.11a,15 Although the
method has been extensively used, there is one large disad-
vantage: the use of a smelly, toxic, and eco-unfriendly or-
ganic base. Knowing the broad spectrum of the significant
applications of sugar orthoesters, we have focused our inter-
est on improving the synthesis of sugar orthoesters. Herein,
a facile, less toxic, and efficient procedure for the synthesis
of 1,2-orthoesters, including sugar–sugar orthoesters, by us-
Result and discussion
Our studies started with the reaction of peracetylated glu-
copyranosyl bromide with methanol in the presence of tetra-
butylammonium bromide, anhydrous sodium bicarbonate,
˚
and a 4 A molecular sieve in dry acetonitrile solvent
(Scheme 1). The reaction was carried out at room tempera-
ture for 4 h, affording the glucopyranosyl methyl orthoester
in an 86% yield (Table 1, entry 1). To optimize the method,
we used toluene, 1,2-dichlorethane, N,N-dimethylformamide
(DMF), and tetrahydrofuran (THF), respectively, as the sol-
vent, and afforded the target product 2 in various yields
(Table 1, entries 2–5).
To establish the feasibility of this reaction as a general
method for the preparation of 1,2-orthoesters (Scheme 2),
we carried out the synthesis of 3,4,6-tri-O-acetyl mannose,
3,4,6-tri-O-acetyl galactose, 3,4-di-O-acetyl rhamnose or-
thoesters, and 3,4,6-tri-O-benzoyl mannose orthoester in
good to excellent yields, and the results are shown in Table 2
(entries 1–4). Since 6-O-tosyl and 6-O-mesyl of these or-
thoesters can be easily substituted by other groups, the li-
brary of sugar orthoesters is greatly expanded. However, the
synthesis of 6-O-tosyl and 6-O-mesyl orthoesters has not
been reported in the literature. Herein, with the suitable pro-
tocol in hand, 6-O-mesyl and 6-O-tosyl mannopyranosyl
bromide were treated by using various alcohols such as
methanol, isopropyl alcohol, and allyl alcohol, and the cor-
responding orthoesters (Table 2, entries 5–10). 6-O-Mesyl
orthosters 13 and 14 (Table 2, entries 5 and 6) and 6-O-tosyl
orthoster 19 (Table 2, entry 11) were obtained in good
yields. Whereas 6-O-mesyl orthoesters 15–18 (Table 2,
entries 7–10) and 6-O-tosyl orthoesters 20 and 21 (Table 2,
entries 12 and 13) were obtained in modest yields. The
Received 21 May 2009. Accepted 4 September 2009. Published
on the NRC Research Press Web site at canjchem.nrc.ca on
28 November 2009.
S. Wei, J. Zhao, and H. Shao.1 Natural Products Research
Centre, Chengdu Institute of Biology, Chinese Academy of
Sciences, Chengdu 610041, China.
1Corresponding author (e-mail: shaohw@cib.ac.cn).
Can. J. Chem. 87: 1733–1737 (2009)
doi:10.1139/V09-146
Published by NRC Research Press

1734
Can. J. Chem. Vol. 87, 2009
Scheme 1. The synthesis of glucopyranosyl methyl orthoester.
Table 2. Preparation for various orthoesters using anhydrous so-
dium bicarbonate.
Table 1. Optimization of the synthesis of glucopyra-
nosyl methyl orthoester.
Entry
Slovent
MeCN
Toluene
ClCH2CH2Cl
DMF
Time (h)
Yield (%)
1
2
3
4
5
3
6
6
4
8
86
69
71
60
75
THF
sugar–sugar orthoesters are extremely important intermedi-
ates for oligosaccharide synthesis. Comparing simple sugar
orthoesters, the reaction pathways of sugar–sugar orthoesters
are relatively simplified for oligosaccharide preparation; the
consideration is mainly focused on intra- and inter-molecular
rearrangement of the alkoxide.8a Sugar–sugar orthoesters
are usually synthesized by the reaction of a glycosyl bro-
mide donor with a glycosyl acceptor with only one free
hydroxyl group in dichloromethane in the presence of sil-
ver triflate and 2,4-lutidine.8a Although this method is effi-
cient, both silver triflate and 2,4-lutidine are toxic and
expensive. We hoped that our newly developed method
could be applied to the synthesis of sugar–sugar orthoesters.
Hence, 3 and 22 were treated in the presence of tetrabuty-
lammonium bromide and anhydrous sodium bicarbonate, the
reaction was completed at room temperature for 12 h, and
readily afforded the sugar–sugar orthoester 24 in an excel-
lent yield (90%). Encouraged by the success in synthesiz-
ing 24, we subsequently prepared sugar–sugar orthoesters
25–28 in good yields (Table 2, entries 15–18).
In summary, we developed a facile and effective protocol
for the synthesis of various sugar 1,2-orthoesters and sugar–
sugar orthoesters by using anhydrous sodium bicarbonate as
an inexpensive and environmentally friendly base. The ap-
proach, in terms of low toxicity of reagents, simplicity,
economy, and efficiency, will be a general, useful, and at-
tractive strategy for the synthesis of sugar 1,2-orthoesters.
Scheme 2. The synthesis of glucopyranosyl various orthoester.
Experimental
Reactions were monitored by thin layer chromatography
(TLC) using silica gel HSGF254 plates. Flash chromatog-
raphy was performed using silica gel HG/T2354–92. 1H
and 13C NMR (600 and 150 MHz, respectively) spectra
Published by NRC Research Press

Wei et al.
1735
1
were recorded in CDCl3. H NMR chemical shifts are re-
ported in ppm (d) relative to tetramethylsilane (TMS) with
the solvent resonance employed as the internal standard
(CDCl3, d 7.26 ppm). Data are reported as follows: chem-
ical shift, multiplicity (s = singlet, d = doublet, t = triplet,
m = multiplet), integration, and coupling constants (Hz).
13C NMR chemical shifts are reported in ppm from tetra-
methylsilane (TMS) with the solvent resonance as the in-
ternal standard (CDCl3, d 77.0 ppm). HR-MS (ESI)
spectra were recorded on BioTOF Q. Optical rotations
were acquired on a PerkinElmer M341 Digital Polarimeter.
d: 5.41 (d, 1H, J = 2.3), 5.06 (m, 2H), 4.59 (dd, 1H, J =
2.3, 3.9), 3.51 (m, 1H), 3.27 (s, 3H), 2.12 (s, 3H), 2.06 (s,
3H), 1.73 (s, 3H), 1.23 (d, 3H, J = 6.2).
Compound 12
25
Yield: 91%. White solid, mp 150–152 8C. ½aꢁD –129 (c
1
0.7, EtOAc). H NMR (CDCl3) d: 8.01 (d, 2H, J = 7.6),
7.90–7.89 (m, 4H), 7.71–7.69 (m, 2H), 7.53–7.47 (m, 3H),
7.42–7.32 (m, 6H), 7.30–7.26 (m, 3H), 5.88 (dd, 1H, J =
9.5, 9.6), 5.80 (d, 1H, J = 2.9), 5.66 (dd, 1H, J = 4.1, 10.0),
5.08 (dd, 1H, J = 3.3, 3.7), 4.51 (dd, 1H, J = 3.1, 11.9), 4.35
(dd, 1H, J = 4.7, 12.1), 4.14–4.09 (m, 1H), 3.23 (s, 3H).
General procedure for the synthesis of 1,2-orthoesters 2,
9–21
Compound 13
25
Yield: 88%. White solid, mp 128–129 8C. ½aꢁD –2.5 (c
The acetobromo glycoside (1 mmol) was dissolved in dry
acetonitrile (4 mL), then alcohol (10 mmol), tetrabutylam-
monium bromide (0.7 mmol), anhydrous sodium bicarbonate
1
0.2, EtOAc). H NMR (CDCl3) d: 5.51 (d, 1H, J = 2.5),
5.25 (dd, 1H, J = 9.4, 9.8), 5.17 (dd, 1H, J = 3.8, 10.0),
4.63 (dd, 1H, J = 3.1, 3.1), 4.3 (dd, 1H, J = 5.5, 11.1), 4.28
(dd, 1H, J = 2.7, 11.1), 3.79 (m, 1H), 3.28 (s, 3H), 3.05 (s,
3H), 2.12 (s, 3H), 2.08 (s, 3H), 1.73 (s, 3H). 13C NMR
(CDCl3) d: 170.3, 169.6, 124.3, 97.5, 76.2, 71.6, 70.2, 67.2,
65.5, 50.1, 37.7, 24.0, 20.7, 20.6. HR-MS (ESI) anal. calcd.
for C14H22NaO11S [M + Na]: 421.0775; found: 421.0772.
˚
(2 mmol), and molecular sieves 4 A; (400 mg) were added.
The reaction mixture was vigorously stirred for 3–7 h at
room temperature. TLC indicated when the reaction was
complete. The solvent was evaporated to dryness and the
residue was purified by silica gel column chromatrography.
General procedure for the synthesis of sugar–sugar
orthoesters 24–28
The glycosyl acceptor (1 mmol) and acetobromo glyco-
side (2 mmol) were dissolved in dry acetonitrile (10 mL),
then tetrabutylammonium bromide (1 mmol), anhydrous so-
Compound 14
25
Yield: 83%. White solid, mp 145–146 8C. ½aꢁD –1 (c 0.2,
1
EtOAc). H NMR (CDCl3) d: 5.49 (d, 1H, J = 2.5), 5.25 (dd,
1H, J = 9.5, 9.7), 5.17 (dd, 1H, J = 3.9, 9.9), 4.61 (dd, 1H,
J = 3.1, 3.5), 4.33 (dd, 1H, J = 5.5, 11.1), 4.28 (dd, 1H, J =
2.7, 11.0), 3.78 (m, 1H), 3.59–3.50 (m, 2H), 3.05 (s, 3H),
2.12 (s, 3H), 2.08 (s, 3H), 1.73 (s, 3H), 1.18 (t, 3H, J =
7.0). 13C NMR (CDCl3) d: 170.3, 169.6, 124.0, 97.5, 76.0,
71.6, 70.2, 67.3, 65.6, 58.4, 37.7, 24.3, 20.7, 20.6, 15.1.
HR-MS (ESI) anal. calcd. for C15H24NaO11S [M + Na]:
435.0932; found: 435.0936.
˚
dium bicarbonate (4 mmol), and molecular sieves 4 A;
(600 mg) were added. The reaction mixture was vigorously
stirred at room temperature for 12–15 h. TLC indicated
when the reaction was complete. The solvent was evapo-
rated to dryness and the residue was purified by silica gel
column chromatrography.
Characterization data
Compound 15
25
Yield: 77%. White solid, mp 127–129 8C. ½aꢁD +11 (c
Compound 2
1
0.1, EtOAc). H NMR (CDCl3) d: 5.87 (m, 1H), 5.51 (d,
25
1
Yield: 86%. Syrup. ½aꢁ +31 (c 0.8, EtOAc). H NMR
(CDCl3) d: 5.72 (d, 1H, JD= 5.1 Hz), 5.19 (dd, 1H, J = 2.8,
3.0), 4.90 (dd, 1H, J = 2.8, 9.6), 4.32 (m, 1H), 4.20 (m, 2H),
3.95 (m, 1H), 3.29 (s, 3H), 2.11 (s, 3H), 2.10 (s, 3H,), 2.09
(s, 3H), 1.71 (s, 3H).
1H, J = 2.8), 5.27–5.24 (m, 2H), 5.18–5.14 (m, 2H), 4.62
(dd, 1H, J = 3.1, 3.8), 4.33 (dd, 1H, J = 5.6, 11.3), 4.28
(dd, 1H, J = 3.0, 11.3), 4.06–4.00 (m, 2H), 3.79 (m, 1H),
3.05 (s, 3H), 2.12 (s, 3H), 2.08 (s, 3H), 1.75 (s, 3H). 13C
NMR (CDCl3) d: 170.2, 169.6, 133.9, 124.1, 116.8, 97.6,
76.0, 71.7, 70.1, 67.3, 65.5, 64.0, 37.7, 24.4, 20.7, 20.6.
HR-MS (ESI) anal. calcd. for C16H24NaO11S [M + Na]:
447.0932; found: 447.0925.
Compound 9
25
Yield: 84%. White needle, mp 107–108 8C. ½aꢁD –24 (c
1
0.2, EtOAc). H NMR (CDCl3) d: 5.49 (d, 1H, J = 2.5),
5.30 (dd, 1H, J = 9.7, 9.8), 5.15 (dd, 1H, J = 4.0, 10.0),
4.61 (dd, 1H, J = 2.9, 3.5), 4.24 (dd, 1H, J = 5.0, 12.2),
4.14 (dd, 1H, J = 1.9, 11.7), 3.68 (m, 1H), 3.28 (s, 3H),
2.12 (s, 3H), 2.07 (s, 3H), 2.05 (s, 3H), 1.74 (s, 3H).
Compound 16
25
Yield: 70%. White solid, mp 130-132 8C. ½aꢁD +1 (c 0.2,
1
EtOAc). H NMR (CDCl3) d: 5.53 (d, 1H, J = 2.9), 5.25 (dd,
1H, J = 9.4, 9.7), 5.18 (dd, 1H, J = 4.0, 10.0), 4.68 (dd, 1H,
J = 3.2, 3.2), 4.33 (dd, 1H, J = 5.6, 11.5), 4.29 (dd, 1H, J =
2.8, 11.2), 4.18 (d, 2H, J = 2.1), 3.80 (m, 1H), 3.05 (s, 3H),
2.38 (t, 1H, J = 1.9), 2.12 (s, 3H), 2.08 (s, 3H), 1.77 (s, 3H).
13C NMR (CDCl3) d: 170.2, 169.6, 123.9, 97.6, 79.4, 76.0,
73.7, 71.8, 69.9, 67.2, 65.4, 51.1, 37.7, 24.0, 20.7. HR-MS
(ESI) anal. calcd. for C16H22NaO11S [M + Na]: 445.0775;
found: 445.0783.
Compound 10
25
1
Yield: 80%. Syrup. ½aꢁD +80 (c 0.2, EtOAc). H NMR
[(CD3)2CO] d: 5.87 (d, 1H, J = 4.6), 5.40 (dd, 1H, J = 2.9,
3.1), 5.06 (dd, 1H, J = 3.4, 6.5), 4.42–4.40 (m, 2H), 4.17
(dd, 1H, J = 7.0, 11.3), 4.10 (dd, 1H, J = 5.8, 11.3), 3.23 (s,
3H), 2.08 (s, 3H), 2.01 (s, 3H), 2.00 (s, 3H), 1.60 (s, 3H).
Compound 11
Compound 17
25
25
1
Yield: 66%. ½aꢁD +20 (c 0.4, EtOAc). H NMR (CDCl3)
Yield: 60%. White solid, mp 109–111 8C. ½aꢁD +1 (c 0.4,
Published by NRC Research Press

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Can. J. Chem. Vol. 87, 2009
1
EtOAc). H NMR (CDCl3) d: 5.48 (d, 1H, J = 2.7), 5.25 (dd,
1H, J = 9.5, 9.5), 5.17 (dd, 1H, J = 4.1, 9.9), 4.62 (dd, 1H,
J = 2.9, 3.7), 4.33 (dd, 1H, J = 5.8, 11.3), 4.28 (dd, 1H, J =
2.9, 11.2), 3.95 (m, 1H), 3.79 (m, 1H), 3.05 (s, 3H), 2.11 (s,
3H), 2.08 (s, 3H), 1.73 (s, 3H), 1.15 (d, 3H, J = 6.2), 1.14
(d, 3H, J = 9.1). 13C NMR (CDCl3) d: 170.2, 169.6, 124.1,
97.4, 75.5, 71.7, 70.1, 67.4, 66.6, 65.6, 37.7, 24.4, 23.7,
20.7. HR-MS (ESI) anal. calcd. for C16H26NaO11S [M +
Na]: 449.1088; found: 449.1011.
1H, J = 6.2, 9.2), 2.11 (s, 3H), 2.06 (s, 3H), 2.04 (s, 3H),
1.76 (s, 3H), 1.53 (s, 3H), 1.42 (s, 3H), 1.33 (s, 3H), 1.32
(s, 3H).
Compound 25
25
1
Yield: 76%. Syrup. ½aꢁ –34.3 (c 0.3, EtOAc). H NMR
[(CD3)2CO)] d: 5.61 (d, 1DH, J = 2.2), 5.44 (d, 1H, J = 5.0),
5.20 (dd, 1H, J = 4.0, 10.0), 4.97 (dd, 1H, J = 9.7, 9.8), 4.65
(dd, 1H, J = 2.4, 4.0), 4.60 (dd, 1H, J = 2.0, 7.9), 4.32 (dd,
1H, J = 2.2, 4.9), 4.23 (dd, 1H, J = 1.4, 7.9), 3.91 (m, 1H),
3.69 (m, 1H), 3.64 (dd, 1H, J = 5.6, 10.1), 3.56 (dd, 1H, J =
6.7, 9.8), 2.03 (s, 6H), 1.66 (s, 3H), 1.47 (s, 3H), 1.36 (s,
3H), 1.31 (s, 3H), 1.30 (s, 3H), 1.16 (d, 3H, J = 6.2). 13C
NMR (CDCl3) d: 169.6, 169.5, 123.8, 108.7, 108.1, 97.3,
96.3, 77.3, 71.0, 70.7, 70.5, 66.9, 61.4, 25.5, 24.8, 24.3,
23.8, 19.8, 16.9. HR-MS (ESI) anal. calcd. for C24H36NaO13
[M + Na]: 555.2048; found: 555.2037.
Compound 18
25
Yield: 68%. White solid, mp 141–142 8C. ½aꢁD +10 (c
1
0.2, EtOAc). H NMR (CDCl3) d: 7.37–7.26 (m, 5H), 5.52
(d, 1H, J = 2.7), 5.26 (dd, 1H, J = 9.5, 9.7), 5.16 (dd, 1H,
J = 3.9, 9.9), 4.64–4.54 (m, 3H), 4.35–4.28 (m, 2H), 3.80
(m, 1H), 3.05 (s, 3H), 2.10 (s, 3H), 2.08 (s, 3H), 1.81 (s,
3H). 13C NMR (CDCl3) d: 170.2, 169.6, 137.4, 128.6,
128.4, 127.7, 127.5, 127.0, 124.2, 97.6, 76.0, 71.7, 70.0,
67.3, 65.5, 65.0, 37.7, 24.4, 20.7; HR-MS (ESI) anal. calcd
for C20H26NaO11S [M + Na]: 497.1088; found: 497.1079.
Compound 26
25
1
Yield: 78%. Syrup. ½aꢁD –18.5 (c 0.2, EtOAc). H NMR
[(CD3)2CO] d: 5.72 (d, 1H, J = 5.3), 5.44 (d, 1H, J = 4.9),
5.13 (dd, 1H, J = 2.8, 2.8), 4.86 (dd, 1H, J = 2.0, 9.5), 4.60
(dd, 1H, J = 2.4, 7.9), 4.45 (m, 1H), 4.32 (dd, 1H, J = 2.4,
5.2), 4.25 (dd, 1H, J = 1.8, 7.9), 4.15 (d, 2H, J = 4.4), 3.99
(m, 1H), 3.87 (m, 1H), 3.67 (dd, 1H, J = 6.3, 9.7), 3.52 (dd,
1H, J = 6.5, 9.7), 2.05 (s, 6H), 2.01 (s, 3H), 1.67 (s, 3H,
CH3), 1.45 (s, 3H), 1.37 (s, 3H), 1.31 (s, 3H), 1.30 (s, 3H).
Compound 19
25
1
Yield: 80%. Syrup. ½aꢁ +30.5 (c 0.2, EtOAc). H NMR
(CDCl3) d: 7.78 (d, 2H, JD= 8.3), 7.34 (d, 2H, J = 7.9), 5.41
(d, 1H, J = 2.7), 5.16 (dd, 1H, J = 9.2, 9.6), 5.11 (dd, 1H,
J = 3.8, 9.8), 4.56 (dd, 1H, J = 2.9, 3.7), 4.11 (m, 2H), 3.72
(m, 1H), 3.24 (s, 3H), 2.45 (s, 3H), 2.10 (s, 3H), 2.03 (s,
3H), 1.59 (s, 3H). 13C NMR (CDCl3) d: 170.3, 169.5, 145.0,
132.5, 129.8, 128.1, 124.3, 97.4, 76.3, 71.3, 70.2, 67.9, 65.9,
50.0, 24.0, 21.6, 20.7, 20.6; HR-MS (ESI) anal. calcd for
C20H26NaO11S [M + Na]: 497.1088; found: 497.1081.
Compound 27
25
1
Yield: 78%. Syrup. ½aꢁD +9.5 (c 0.2, EtOAc). H NMR
[(CD3)2CO] d: 5.87 (d, 1H, J = 4.9), 5.45 (dd, 1H, J = 4.9),
5.40 (dd, 1H, J = 2.5, 2.9), 5.07 (dd, 1H, J = 3.5, 6.4), 4.61
(dd, 1H, J = 2.2, 7.8), 4.43–4.40 (m, 2H), 4.27 (m, 1H), 4.18
(dd, 1H, J = 7.2, 11.5), 4.10 (dd, 1H, J = 5.5, 11.3), 4.04
(dd, 1H, J = 7.2, 14.1), 3.90 (dd, 1H, J = 4.9, 6.7), 3.68 (m,
1H), 3.55 (m, 1H), 2.13–2.01 (m, 9H), 1.63 (s, 3H), 1.46 (s,
3H), 1.37 (s, 3H), 1.31 (s, 3H), 1.30 (s, 3H).
Compound 20
25
1
Yield: 78%. Syrup. ½aꢁ +19.7 (c 0.6, EtOAc). H NMR
(CDCl3) d: 7.78 (d, 2H, JD= 7.3), 7.34 (d, 2H, J = 7.7), 5.40
(m, 1H), 5.27–5.11 (m, 2H), 4.55 (m, 1H), 4.13–4.07 (m,
2H), 3.72 (m, 1H), 3.51 (m, 2H), 2.44 (s, 3H), 2.10 (s, 3H),
2.02 (s, 3H), 1.60 (s, 3H), 1.16 (t, 3H, J = 6.72). 13C NMR
(CDCl3) d: 170.3, 169.5, 145.0, 132.5, 129.8, 128.1, 124.0,
97.4, 76.1, 71.3, 70.2, 68.0, 65.9, 58.2, 24.3, 21.6, 20.7,
20.6, 15.0 HR-MS (ESI) anal. calcd for C21H28NaO11S
[M + Na]: 511.1245; found: 511.1268.
Compound 28
25
1
Yield: 80%. Syrup. ½aꢁ +10 (c 0.3, EtOAc). H NMR
(CDCl3) d: 7.34–7.26 (m, D15H), 5.39 (d, 1H, J = 2.5), 5.27
(dd, 1H, J = 9.6, 9.6), 5.12 (dd, 1H, J = 3.9, 9.8), 4.90 (dd,
2H, J = 7.8, 10.9), 4.82 (d, 1H, J = 11.0), 4.77 (d, 1H, J =
11.0), 4.69 (d, 1H, J = 11.0), 4.62 (d, 1H, J = 10.9), 4.48
(dd, 1H, J = 2.9, 3.3), 4.28 (d, 1H, J = 7.8), 4.23 (dd, 1H,
J = 5.1, 12.3), 4.14 (dd, 1H, J = 2.6, 12.2), 3.75 (d, 1H, J =
8.8), 3.68–3.60 (m, 3H), 3.55 (s, 3H), 3.51 (d, 1H, J = 9.2),
3.41 (m, 2H), 2.07 (s, 3H), 2.04 (s, 3H), 2.00 (s, 3H), 1.74
(s, 3H). 13C NMR (CDCl3) d: 170.6, 170.3, 169.4, 138.6,
138.5, 138.3, 128.5, 128.4, 128.1, 128.0, 127.9, 127.8,
127.7, 127.6, 124.2, 104.6, 97.4, 84.6, 82.3, 77.7, 76.4,
75.6, 74.9, 74.7, 73.8, 71.5, 70.3, 65.7, 62.5, 61.8, 57.0,
24.4, 20.7, 20.6. HR-MS (ESI) anal. calcd. for C42H50NaO15
[M + Na]: 817.3042; found: 817.3018.
Compound 21
25
1
Yield: 71%. Syrup. ½aꢁ +23 (c 0.2, EtOAc). H NMR
(CDCl3) d: 7.78 (d, 2H, J D= 8.2), 7.34 (d, 2H, J = 8.0), 5.43
(d, 1H, J = 2.8), 5.18–5.11 (m, 2H), 4.62 (dd, 1H, J = 3.2,
3.3), 4.15 (d, 2H, J = 1.8), 4.15–4.07 (m, 4H), 3.76 (m, 1H),
2.45 (s, 3H), 2.37 (t, 1H, J = 2.3), 2.10 (s, 3H), 2.03 (s, 3H),
1.63 (s, 3H). 13C NMR (CDCl3) d: 170.2, 169.5, 145.1,
132.5, 130.0, 129.8, 128.1, 123.9, 97.5, 79.4, 76.0, 73.7,
71.6, 69.9, 68.0, 65.7, 51.0, 24.0, 21.6, 20.7, 20.6, 14.2;
HR-MS (ESI) anal. calcd for C22H26NaO11S [M + Na]:
521.1088; found: 521.1065.
Compound 24
Supplementary data
25
Yield: 90%. White solid, mp 121–123 8C. ½aꢁD –27.7 (c
1
0.3, EtOAc). H NMR (CDCl3) d: 5.50 (m, 2H), 5.28 (dd,
Supplementary data for this article are available on the
journal Web site (canjchem.nrc.ca) or may be purchased
from the Depository of Unpublished Data, Document Deliv-
ery, CISTI, National Research Council Canada, Ottawa, ON
K1A 0R6, Canada. DUD 5297. For more information on ob-
1H, J = 9.4, 9.8), 5.18 (dd, 1H, J = 4.1, 10.0), 4.62 (dd, 1H,
J = 3.1, 3.5), 4.58 (dd, 1H, J = 2.4, 7.9), 4.29 (dd, 1H, J =
2.4, 5.1), 4.24–4.22 (m, 2H), 4.15 (dd, 1H, J = 2.8, 11.9),
3.91 (dd, 1H, J = 5.5, 6.1), 3.74–3.69 (m, 2H), 3.60 (dd,
Published by NRC Research Press

Wei et al.
1737
(8) (a) Kong, F. Carbohydr. Res. 2007, 342 (3–4), 345. doi:10.
1016/j.carres.2006.09.025. PMID:17109835.; (b) Yang, Z.;
Lin, W.; Yu, B. Carbohydr. Res. 2000, 329 (4), 879. doi:10.
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3729. doi:10.1016/S0040-4039(02)00584-1.; (d) Fraser-Reid,
B.; Grimme, S.; Piacenza, M.; Mach, M.; Schlueter, U.
taining material, refer to cisti-icist.nrc-cnrc.gc.ca/cms/
unpub_e.shtml.
Acknowledgment
We are grateful for financial support from the Chinese
Academy of Sciences (Hundreds of Talents Program).
Chem. Eur. J. 2003,
200304856.
9 (19), 4687. doi:10.1002/chem.
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