α-Selective synthesis of 2-deoxy-glycosides and disaccharides

Article abstract of DOI:10.1080/07328303.2018.1439498

A metal-free catalytic method for the synthesis of 2-deoxy glycosides and disaccharides has been developed using stable 2-deoxy glucosyl and galactosyl acetate donors. They could react with a variety of acceptors in the presence of catalytic amount of TMSOTf at 0°C to form glycosides, glycoconjugates, and disaccharides with excellent α-selectivity (> 19:1) and yields (up to 99%) in a short time (0.5 h). With this expedient method, several new compounds against human K562 and SMMC7721 cell lines were obtained and tested with in vitro antitumor bioactivities.

Full text of DOI:10.1080/07328303.2018.1439498

Journal of Carbohydrate Chemistry
ISSN: 0732-8303 (Print) 1532-2327 (Online) Journal homepage: http://www.tandfonline.com/loi/lcar20
α-Selective synthesis of 2-deoxy-glycosides and
disaccharides
Guofang Yang, Xiaosheng Luo, Hong Guo, Qingbing Wang, Jiafen Zhou,
Tianyun Huang, Jie Tang, Junjie Shan & Jianbo Zhang
To cite this article: Guofang Yang, Xiaosheng Luo, Hong Guo, Qingbing Wang, Jiafen
Zhou, Tianyun Huang, Jie Tang, Junjie Shan & Jianbo Zhang (2018): α-Selective synthesis
of 2-deoxy-glycosides and disaccharides, Journal of Carbohydrate Chemistry, DOI:
10.1080/07328303.2018.1439498
To link to this article: https://doi.org/10.1080/07328303.2018.1439498
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JOURNAL OF CARBOHYDRATE CHEMISTRY
, VOL. , NO. , –
https://doi.org/./..
α-Selective synthesis of -deoxy-glycosides and
disaccharides
Guofang Yanga, Xiaosheng Luoa, Hong Guoa, Qingbing Wanga, Jiafen Zhoua,
Tianyun Huanga, Jie Tanga, Junjie Shanb, and Jianbo Zhanga
aSchool of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China;
bDepartment of Pharmacology, Beijing Institute of Pharmacology and Toxicology, Beijing, China
ABSTRACT
ARTICLE HISTORY
Received  November 
Revised  February 
Accepted  February 
A metal-free catalytic method for the synthesis of 2-deoxy gly-
cosides and disaccharides has been developed using stable 2-
deoxy glucosyl and galactosyl acetate donors. They could react
with a variety of acceptors in the presence of catalytic amount of
TMSOTf at 0°C to form glycosides, glycoconjugates, and disaccha-
rides with excellent α-selectivity (> 19:1) and yields (up to 99%)
in a short time (0.5 h). With this expedient method, several new
compounds against human K562 and SMMC7721 cell lines were
obtained and tested with in vitro antitumor bioactivities.
KEYWORDS
-deoxy glycosides; -deoxy
disaccharides; TMSOTf;
α-selective glycosylation;
antitumor activity
GRAPHICAL ABSTRACT
Introduction
2-Deoxyglycosides and 2-deoxysugar-containing oligosaccharides are common in
naturally glycosylated products with a wide range of biological activities,[1] espe-
cially antitumor activities.[2–9] Owing to their important biological relevance, the
synthesis of 2-deoxysugars and their derivatives has become an important field
in carbohydrate chemistry and natural product synthesis.[10–11] However, the cre-
ation of 2-deoxy glycosidic linkages directly from 2-deoxy glycosyl donors is
more challenging than other glycosidic bond formation due to the lack of stereo-
directing anchimeric assistance from the C-2 position, which leads to a mixture
of anomers at most situations.[12–16] Some remarkable progress has been made in
the past few years in the synthesis of 2-deoxy glycosides by acid-catalyzed activa-
tion of glycals,[17–22] anomeric esters,[23] glycosyl halides,[24] thioglycosides,[25–26]
CONTACT Jianbo Zhang
jbzhang@chem.ecnu.edu.cn
 Chemistry Building, Dongchuan Road, Shanghai
, China; Junjie Shan
shanjunjie@.com  Taiping Road, Beijing , China.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lcar.
©  Taylor & Francis Group, LLC

2
G. YANG ET AL.
O-glycosides,[27] and 2,3-anhydrosugars.[28] However, unstable deoxy glycosyl
donors, harsh reaction conditions, excess catalysts, high price, complicated oper-
ation, low efficiency and poor selectivity are usually encountered in the practice.
Hence, there is still a need to explore general promoter systems for convenient and
stereoselective synthesis of 2-deoxy glycosides.
In 2008, Ye et al.[29] reported the use of 3,4-O-carbonate protected thioglyco-
sides to afford α-2-deoxy glycosides in good stereoselectivity by the preactivation
protocol. In 2014, Mong et al.[30] applied it to activating 2-deoxythioglycosides for
DMF modulated iterative one-pot glycosylation. Recently, Zeng et al.[31] reported
the mild glycosylation conditions based on transition-metal catalyzed activation of
ortho-alkynylbenzoate glycosides,[32–33] which was employed for the assembly of
disaccharide in a 90% yield and in an α/β ratio of 8:1. Previously, α-2-deoxy aro-
matic glycosides was achieved when the glycosylation of 2-deoxyglycosyl acetates
and phenols was carried out in the presence of catalytic amount of TMSOTf in our
group.[34] In order to form a complete reaction system, this method has been applied
to synthesize other kinds of α-2-deoxy alkyl glycosides and oligosaccharides with
high yields and good α-selectivity.
Results and discussion
At the outset, the coupling of acetylated 2-deoxy sugar donor 1 and n-butyl alco-
hol 2d furnished glycoside in a 90% yield and in an α/β ratio of 6:1 in the presence
of TMSOTf. We next explored the use of other acceptors. As anticipated, the reac-
tions between 2-deoxy glucosyl donor 1 and a series of acceptors including alcohols,
amino acids, and sterols were carried out and the results are shown in Table 1.
We found that primary alcohol acceptors (Table 1, entries 1–9) gave good to
excellent yields (88%–98%) and high α-selectivity (α:β = 4:1 up to 10:1). The use
of secondary alcohols as acceptors (Table 1, entries 10–12) led to a slight decrease
in the yield, probably because of steric hindrance. In addition, when hindered and
relatively complex acceptors, such as amino acids, were employed (Table 1, entries
13–15), they could also afforded 2-deoxyglycosides in excellent yields and high
α-selectivity. Encouraged by these results, we further extended the scope of the
2-deoxyglycosylation reaction to sterols (Table 1, entries 16–18), and the reactions
proceeded well to give yields of 88–93% and in this instance α/β ratios of 3:1–5:1
were observed. The results showed that good yields and stereoselectivity could be
obtained when 2-deoxyglucosyl acetates as glycosyl donors were used.
Next, we sought to extend this glycosylation method to the generation of
2-deoxy galactosylglycosides. Excitingly, the system could also be applied to
2-deoxygalactosyl donor 4 and high yields and α:β stereoselectivity were obtained
with these reaction as shown in Table 2.
From Table 2, we could conclude that not only primary alcohols (Table 2, entries
1–9) but also hindered secondary alcohols (Table 2, entries 10–12) could afford
excellent results. All the reactions provided the corresponding 2-deoxy-α-alkyl-O-
glycosides as the only detectable glycosylation products with high yields (84%–99%)

JOURNAL OF CARBOHYDRATE CHEMISTRY
3
Table . Stereoselective glycosylation reaction of -deoxyglucose.
Entry
a
Acceptors
Products
Yieldc (%)

α:βd
2a
3a
:
a
2b
3b

.:
a

2c
2d
3c


:
:
3d
b

2e
2f
3e
3f





:
:
:

2g
2h
2i
3g
3h
3i
b

:
:

2j
3j

:

2k
3k
3l



:
:


2l
2m
3m
> :


2n
3n
3o


> :
> :
2o
(Continued on next page)

4
G. YANG ET AL.
Table . Continued
Entry
Acceptors
Products
Yieldc (%)
α:βd



Cholesterol 2p
Diosgenin 2q
DHEA 2r
3p
3q
3r



:
:
:
aROH (. equiv.); bTMSOTf (. equiv.); cIsolated yield; dDetermined byH NMR.
and α-stereoselectivity. Since some amino acid acceptors are sterically hindered and
bulkier than typical primary alcohols and secondary alcohols, 5n and 5o (Table 2,
entries 14 and 15) were afforded in slightly lower yields (87% and 84%), but they,
as well as 5m the glycosylation product of another amino acid, were formed with
higher α-selectivity. Compared with Table 1, we can also find that between glucosyl
donor and galactosyl donor, the stereoselectivity of the latter was generally better,
which was probably resulted from yielding intermediate at the β-face due to the
participation of the C4-acetoxyl group of galactosyl donor.[35–36]
As we know, 2-deoxysugar-containing oligosaccharides are common in naturally
glycosylated products,[1] such as landomycins,[37] olivomycins,[38] vancomycin,[39]
and anthracyclines.[40] We would like to further explore the TMSOTf catalyzed
reaction in the synthesis of 2-deoxysugar-containing disaccharides with differ-
ent glycosyl acceptors. Delightfully, we also obtained high yields and remarkable
α-stereoselectivity during the coupling reaction between 2-deoxyglycosyl acetate
donors and glycosyl acceptors, as shown in Table 3, which were difficult to achieve
under conventional conditions.[31]
Glycosyl acceptors with a primary alcohol, with either benzyl or benzoyl pro-
tecting groups, and with either trichloroethyl or thiophenyl linked to the anomeric
position (Table 3, entries 1 and 5) gave excellent isolated yields (90–99%) and
stereoselectivity (>19:1) of the desired product. This high stereoselectivity was
maintained regardless of the position of the free hydroxyl group in the acceptors.
Couplings to secondary hydroxyl groups at C-2, C-3, and C-4 (Table 3, entries
2–4) also proceeded extremely well with excellent isolated yields (87–99%) and
stereoselectivity. It should be noted that the more challenging reactions of glucosyl
donor gave lower α-selectivity than that of galactosyl donor. Nevertheless, the gly-
cosylation could also furnish the expected disaccharide 7c as the major product in
excellent yield of 95% (Table 3, entry 3). These results highlighted that the TMSOTf
catalyzed reaction is tolerant of most commonly used protecting groups, such as
benzyl ethers and benzoyl esters. Furthermore, the reaction worked well across the
board and the overall mild reaction condition makes this procedure general.
Cardiac glycosides show antitumor activities and their deoxy-sugar chains are
vital for their antitumor effects.[41] In order to study the structure-activity relation-
ship of cardiac glycosides toward tumors and get more potent antitumor agents, a
series of 2-deoxy glycosides and disaccharides synthesized by this novel glycosyla-
tion method were evaluated in vitro against the human K562 and SMMC7721 cell
lines by the standard MTT assay[42] for their antitumor activity. Interestingly, they

JOURNAL OF CARBOHYDRATE CHEMISTRY
5
Table . Stereoselective glycosylation reaction of -deoxygalactose.
Entry
a
Acceptors
Products
Yield c (%)

α:β d
2a
5a
:
a
2b
5b

:
a

2c
2d
5c


:
:
5d
b

2e
2f
5e
5f





.:
:

2g
2h
2i
5g
5h
5i
.:
:
b

:

2j
5j

:

2k
5k
5l



.:
:


2l
2m
5m
> :


2n
5n
5o


> :
> :
2o
(Continued on next page)

6
G. YANG ET AL.
Table . Continued
Entry
Acceptors
Products
Yield c (%)
α:β d



Cholestsrerol 2p
Diosgenin 2q
DHEA 2r
5p
5q
5r



:
:
:
aROH (. equiv.); bTMSOTf (. equiv.); cIsolated yield; dDetermined by H NMR.
Table . α-Selective -deoxyglycosylation for the synthesis of -deoxysugar-containing
disaccharides.
Entry

Acceptor
Product
Yield (%)a
α:βb
R = H, R = AcO 7a
R = AcO, R = H 8a


>:
>:
6a


R = H, R = AcO 7b
R = AcO, R = H 8b


>:
>:
6b
6c
R = H, R = AcO7c
R = AcO, R = H 8c


:
>:

R = H, R = AcO 7d
R = AcO, R = H 8d


>:
>:
6d
6e
c
R = H, R = AcO 7e
R = AcO, R = H 8e


>:
>:
aIsolated yield; bRatio determined by H NMR.; cThe acceptor was used in . equiv.

JOURNAL OF CARBOHYDRATE CHEMISTRY
7
Table . In vitro antitumor activity test of synthetic compounds against human K and SMMC
cell linesa.
Inhibition rate (%)
Entry
Compound
Sample concentration (µg/mL)
K
SMMC

DDPb
3o
3p
7a

.
.
.
.
.
.
—
—
.
.













.
.
.
.
.
.
7c
8a
8b
8c

aDMSO was used as solvent; bDDP: cis-Dichlorodiamminoplatinum-II.
were proven to possess good antitumor activity as shown inTable 4. Further research
is still in progress.
In conclusion, we developed a metal-free catalytic α-selective glycosylation
method for the synthesis of 2-deoxy glycosides using TMSOTf as the catalyst. Fur-
thermore, the application of this method to disaccharide synthesis was also demon-
strated. With this new method, several new 2-deoxy glycosides and disaccharides
with moderate antitumor activity against human K562 and SMMC7721 cell lines
were synthesized. As a number of natural products are glycosylated with deoxy-
sugars, this novel glycosylation method should be useful for their preparation as
well.
Experimental section
General procedures
All chemicals were purchased as reagent grade and used without further purifi-
cation, unless otherwise noted. Dichloromethane (CH2Cl2), pyridine, and toluene
were distilled over calcium hydride (CaH2). Methanol was distilled from magne-
sium. DMF was stirred with CaH2 and distilled under reduced pressure. All reac-
tions were carried out under nitrogen atmosphere with freshly distilled solvents,
unless otherwise noted. Reactions were monitored by analytical thin-layer chro-
matography (TLC) on silica gel GF254 precoated on glass plates (10–40 µm, Yan-
tai, China). Spots were detected under UV (254 nm) and/or by staining with 10%
(v/v) H2SO4 in ethanol. Solvents were evaporated under reduced pressure and below
˚
40°C (bath temerature). Molecular sieves (4A) used for reactions were crushed
and activated in vacuo at 390°C for 8 h. Organic solutions of crude products were
dried over anhydrous Na2SO4. Column chromatography was performed on silica
gel (10–40 µm, Yantai, China). 1H NMR and 13C NMR spectra were recorded with a
Bruker DRX 500 spectrometer. Chemical shifts (in ppm) were referenced to tetram-
ethylsilane (δ = 0 ppm) in deuterated chloroform. Mass Spectra experiments were

8
G. YANG ET AL.
performed on LTQ-XL (Thermo Scientific, USA) with an electrospray (ESI) ion
source.
Allyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranoside (3a)
˚
Glycosyl donor (30.0 mg, 0.09 mmol) and 4A molecular sieves (30.0 mg) were
weighed into a 25 mL round-bottom flask under N2, followed by the addition of
the acceptor (12.2 µL, 0.11 mmol, 1.2 equiv.) and TMSOTf (5.4 µL, 0.03 mmol, 0.3
equiv.) in anhydrous dichloromethane. The solution was then stirred under N2 until
the reaction was determined to be complete by TLC analysis of the crude material.
The solution was then concentrated in vacuum and purified by column chromatog-
raphy (hexane/EtOAc = 5:1) to afford 3a as a colorless syrups (29 mg, 98% yield). 1H
NMR (500 MHz; CDCl3) δ 5.89–5.91 (1H, m), 5.34 (1H, ddd, J = 5.4, 9.5, 11.7 Hz),
5.28 (1H, dd, J = 1.5, 15.7 Hz), 5.21 (1H, dd, J = 1.2, 10.3 Hz), 4.99–5.03 (2H, m),
4.32 (1H, dd, J = 4.5, 12.2 Hz), 4.13 (1H, dd, J = 5.2, 7.7 Hz), 4.06 (1H, dd, J =
2.1, 12.2 Hz), 3.98–3.99 (2H, m), 2.27 (1H, dt, J = 5.2, 7.7 Hz), 2.10 (3H,s), 2.04
(3H, s), 2.01 (3H, s), 1.85 (1H, dt, J = 3.6, 11.7 Hz); ESI-MS: Calcd for C15H22O8Na
[M+Na]+: 353.12, found 353.11.
Benzyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranoside (3b)
Compound 3b was obtained as colorless syrups (33.2 mg, 97% yield) from the reac-
tion between 1 (30.0 mg, 0.09 mmol) and 2b (18.7 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 7.29–7.37 (5H, m), 5.36 (1H, ddd, J = 2.5, 5.0, 11.5 Hz), 4.99- 5.04 (2H, m),
4.66 (1H, d, J = 12.0 Hz), 4.50 (1H, d, J = 12.0 Hz), 4.29 (1H, dd, J = 4.5, 12.5 Hz),
3.97–4.01 (2H, m), 2.28 (1H, dd, J = 5.4, 12.8 Hz), 2.09 (3H, s), 2.03 (3H, s), 2.00
(3H, s), 1.84 (1H, dt, J = 3.5, 12.8 Hz); ESI-MS: Calcd for C19H24O8Na [M+Na]+:
403.14, found 403.12.
Propargyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranoside (3c)
Compound 3c was obtained as colorless syrups (29.9 mg, 93% yield) from the
reaction between 1 (30.0 mg, 0.09 mmol) and 2c (5.2 µL, 0.11 mmol, 1.2 equiv.)
1
under the same conditions described above for the synthesis of 3a. H NMR
(500 MHz; CDCl3) δ 5.32 (1H, ddd, J = 5.5, 9.5, 11.5 Hz), 5.16 (1H, d, J =
2.7 Hz), 5.03 (1H, t, J = 10.0 Hz), 4.37 (1H, d, J = 1.9 Hz), 4.31 (1H, dd, J =
4.2, 12.2 Hz), 4.22 (2H, d, J = 2.0 Hz), 4.06 (1H, dd, J = 2.0, 12.0 Hz), 4.01 (1H,
ddd, J = 2.0, 4.0, 10.0 Hz), 2.44 (1H, dd, J = 10.3, 12.8 Hz), 2.28 (1H, dd, J =
5.2, 13.1 Hz), 2.09 (3H, s), 2.04 (3H, s), 2.02 (1H, dd, J = 12.5, 5.5 Hz), 1.86 (1H,
dt, J = 3.5, 12.8 Hz); ESI-MS: Calcd for C15H20O8Na [M+Na]+: 351.11, found
351.08.

JOURNAL OF CARBOHYDRATE CHEMISTRY
9
n-Butyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranoside (3d)
Compound 3d was obtained as colorless syrups (28.0 mg, 90% yield) from the reac-
tion between 1 (30.0 mg, 0.09 mmol) and 2d (9.8 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.33 (1H, ddd, J = 5.0, 9.5, 11.6 Hz), 4.99 (1H, t, J = 9.8 Hz), 4.94 (1H, d,
J = 3.0 Hz), 4.30 (1H, dd, J = 4.7, 12.2 Hz), 4.06 (1H, dd, J = 2.1, 12.2 Hz), 3.97 (1H,
ddd, J = 2.1, 4.5, 6.8 Hz), 3.63 (1H, dt, J = 3.0, 6.7 Hz), 3.39 (1H, dt, J = 3.3, 6.4 Hz),
2.22 (1H, dd, J = 5.0, 12.2 Hz), 2.09 (3H, s), 2.04 (3H, s), 2.02 (3H, s), 1.82 (1H, dt,
J = 2.8, 12.2 Hz), 1.55–1.59 (2H, m), 1.37–1.39 (2H, m), 0.93 (3H, t, J = 7.4 Hz);
13C NMR (125 MHz; CDCl3) δ 170.7, 170.1, 169.9, 96.8, 69.4, 69.1, 67.7, 67.5, 62.4,
35.0, 31.4, 20.9, 20.7, 19.3, 13.8. ESI-MS: Calcd for C16H26O8Na [M+Na]+: 369.15,
found 369.14.
n-Pentyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranoside (3e)
Compound 3e was obtained as colorless syrups (31.0 mg, 96% yield) from the reac-
tion between 1 (30.0 mg, 0.09 mmol) and 2e (11.9 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) 5.33 (1H, ddd, J = 4.3, 5.3, 11.3 Hz), 4.99 (1H, t, J = 9.8 Hz), 4.93 (1H, d,
J = 2.8 Hz), 4.31 (1H, dd, J = 4.6, 12.2 Hz), 4.04 (1H, d, J = 12.2 Hz), 3.95 (1H,
ddd, J = 2.0, 2.3, 10.0 Hz), 3.59–3.64(1H, m), 3.35- 3.40 (1H, m), 2.22 (1H, dd, J =
5.3, 12.8 Hz), 2.09 (3H, s), 2.04 (3H, s), 2.01 (3H, s), 1.82 (1H, dt, J = 3.5, 12.6 Hz),
1.58 (2H, t, J = 6.4 Hz), 1.25–1.34 (4H, m), 0.91 (3H, t, J = 6.4 Hz); 13C NMR (125
MHz; CDCl3) δ 170.6, 170.1, 169.8, 96.8, 69.4, 69.1, 67.8, 67.6, 62.3, 35.0, 29.6, 29.2,
29.0, 28.2, 20.9, 20.6, 13.9. ESI-MS: Calcd for C17H32O8N [M+NH4]+: 378.2, found
377.9.
n-Hexyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranoside (3f)
Compound 3f was obtained as colorless syrups (34.0 mg, 94% yield) from the reac-
tion between 1 (30.0 mg, 0.09 mmol) and 2f (13.9 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.33 (1H, ddd, J = 5.0, 9.5, 12.0 Hz), 4.99 (1H, t, J = 9.5 Hz), 4.93 (1H,
d, J = 3.5 Hz), 4.29 (1H, dd, J = 4.5, 12.0 Hz), 4.05 (1H, dd, J = 2.0, 12.5 Hz), 3.96
(1H, ddd, J = 2.0, 4.0, 10.0 Hz), 3.61 (1H, dt, J = 2.5, 6.5 Hz), 3.37 (1H, dt, J = 2.5,
6.5 Hz), 2.22 (1H, dd, J = 5.0, 12.0 Hz), 2.09 (3H, s), 2.04 (3H, s), 2.01 (3H, s), 1.81
(1H, dt, J = 3.5, 12.0 Hz), 1.56–1.59 (2H, m), 1.28–1.35 (6H, m), 0.89 (3H, t, J =
7.0 Hz); ESI-MS: Calcd for C18H30O8Na [M+Na]+: 397.18, found 397.16.
n-Octyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranoside (3g)
Compound 3g was obtained as colorless syrups (34.4 mg, 95% yield) from the reac-
tion between 1 (30.0 mg, 0.09 mmol) and 2g (20.9 µL, 0.11 mmol, 1.2 equiv.) under

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G. YANG ET AL.
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.33 (1H, ddd, J = 5.5, 9.5, 11.6 Hz), 4.99 (1H, t, J = 9.8 Hz), 4.94 (1H,
d, J = 3.0 Hz), 4.30 (1H, dd, J = 4.5, 12.5 Hz), 4.06 (1H, dd, J = 2.0, 12.0 Hz),
3.97 (1H, ddd, J = 2.0, 5.0, 10.5 Hz), 3.62 (1H, dt, J = 7.30, 10.0 Hz), 3.39 (1H,
dt, J = 6.0, 9.5 Hz), 2.22 (1H, dd, J = 5.5, 11.6 Hz), 2.09 (3H, s), 2.04 (3H, s), 2.10
(3H, s), 1.82 (1H, dty J = 3.5, 11.6 Hz), 1.57–1.59 (2H, m), 1.26–1.35 (10H, m),
0.89 (3H, t, J = 7.0 Hz); ESI-MS: Calcd for C20H34O8Na [M+Na]+: 425.21, found
425.19.
n-Nonyl 2-deoxy-3,4,6-tri-O-acetyl- α -D-glucopyranoside (3h)
Compound 3h was obtained as colorless syrups (72.0 mg, 96% yield) from the reac-
tion between 1 (60.0 mg, 0.18 mmol) and 2h (38.2 µL, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.33 (1H, ddd, J = 3.4, 5.4, 11.4 Hz), 4.99 (1H, t, J = 9.8 Hz), 4.93 (1H,
d, J = 3.0 Hz), 4.29 (1H, dd, J = 4.6, 12.2 Hz), 4.04 (1H, dd, J = 1.6, 12.2 Hz),
3.96(1H, ddd, J = 2.1, 2.3, 10.1 Hz), 3.59–3.64 (1H, m), 3.35–3.39 (1H, m), 2.23 (1H,
dd, J = 5.4, 12.8 Hz), 2.09(3H, s), 2.04 (3H, s), 2.01 (3H, s), 1.82 (1H, dt, J = 3.6,
12.1 Hz), 1.58 (2H, t, J = 6.8 Hz), 1.25–1.33 (12H, m), 0.88(3H, t, J = 0.88 Hz); 13C
NMR (125 MHz; CDCl3) δ 170.6, 170.1, 169.8, 96.8, 69.4, 69.1, 67.8, 67.6, 62.4, 35.0,
31.8, 29.6, 29.4, 29.3, 29.2, 26.1, 22.6, 20.9, 20.7, 14.0. ESI-MS: Calcd for C21H40O8N
[M+NH4]+: 434.3, found 433.9.
n-Decyl 2-deoxy-3,4,6-tri-O-acetyl- α -D-glucopyranoside (3i)
Compound 3i was obtained as colorless syrups (34.0 mg, 88% yield) from the reac-
tion between 1 (30.0 mg, 0.09 mmol) and 2i (20.9 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.33 (1H, ddd, J = 5.5, 9.5, 12.5 Hz), 4.99 (1H, t, J = 9.7 Hz), 4.94 (1H,
d, J = 3.0 Hz), 4.30 (1H, dd, J = 4.5, 12.5 Hz), 4.05 (1H, dd, J = 2.0, 12.0 Hz), 3.95
(1H, ddd, J = 2.0, 4.5, 10.5 Hz), 3.61 (1H, dt, J = 7.0, 13.0 Hz), 3.37 (1H, dt, J = 6.5,
9.5 Hz), 2.22 (1H, dd, J = 5.5, 12.5 Hz), 2.09 (3H, s), 2.04 (3H, s), 2.00 (3H, s), 1.82
(1H, dt, J = 4.0, 12.5 Hz), 1.55–1.61 (2H, m), 1.27–1.30 (14H, m), 0.93 (3H, t, J =
7.0 Hz); 13C NMR (125 MHz; CDCl3) δ 170.7, 170.2, 169.9, 96.8, 69.4, 69.2, 67.8,
67.7, 62.4, 35.0, 31.8, 29.5, 29.5, 29.3, 29.3, 29.2, 26.1, 22.6, 20.9, 20.7, 14.0. ESI-MS:
Calcd for C22H38O8Na [M+Na]+: 453.25, found 453.21.
i-Propyl 2-deoxy-3,4,6-tri-O-acetyl- α -D-glucopyranoside (3j)
Compound 3j was obtained as colorless syrups (27.0 mg, 90% yield) from the reac-
tion between 1 (30.0 mg, 0.09 mmol) and 2j (8.4 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.33 (1H, ddd, J = 5.5, 9.5, 12.5 Hz), 5.05 (1H, d, J = 3.0 Hz), 4.97 (1H, t,

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11
J = 10.0 Hz), 4.27 (1H, dd, J = 5.0, 12.0 Hz), 4.01–4.06 (2H, m), 3.84–3.87 (1H, m),
2.16 (1H, dd, J = 5.5, 12.0 Hz), 2.08 (3H, s), 2.03 (3H, s), 2.00 (3H, s), 1.83 (1H, dt,
J = 3.5, 12.0 Hz), 1.20 (3H, d, J = 6.0 Hz), 1.03 (3H, d, J = 6.0 Hz). ESI-MS: Calcd
for C15H24O8Na [M+Na]+: 355.14, found 355.08.
Cyclohexyl 2-deoxy-3,4,6-tri-O-acetyl- α -D-glucopyranoside (3k)
Compound 3k was obtained as colorless syrups (27.8 mg, 83% yield) from the reac-
tion between 1 (30.0 mg, 0.09 mmol) and 2k (11.5 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.35 (1H, ddd, J = 5.4, 9.5, 11.6 Hz), 5.11 (1H, d, J = 3.0 Hz), 4.98 (1H, t,
J = 9.7 Hz), 4.28 (1H, dd, J = 5.2, 12.6 Hz), 4.05–4.08 (2H, m), 3.51–3.55 (1H, m),
2.18 (1H, dd, J = 4.5, 11.9 Hz), 2.09 (3H, s), 2.04 (3H, s), 2.01 (3H, s), 1.84 (3H, td,
J = 3.8, 11.8 Hz), 1.73–1.74 (2H, m), 1.21–1.29 (6H,m)
2-Butyl 2-deoxy-3,4,6-tri-O-acetyl- α -D-glucopyranoside (3l)
Compound 3l was obtained as colorless syrups (28.0 mg, 90% yield) from the reac-
tion between 1 (30.0 mg, 0.09 mmol) and 2k (9.8 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ5.33 (1H, ddd, J = 5.5, 9.0, 14.5 Hz), 5.07 (1H, d, J = 3.0 Hz), 5.04 (1H, d,
J = 3.0 Hz), 4.97 (2H, t, J = 9.5 Hz), 4.26–4.29 (2H, m), 4.08 (2H, d, J = 1.5 Hz),
4.06 (2H, d, J = 12.0 Hz), 3.61–3.65 (2H, m), 2.20 (2H, dd, J = 5.5, 12.0 Hz), 2.08
(3H, s), 2.04 (3H, s), 2.01 (3H, s), 1.85 (1H, dd, J = 3.0, 12.0 Hz), 1.42–1.64 (4H, m),
1.19 (3H, d, J = 6.5 Hz), 1.11 (3H, d, J = 6.0 Hz), 0.93 (3H, t, J = 7.5 Hz), 0.88 (3H,
t, J = 7.5 Hz); 13C NMR (125 MHz; CDCl3) δ 169.5, 160.5, 168.9, 168.7, 95.4, 92.8,
75.1, 72.4, 68.5, 68.4, 68.0, 68.0, 66.7, 66.6, 61.3, 61.3, 34.3, 34.2, 28.7, 27.7, 19.7, 19.5,
19.5, 19.4, 17.1, 9.1, 8.3. ESI-MS: Calcd for C16H26O8Na [M+Na]+: .369.15, found
369.14.
O-(2-deoxy-3,4,6-tri-O-acetyl- α -D-glucopyranosyl)-N-Fmoc-L-serine
methyl ester (3m)
Compound 3m was obtained as a white solid (101.5 mg, 92% yield) from the reac-
tion between 1 (60.0 mg, 0.18 mmol) and 2m (75.1 mg, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 7.32–7.78 (8H, m), 5.82 (1H, d, J = 8.2 Hz), 5.27 (1H, ddd, J = 3.3, 5.0,
11.1 Hz), 4.98 (1H, d, J = 11.3 Hz), 4.93 (1H, s), 4.57 (1H, d, J = 7.8 Hz), 4.41 (2H, d,
J = 4.9 Hz), 4.28 (2H, dd, J = 4.8, 11.4 Hz), 4.07 (1H, d, J = 12.8 Hz), 3.93 (2H, d, J =
13.0 Hz), 3.80 (3H, s), 2.23 (1H, dd, J = 5.4, 13.0 Hz), 2.07 (3H, s), 2.04 (3H, s), 2.02
(3H, s), 1.83 (1H, td, J = 3.5, 12.8 Hz). 13C NMR (125 MHz; CDCl3) δ 170.5, 170.3,
170.1, 169.8, 155.8, 143.7, 141.2, 127.6, 127.0, 125.0, 119.9, 97.9, 69.1, 68.8, 68.6, 68.5,

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G. YANG ET AL.
67.2, 62.1, 54.2, 52.7, 47.0, 34.7, 29.6, 20.8, 20.6. ESI-MS: Calcd for C31H35NO12Na
[M+Na]+: 636.21, found 636.33.
O-(2-deoxy-3,4,6-tri-O-acetyl- α-D-glucopyranosyl)-N-Fmoc-L-threnine
methyl ester (3n)
Compound 3n was obtained as a white solid (95.0 mg, 84% yield) from the reaction
between 1 (60.0 mg, 0.18 mmol) and 2n (78.1 mg, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 7.33–7.79 (8H, m), 5.56 (1H, d, J = 9.5 Hz), 5.28–5.29 (1H, m), 4.95–
4.99 (2H,m), 4.42–4.44 (3H, m), 4.35 (1H, d, J = 5.5 Hz), 4.28 (2H, dd, J = 5.5,
7.0 Hz), 4.04–4.08 (2H, m), 3.74 (3H, s), 2.13 (1H, dd, J = 4.5, 12.5 Hz), 2.08 (3H,
s), 2.06 (3H, s), 2.03 (3H, s), 1.80 (1H, td, J = 2.5, 12.5 Hz), 1.30 (3H, d, J = 1.0 Hz).
13C NMR (125 MHz; CDCl3) δ 170.9, 170.6, 170.2, 169.8, 156.6, 143.8, 143.7, 141.2,
127.6, 127.0, 125.1, 119.9, 98.4, 76.2, 69.4, 68.6, 68.4, 67.4, 62.3, 58.6, 52.5, 47.1, 35.1,
29.6, 20.9, 20.6, 18.2. ESI-MS: Calcd for C32H37NO12Na [M+Na]+: 650.22, found
650.33.
O-(2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranosyl)-N-Fmoc-L-threnine
methyl ester (3o)
Compound 3o was obtained as a white solid (105.1 mg, 85% yield) from the reaction
between 1 (60.0 mg, 0.18 mmol) and 2o (112.6 mg, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 7.30–7.38 (8H, m), 6.99 (4H, s), 5.62 (1H, s), 5.51 (1H, ddd, J = 3.9, 5.5,
11.1 Hz), 5.25 (1H, d, J = 8.0 Hz), 5.09 (1H, t, J = 9.9 Hz), 4.63 (1H, d, J = 7.5 Hz),
4.46 (1H, dd, J = 7.2, 10.5 Hz), 4.36 (1H, dd, J = 6.8, 10.5 Hz), 4.29 (1H, dd, J = 4.0,
12.2 Hz), 4.20 (1H, t, J = 6.5 Hz), 4.03(1H, d, J = 8.6 Hz), 3.96 (1H, d, J = 12.5 Hz),
3.73 (3 H, s), 3.06 (2H, dd, J = 5.5, 13.0 Hz), 2.45 (1 H, dd, J = 5.2, 13.0 Hz), 2.05
(3 H, s), 2.04 (3 H, s), 2.02 (3 H, s), 1.98 (1 H, dd, J = 3.2, 12.2 Hz); 13C NMR (125
MHz; CDCl3) δ 14.1, 20.6, 20.7, 20.9, 22.6, 29.3, 29.6, 31.9, 35.0, 37.3, 47.1, 52.3,
54.8, 61.9, 66.8, 68.5, 68.8, 69.0, 95.3, 116.4, 120.0, 124.9, 125.0, 127.0, 127.7, 129.6,
130.3, 141.3, 143.6, 143.7,155.3, 155.5, 169.8, 170.2, 170.6, 171.8. ESI-MS: Calcd for
C37H39NO12Na [M+Na]+: 712.24, found 712.33.
Cholesteryl 2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranoside (3p)
Compound 3p was obtained as a white solid (52.1 mg, 92% yield) from the reaction
between 1 (30.0 mg, 0.09 mmol) and 2p (56.3 mg, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 0.68 (3 H, s), 0.85 (3 H, d, J = 2.1 Hz), 0.87 (3 H, d, J = 2.1 Hz), 0.91
(4 H, d, J = 6.5 Hz), 1.00 (3 H, s), 1.03–1.17 (7 H, m), 1.25 (3 H, s), 1.32–1.37 (4 H,
m), 1.43–1.58 (8 H, m), 1.80–1.86 (4 H, m), 2.00 (3 H, s), 2.05 (3 H, s), 2.08 (3 H, s),
2.18 (1 H, dd, J = 5.2, 12.5 Hz), 2.30–2.33 (2 H, m), 3.42–3.44 (1 H, m), 4.07 (2 H,

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dd, J = 4.3 Hz), 4.28 (1 H, ddd, J = 2.1 Hz), 4.99 (1 H, t, J = 9.6 Hz), 5.11 (1 H, d,
J = 2.7 Hz), 5.32–5.37 (2 H, m). ESI-MS: Calcd for C39H62O8Na [M+H]+: 659.44,
found 659.11.
Diosgenyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranoside (3q)
Compound 3q was obtained as a white solid (114.0 mg, 93% yield) from the reaction
between 1 (60.0 mg, 0.18 mmol) and 2q (89.6 mg, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz,
CDCl3) δ 0.80 (6 H, d, J = 3.6 Hz), 0.88–0.95 (2 H, m), 0.97 (3 H, d, J = 6.9 Hz), 1.03
(3 H, s), 1.11–1.21 (3 H, m), 1.26 (3 H, s), 1.44–1.51 (6 H, m), 1.63–1.69 (2 H, m),
1.73–1.80 (3 H, m), 1.84–1.89 (4 H, m), 2.02 (3 H, s), 2.05 (3 H, s), 2.09 (3 H, s), 2.19
(1 H, dd, J = 5.7, 12.5 Hz), 2.32–2.34 (2 H, m), 3.38 (1 H, t, J = 10.8 Hz), 3.43–3.49
(2 H, m), 4.07 (2 H, d, J = 10.6 Hz), 4.28 (1 H, dd, J = 5.2, 12.6 Hz), 4.41 (1 H, dd,
J = 7.0, 7.8 Hz), 4.98 (1 H, t, J = 9.6 Hz), 5.12 (1 H, d, J = 2.9 Hz), 5.33–5.38 (1 H,
m); 13C NMR (125 MHz, CDCl3) δ 14.5, 16.2, 17.1, 19.3, 20.7, 20.8, 20.9, 27.7, 28.7,
29.6, 30.2, 31.3, 31.4, 31.8, 32.0, 35.5, 36.8, 36.9, 39.7, 39.9, 40.2, 41.5, 50.0, 54.7, 56.4,
62.0, 62.5, 66.8, 67.8, 69.1, 69.6, 80.7, 95.0, 109.2, 121.5, 140.6, 169.9, 170.2, 170.7.
ESI-MS: Calcd for C39H58O10Na [M+Na]+: 709.39, found 709.29.
Prasteryl 2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranoside (3r)
Compound 3r was obtained as a white solid (88.0 mg, 88% yield) from the reaction
between 1 (60.0 mg, 0.18 mmol) and 2r (63.5 mg, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz,
CDCl3) δ 0.88 (3 H, s), 1.03 (3 H, s), 0.96–1.05 (2 H, m), 1.25–1.31 (3 H, m), 1.44–
1.56 (3 H, m), 1.62–1.68 (3 H, m), 1.80–1.88 (4 H, m), 1.95 (1 H, td, J = 4.9, 13.3 Hz),
2.01 (3 H, s), 2.05 (3 H, s), 2.08 (3 H, s), 2.06–2.13 (2 H, m), 2.18 (1 H, dd, J = 4.9,
12.3 Hz), 2.33 (2 H, d, J = 7.5 Hz), 2.45 (1 H, dd, J = 8.7, 10.6 Hz), 3.43–3.45 (1
H, m), 4.06 (2 H, d, J = 10.6 Hz), 4.27 (1 H, dd, J = 5.3, 12.7 Hz), 4.98 (1H, t, J =
9.7 Hz), 5.11 (1 H, d, J = 2.5 Hz), 5.33–5.37 (2 H, m). ESI-MS: Calcd for C31H44O9Na
[M+Na]+: 583.29, found 583.21.
Allyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranoside (5a)
Compound 5a was obtained as colorless syrups (30.0 mg, 94% yield) from the reac-
tion between 4 (30.0 mg, 0.09 mmol) and 2a (12.2 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.87–5.93 (1H, m), 5.27–5.33 (3H, m), 5.19 (1H, d, J = 10.0 Hz), 5.05 (1H,
d, J = 2.5 Hz), 4.14 (2H, dd, 6.0, 13.0 Hz), 4.08 (2H, d, J = 6.5 Hz), 53.97 (1H, dd,
J = 6.0, 12.5 Hz), 2.13 (3H, s), 2.07 (1H, dt, J = 4.0, 12.5 Hz), 2.06 (3H, s), 1.98 (3H,
s), 1.88 (1H, dd, J = 5.0 12.5 Hz). ESI-MS: Calcd for C15H22O8Na [M+Na]+: 353.12,
found 353.11.

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G. YANG ET AL.
Benzyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranoside (5b)
Compound 5b was obtained as colorless syrups (68.0 mg, 99% yield) from the reac-
tion between 4 (60.0 mg, 0.18 mmol) and 2b (37.4 µL, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 7.29–7.40 (5H, m), 5.37 (1H, s), 5.34–5.36 (1H, m), 5.13 (1H, d, J =
3.2 Hz), 4.71 (1H, d, J = 11.8 Hz), 4.52 (1H, d, J = 11.8 Hz), 4.23 (1H, t, J = 6.6 Hz),
4.11–4.14 (2H, m), 2.16 (3H, s), 2.12 (1H, dd, J = 3.1, 12.1 Hz), 2.08 (3H, s), 2.0
(3H, s), 1.94 (1H, dd, J = 5.0, 12.5 Hz). ESI-MS: Calcd for C19H24O8Na [M+Na]+:
403.14, found 403.12.
Propargyl 2-deoxy-3,4,6-tri-O-acetyl-α-D- galactopyranoside (5c)
Compound 5c was obtained as colorless syrups (29.0 mg, 98% yield) from the reac-
tion between 4 (30.0 mg, 0.09 mmol) and 2c (12.2 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.34 (1H, s), 5.30 (1H, ddd, J = 3.0, 5.0, 8.0 Hz), 5.22 (1H, d, J = 3.0 Hz),
4.22 (2H, t, J = 2.5 Hz), 4.11–4.18 (1H, m), 4.09 (2H, dd, J = 3.0, 6.5 Hz), 2.45 (1H,
t, J = 2.5 Hz), 2.14 (3H, s), 2.12 (1H, dd, J = 3.5, 12.5 Hz), 2.05 (3H, s), 1.98 (3H, s),
1.90 (1H, dd, J = 5.0, 12.5 Hz). ESI-MS: Calcd for C15H20O8Na [M+Na]+: 351.11,
found 351.08.
n-Butyl 2-deoxy-3,4,6-tri-O-acetyl-α-D- galactopyranoside (5d)
Compound 5d was obtained as colorless syrups (28.0 mg, 90% yield) from the reac-
tion between 4 (30.0 mg, 0.09 mmol) and 2d (12.2 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.33 (1H, s), 5.29 (1H, ddd, J = 3.1, 4.7, 12.4 Hz), 5.00 (1H, d, J = 3.1 Hz),
4.14 (1H, dd, J = 6.6, 13.0 Hz), 4.07–4.10 (2H, m), 3.65 (1H, dt, J = 6.7, 13.4 Hz),
3.40 (1H, dt, J = 6.7, 13.4 Hz), 2.13 (3H, s), 2.09 (1H, dd, J = 3.5, 12.6 Hz), 2.04
(3H, s), 1.98 (3H, s), 1.86 (1H, dd, J = 4.9, 12.6 Hz), 1.55–1.59 (2H, m), 1.26–1.39
(2H, m), 0.93 (1H, t, J = 7.4 Hz); 13C NMR (125 MHz; CDCl3) δ 170.5, 170.3, 170.0,
97.4, 67.5, 66.7, 66.6, 66.3, 62.5, 31.5, 30.3, 20.8, 20.6, 19.3, 13.8. ESI-MS: Calcd for
C16H26O8Na [M+Na]+: 369.15, found 369.14.
n-Pentyl 2-deoxy-3,4,6-tri-O-acetyl-α-D- galactopyranoside (5e)
Compound 5e was obtained as colorless syrups (31.5 mg, 97% yield) from the reac-
tion between 4 (30.0 mg, 0.09 mmol) and 2e (12.2 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.33 (1H, s), 5.30(1H, dd, J = 2.9, 12.3 Hz), 5.00 (1H, s), 4.14 (1H, dd,
J = 5.8, 6.2 Hz), 4.08–4.09 (2H, m), 3.61–3.65 (1H, m), 3.37–3.41 (1H, m), 2.13 (3H,
s), 2.08 (1H, dt, J = 3.4, 12.5 Hz), 2.05 (3H, s), 1.98 (3H, s), 1.85 (1H, dd, J = 4.9,
12.6 Hz), 1.58 (2H, t, J = 6.0 Hz), 1.25–1.33 (4H, m), 0.91 (3H, t, J = 6.3 Hz); 13
C

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15
NMR (125 MHz; CDCl3) δ 170.4, 170.2, 169.9, 97.3, 67.8, 66.7, 66.5, 66.2, 62.5, 30.2,
29.6, 29.0, 28.3, 22.3, 20.8, 20.6, 13.9. ESI-MS: Calcd for C17H32O8N [M+NH4]+:
378.2, found 377.9.
n-Hexyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranoside (5f)
Compound 5f was obtained as colorless syrups (31.5 mg, 94% yield) from the reac-
tion between 4 (30.0 mg, 0.09 mmol) and 2f (12.2 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.35 (1H, s), 5.32 (1H, ddd, J = 3.1, 4.7, 12.4 Hz), 5.01 (1H, d, J = 3.1 Hz),
4.15 (1H, t, J = 6.7 Hz), 4.07–4.10 (2H, m), 3.65 (1H, dt, J = 6.7, 13.4 Hz), 3.40
(1H, dt, J = 3.0, 6.5 Hz), 2.14 (3H, s), 2.07 (1H, dd, J = 3.6, 12.6 Hz), 2.06 (3H, s),
1.99 (3H, s), 1.86 (1H, dd, J = 6.8, 12.4 Hz), 1.57–1.60 (2H, m), 1.26–1.36 (6H, m),
0.86 (3H, t, J = 7.1 Hz). ESI-MS: Calcd for C18H30O8Na [M+Na]+: 397.18, found
397.13.
n-Octyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranoside (5g)
Compound 5g was obtained as colorless syrups (34.5 mg, 95% yield) from the reac-
tion between 4 (30.0 mg, 0.09 mmol) and 2g (17.2 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.31 (1H, S), 5.27 (1H, ddd, J = 3.1, 4.8, 12.3 Hz), 4.97 (1H, d, J = 3.1 Hz),
4.12 (1H, dd, J = 5.6, 6.5 Hz), 4.03–4.08 (2H, m), 3.61 (1H, dt, J = 6.8, 9.5 Hz), 3.37
(1H, dt, J = 6.8, 9.5 Hz), 2.11 (3H, s), 2.09 (1H, dd, J = 3.6, 12.5 Hz), 2.03 (3H, s),
1.97 (3H, s), 1.84 (1H, dd, J = 4.9, 12.3 Hz), 1.23–1.33 (12H, m), 0.86 (3H, t, J =
7.1 Hz). ESI-MS: Calcd for C20H34O8Na [M+Na]+: 425.21, found 425.20.
n-Nonyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranoside (5h)
Compound 5h was obtained as colorless syrups (29 mg, 99% yield) from the reaction
between 4 (30.0 mg, 0.09 mmol) and 2h (19.1 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.33 (1H, s), 5.30 (1H, ddd, J = 3.0, 4.8, 12.4 Hz), 4.99 (1H, d, J = 2.9 Hz),
4.13 (1H, dd, J = 6.2, 6.7 Hz), 4.08–4.10 (2H, m), 3.60–3.65 (1H, m), 3.36–3.41 (1H,
m), 2.13 (3H, s), 2.08 (1H, dt, J = 3.6, 12.6 Hz), 2.05 (3H, s), 1.98 (3H, s), 1.85 (1H,
dd, J = 4.9, 12.7 Hz), 1.57 (2H, t, J = 6.7 Hz), 1.25–1.30 (12H, m), 0.88 (3H, t, J =
6.6 Hz); 13C NMR (125 MHz; CDCl3) δ 170.4, 170.3, 170.0, 97.3, 67.8, 66.7, 66.5,
66.2, 62.5, 31.8, 30.2, 29.6, 29.4, 29.3, 29.2, 26.1, 22.6, 20.8, 20.6, 14.0. ESI-MS: Calcd
for C21H40O8N [M+NH4]+: 434.3, found 433.9.
n-Decyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranoside (5i)
Compound 5i was obtained as colorless syrups (34 mg, 88% yield) from the reac-
tion between 4 (30.0 mg, 0.09 mmol) and 2i (12.2 µL, 0.11 mmol, 1.2 equiv.)

16
G. YANG ET AL.
1
under the same conditions described above for the synthesis of 3a. H NMR
(500 MHz; CDCl3) δ 5.31 (1H, s), 5.27 (1H, ddd, J = 3.2, 4.7, 12.4 Hz), 4.97
(1H, d, J = 3.1 Hz), 4.11 (1H, dd, J = 6.6, 6.7 Hz), 4.06 (2H, m), 3.60 (1H,
dt, J = 6.6, 13.2 Hz), 3.36 (1H, dt, J = 6.6, 13.2 Hz), 2.10 (3H, s), 2.05 (1H,
dt, J = 2.4, 12.6 Hz), 2.10 (3H, s), 2.05 (1H, dd, J = 2.4, 12.6 Hz), 2.02 (3H,
s), 1.96 (3H, s), 1.83 (1H, dd, J = 5.0, 12.6 Hz), 1.52–1.56 (2H, m), 1.24–1.30
(14H, m), 0.86 (3H, t, J = 6.7 Hz); 13C NMR (125 MHz; CDCl3) δ 170.4, 140.3,
170.0, 97.4, 67.9, 66.7, 66.5, 66.3, 62.5, 31.8, 60.2, 29.6, 29.5, 29.4, 29.3, 26.2, 22.6,
20.8, 20.6, 19.3, 14.0. ESI-MS: Calcd for C22H38O8Na [M+Na]+: 453.25, found
453.21.
i-Propyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranoside (5j)
Compound 5j was obtained as colorless syrups (27 mg, 90% yield) from the reac-
tion between 4 (30.0 mg, 0.09 mmol) and 2j (8.4 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.31 (1H, s), 5.29 (1H, ddd, J = 3.0, 4.8, 12.3 Hz), 5.11 (1H, d, J = 3.2 Hz),
4.20 (1H, t, J = 6.4, 6.7 Hz), 4.06 (2H, dd, J = 2.0, 6.0 Hz), 3.85–3.87 (1H, m), 2.12
(3H, s), 2.07 (1H, dt, J = 3.7, 12.4 Hz), 2.03 (3H, s), 1.96 (3H, s), 1.78 (1H, dd, J =
4.9, 12.4 Hz), 1.19 (3H, d, J = 6.1 Hz), 1.13 (3H, d, J = 6.1 Hz). ESI-MS: Calcd for
C15H24O8Na [M+Na]+: 355.14, found 355.11.
Cyclohexyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranoside (5k)
Compound 5k was obtained as colorless syrups (29.1 mg, 87% yield) from the reac-
tion between 4 (30.0 mg, 0.09 mmol) and 2k (11.5 µL, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 5.33 (1H, s), 5.31 (1H, ddd, J = 3.1, 4.7, 12.2 Hz), 5.17 (1H, d, J = 3.1 Hz),
4.24 (1H, t, J = 6.4 Hz), 4.06–4.11 (2H, m), 3.54–3.56 (1H, m), 2.14 (3H, s), 2.06
(1H, dd, J = 3.6, 6.5 Hz), 2.04 (3H, s), 2.00 (3H, s), 1.82 (1H, td, J = 2.9, 11.6 Hz),
1.55–1.59 (2H, m), 1.24–1.29 (6H, m). ESI-MS: Calcd for C18H28O8Na [M+Na]+:
395.17, found 395.16.
2-Butyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranoside (5l)
Compound 5l was obtained as colorless syrups (55 mg, 89% yield) from the reac-
tion between 4 (60.0 mg, 0.18 mmol) and 2l (19.6 µL, 0.22 mmol, 1.2 equiv.)
under the same conditions described above for the synthesis of 3a. 1H NMR (500
MHz; CDCl3) δ 5.33 (3H, app.s), 4.33 (1H, t, J = 6.5 Hz), 4.02–4.09 (2H, m), 2.13
(3H, s), 2.08 (1H, dd, J = 3.5, 12.2 Hz), 2.03 (3H, s), 1.98 (3H, s), 1.72 (1H, dd, J =
4.5, 12.2 Hz), 1.25 (9H, s). ESI-MS: Calcd for C16H26O8Na [M+Na]+: 369.15, found
369.14.

JOURNAL OF CARBOHYDRATE CHEMISTRY
17
O-(2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranosyl)-N-Fmoc-L-serine
methyl ester (5m)
Compound 5m was obtained as a white solid (108.1 mg, 98% yield) from the reac-
tion between 4 (60.0 mg, 0.18 mmol) and 2m (75.1 mg, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 7.32–7.78 (8H, m), 5.84 (1H, d, J = 8.5 Hz), 5.34 (1H, s), 5.23 (1H, d, J =
11.2 Hz), 4.99 (1H, s), 4.57 (1H, dd, J = 3.8, 4.3 Hz), 4.41 (2H, dd, J = 6.2, 7.1 Hz),
4.26 (1H, dd, J = 6.8, 7.1 Hz), 4.10 (1H, d, J = 6.2 Hz), 4.05 (2H, d, J = 6.4 Hz),
3.94 (2H, s), 3.79 (3H, s), 2.13 (3H, s), 2.08 (1H, dd, J = 2.8, 12.5 Hz), 2.00 (3H, s),
1.98 (3H, s), 1.85 (1H, dd, J = 4.5, 12.8 Hz). 13C NMR (125 MHz; CDCl3) δ 170.4,
170.3, 170.1, 169.9, 155.8, 143.7, 141.1, 127.6, 127.0, 125.0, 119.9, 98.1, 68.3, 67.2,
67.1, 66.3, 65.8, 62.3, 54.2, 52.6, 46.9, 29.8, 29.5, 20.7, 20.6, 20.5. ESI-MS: Calcd for
C31H35NO12Na [M+Na]+: 636.21, found 636.33.
O-(2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranosyl)-N-Fmoc-L-threnine
methyl ester (5n)
Compound 5n was obtained as a white solid (98.0 mg, 87% yield) from the reaction
between 4 (60.0 mg, 0.18 mmol) and 2n (100.3 mg, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 7.32–7.78 (8H, m), 5.48 (1H, d, J = 9.5 Hz), 5.34 (1H, s), 5.24 (1H, d, J =
12.0 Hz), 5.01 (1H, d, J = 2.5 Hz), 4.41–4.44 (3H,m), 4.37 (1H, d, J = 6.0 Hz), 4.28
(1H, dd, J = 7.0, 7.0 Hz), 4.22 (2H, dd, J = 6.0, 6.5 Hz), 4.09 (2H, d, J = 6.0 Hz), 3.76
(3H, s), 2.13 (3H, s), 2.05 (3H, s), 2.02 (1H, td, J = 3.5, 12.0 Hz), 1.99 (3H, s), 1.76
(1H, dd, J = 4.0 12.0 Hz), 1.31 (3H, d, J = 5.9 Hz). 13C NMR (125 MHz; CDCl3) δ
171.0, 170.4, 170.2, 170.1, 156.6, 143.7, 143.6, 141.2, 127.6, 127.0, 125.0, 119.9, 99.0,
76.0, 67.3, 67.1, 66.4, 65.8, 62.4, 58.6, 52.4, 47.1, 30.2, 29.6, 20.7, 20.6, 18.2. ESI-MS:
Calcd for C32H37NO12Na [M+Na]+: 650.22, found 650.33.
O-(2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranosyl)-N-Fmoc-L-threnine
methyl ester (5o)
Compound 5o was obtained as a white solid (52.1 mg, 84% yield) from the reac-
tion between 4 (30.0 mg, 0.09 mmol) and 2o (56.3 mg, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 7.30–7.38 (8H, m), 6.98 (4H, m), 5.67 (1H, s), 5.47 (1H, ddd, J = 3.7,
4.4, 8.0 Hz), 5.37 (1H, s), 5.22 (1H, d, J = 8.2 Hz), 4.64 (1H, d, J = 7.5 Hz), 4.45
(1H, dd, J = 7.5, 10.5 Hz), 4.36 (1H, dd, J = 6.8, 10.5 Hz), 4.35 (1H, dd, J = 7.5,
10.5 Hz), 4.18 (2 H, d, J = 6.4 Hz), 4.04 (2 H, d, J = 6.4 Hz), 3.74 (3H, s), 3.06
(2H, dd, J = 6.0, 14.0 Hz), 2.23 (1 H, td, J = 3.2, 12.4 Hz), 2.16 (3 H, s), 2.07 (1
H, dd, J = 4.6, 12.8 Hz), 2.03 (3 H, s), 1.91 (3 H, s); 13C NMR (125 MHz; CDCl3) δ
14.1, 20.5, 20.7, 20.8, 29.6, 30.2, 37.3, 47.1, 52.3, 54.8, 61.9, 65.9, 66.3, 66.8, 67.4, 95.9,

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G. YANG ET AL.
166.5, 120.0, 124.9, 125.0, 127.0, 127.7, 129.5, 130.3, 141.3, 143.7, 143.8, 155.5, 170.1,
170.2, 170.3, 171.8. ESI-MS: Calcd for C37H39NO12Na [M+Na]+: 712.24, found
712.33.
Cholesteryl 2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranoside (5p)
Compound 5p was obtained as a white solid (52.1 mg, 84% yield) from the reaction
between 4 (30.0 mg, 0.09 mmol) and 2p (56.3 mg, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 0.68 (3 H, s), 0.85 (3 H, d, J = 1.5 Hz), 0.88 (3 H, d, J = 2.5 Hz), 0.92 (4 H,
d, J = 6.5 Hz), 1.01 (3 H, s), 1.08–1.15 (7 H, m), 1.26–1.34 (8 H, m), 1.48 -1.52 (7 H,
m), 1.81–1.87 (4 H, m), 1.99 (3 H, s), 2.05 (3 H, s), 2.11 (1 H, dd, J = 3.6, 6.5 Hz),
2.14 (3 H, s), 2.32 (2 H, d, J = 7.5 Hz), 3.45–3.48 (1 H, m), 4.06–4.10 (2 H, m), 4.26
(1 H, t, J = 6.5 Hz), 5.18 (1 H, d, J = 2.5 Hz), 5.30–5.37 (3 H, m). ESI-MS: Calcd for
C39H62O8Na [M+H]+: 659.44, found 659.11.
Diosgenyl 2-deoxy-3,4,6-tri-O-acetyl-α-D-galactopyranoside (5q)
Compound 5q was obtained as a white solid (115.0 mg, 93% yield) from the reaction
between 4 (60.0 mg, 0.18 mmol) and 2q (89.6 mg, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz,
CDCl3) δ 0.76 (6 H, d, J = 3.5 Hz), 0.94 (3 H, d, J = 6.9 Hz), 1.00 (3 H, s), 1.23–1.27
(4 H, m), 1.40–1.49 (5 H, m), 1.58–1.65 (7 H, m), 1.70–1.86 (7 H, m), 1.95 (3 H,
s), 2.02 (3 H, s), 2.05 (1 H, dd, J = 3.5, 12.5 Hz), 2.10 (3 H, s), 2.28–2.30 (2 H, m),
3.35 (1 H, t, J = 10.9 Hz), 3.40–3.45 (2 H, m), 4.04–4.08 (2 H, m), 4.23 (1 H, t, J
= 6.5 Hz), 4.37 (1 H, dd, J = 7.7, 16.0 Hz), 5.14 (1 H, d, J = 2.7 Hz), 5.27–5.33 (3
H, m); 13C NMR (125 MHz, CDCl3) δ 14.4, 16.2, 17.1, 19.3, 20.7, 20.7, 20.8, 20.9,
27.8, 28.7, 30.2, 31.3, 31.4, 31.8, 32.0, 36.8, 37.0, 39.9, 40.2, 41.5, 50.7, 56.4, 62.6, 66.3,
66.7, 66.8, 66.9, 80.7, 95.7, 109.2, 121.5, 140.7, 170.0, 170.3, 170.5. ESI-MS: Calcd for
C39H58O10Na [M+Na]+: 709.39, found 709.31.
Prasteryl 2-deoxy-3,4,6-tri-O-acetyl-α-D- galactopyranoside (5r)
Compound 5r was obtained as a white solid (91.0 mg, 90% yield) from the reac-
tion between 4 (60.0 mg, 0.18 mmol) and 2r (63.5 mg, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz,
CDCl3) δ 0.89 (3 H, s), 1.03 (3 H, s), 0.96–1.04 (2 H, m), 1.25–1.31 (3 H, m), 1.45–
1.54 (3 H, m), 1.63–1.68 (3 H, m), 1.81–1.88 (4 H, m), 1.95 (1 H, dd, J = 2.6,
6.8 Hz), 1.98 (3 H, s), 2.04 (3 H, s), 2.06–2.12 (2 H, m), 2.13 (3 H, s), 2.32–2.34
(2 H, m), 2.45 (1 H, dd, J = 8.8, 10.5 Hz), 3.44–3.46 (1 H, m), 4.07–4.11 (2 H,
m), 4.25 (1 H, dd, J = 6.4, 6.7 Hz), 5.17 (1 H, d, J = 2.9 Hz), 5.29–5.33 (2 H, m),
5.39 (1 H, d, J = 4.9 Hz); ESI-MS: Calcd for C31H44O9Na [M+Na]+: 583.29, found
583.24.

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Trichloroethyl 2,3,4-tri-O-benzyl-6-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-
glucopyranosyl)-α-D-glucopyranoside (7a)
Compound 7a was obtained as colorless syrups (69.0 mg, 90% yield) from the reac-
tion between 1 (30.0 mg, 0.09 mmol) and 6a (63.8 mg, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz,
CDCl3) δ 1.80 (dt, J = 1.05, 12.3 Hz, 1 H), 2.01 (s, 3 H), 2.02(s, 3 H), 2.03 (s, 3 H),
2.27 (dd, J = 5.4, 12.9 Hz, 1 H), 3.56 (t, J = 9.6 Hz, 1 H), 3.63 (dd, J = 6.0, 9.8 Hz, 2
H), 3.81 (dd, J = 4.6, 11.4 Hz, 1 H), 3.88–3.97 (m, 3 H), 4.09 (d, J = 11.5 Hz, 1 H),
4.14 (dd, J = 4.5, 12.3 Hz, 2 H), 4.18 (d, J = 11.5 Hz, 1 H), 4.63 (d, J = 11.3 Hz, 1 H),
4.71 (d, J = 11.9 Hz, 1 H), 4.80 (d, J = 11.0 Hz, 2 H), 4.96–5.05 (m, 5 H), 5.28 (ddd,
J = 1.8, 5.4, 9.6 Hz, 1 H), 7.26–7.40 (m, 15 H); 13C NMR (125 MHz, CDCl3) δ 20.6,
20.8, 29.6, 34.7, 62.1, 65.8, 67.9, 68.9, 69.1 70.9, 72.9, 74.9, 75.6, 77.3, 79.4, 80.1, 81.5,
96.2, 97.1, 97.4, 127.4, 127.5, 127.7, 127.8, 127.8, 127.9, 128.3, 128.3, 128.4, 138.1,
138.5, 169.7, 169.9, 170.5; ESI-MS: Calcd for C41H47O13Na [M+Na]+: 875.2, found
874.5.
trichloroethyl 2,3,4-tri-O-benzyl-6-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-
galactopyranosyl)-α-D-glucopyranoside (8a)
Compound 8a was obtained as colorless syrups (74.0 mg, 97% yield) from the reac-
tion between 4 (30.0 mg, 0.09 mmol) and 6a (63.8 mg, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz,
CDCl3) δ 1.90 (dd, J = 5.0, 12.7 Hz, 1 H), 1.97 (s, 3 H), 2.00 (s, 3 H), 2.05 (dt, J =
3.4, 12.6 Hz, 1 H), 2.13 (s, 3 H), 3.53–3.57 (m, 1 H), 3.61 (dd, J = 3.7, 9.7 Hz, 1 H),
3.65 (dd, J = 1.5, 10.3 Hz, 1 H), 3.81 (dt, J = 4.8, 11.5 Hz, 1 H), 3.91 (dd, J = 4.0,
10.5 Hz, 1 H), 3.98–4.03 (m, 3 H), 4.06–4.11 (m, 2 H), 4.18 (dd, J = 4.5, 11.5 Hz, 1
H), 4.63 (d, J = 11.2 Hz, 1 H), 4.82 (d, J = 13.5 Hz, 2 H), 4.98–5.03 (m, 3 H), 5.07 (d,
J = 2.8 Hz, 1 H), 5.24 (ddd, J = 4.5, 7.9, 12.4 Hz, 1 H), 5.29 (d, J = 2.4 Hz, 1 H), 726–
7.41 (m, 15 H); 13C NMR (125 MHz, CDCl3) δ 20.7, 20.8, 29.6, 29.9, 61.5, 62.3, 65.8,
65.9, 66.4, 66.7, 70.8, 72.9, 72.9, 75.1, 75.7, 77.3, 79.3, 79.4, 79.9, 80.0, 81.3, 81.5, 96.1,
97.3, 97.6, 127.5, 127.6, 127.7, 127.8, 127.9, 128.1, 128.3, 128.4, 128.5, 137.9, 138.0,
138.4, 169.8, 170.2,170.3; ESI-MS: Calcd for C41H47O13Na [M+Na]+: 875.2, found
875.5.
4-methoxyphenyl 2,4,6-tri-O-acetyl-3-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-
glucopyranosyl)-α-D-galactopyranoside (7b)
Compound 7b was obtained as colorless syrups (110.0 mg, 89% yield) from the reac-
tion between 1 (60.0 mg, 0.18 mmol) and 6b (90.7 mg, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz,
CDCl3) δ 1.78 (dt, J = 3.0, 11.2 Hz, 1 H), 1.97 (s, 3 H), 2.01 (s, 3 H), 2.03 (s,
3 H), 2.07 (s, 3 H), 2.10 (dd, J = 3.3, 11.2 Hz, 1 H), 2.14 (s, 3 H), 2.19 (s, 3

20
G. YANG ET AL.
H), 3.76 (s, 3 H), 3.90–3.94 (m, 3 H),4.11–4.25 (m, 4 H), 4.81 (d, J = 8.0 Hz,
1 H), 4.97 (t, J = 9.7 Hz, 1 H), 5.10–5.12 (m, 1 H), 5.19 (d, J = 2.4 Hz, 1 H),
5.37–5.42 (m, 2 H), 6.79 (d, J = 9.0 Hz, 2 H), 6.94 (dd, J = 2.2, 9.0 Hz, 2 H);
13C NMR (125 MHz, CDCl3) δ 20.6, 20.6, 20.7, 20.8, 34.0, 55.5, 61.4, 62.1, 64.8,
68.3, 68.5, 69.0, 69.4, 70.7, 72.3, 93.6, 100.9, 114.4, 118.5, 151.0, 155.6, 168.7, 169.7,
169.8, 170.3, 170.5, 170.6; ESI-MS: Calcd for C31H44O17N [M+NH4]+: 702.3, found
702.2.
4-methoxyphenyl 2,4,6-tri-O-acetyl-3-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-
galactopyranosyl)-α-D-galactopyranoside (8b)
Compound 8b was obtained as colorless syrups (69.3 mg, 99% yield) from the reac-
tion between 4 (60.0 mg, 0.18 mmol) and 6b (90.7 mg, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz,
CDCl3) δ 1.67 (dd, J = 5.0, 13.0 Hz, 1 H), 1.96 (s, 3 H), 2.03 (s, 3 H), 2.07 (s, 3
H), 2.08 (dd, J = 7.0, 13.0 Hz, 1 H), 2.14 (s, 3 H), 2.16 (s, 3 H), 2.19 (s, 3 H), 3.77
(s, 3 H), 3.93–3.97 (m, 2 H), 4.04 (dd, J = 5.2, 9.8 Hz, 1 H), 4.11–4.20 (m, 3 H),
4.25 (dd, J = 6.9, 11.4 Hz, 1 H), 4.84 (d, J = 8.0 Hz, 1 H), 5.07 (ddd, J = 3.0, 4.7,
8.0 Hz, 1 H), 5.26 (d, J = 2.8 Hz, 1 H), 5.33 (s, 1 H), 5.39 (dd, J = 2.2, 8.0 Hz, 1
H), 5.44 (d, J = 2.8 Hz, 1 H), 6.80 (d, J = 9.0 Hz, 2 H), 6.96 (dd, J = 3.5, 9.0 Hz, 2
H); 13C NMR (125 MHz, CDCl3) δ 20.5, 20.6, 20.6, 20.7, 29.0, 29.6, 55.5, 61.5, 62.0,
64.9, 65.7, 66.1, 67.1, 69.3, 70.7, 72.0, 94.0, 100.9, 114.4, 118.5, 151.0, 155.6, 169.0,
169.8, 170.2, 170.3, 170.5; ESI-MS: Calcd for C31H44O17N [M+NH4]+: 702.3, found
702.1.
methyl 3,4,6-tri-O-benzyl-2-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-
glucopyranosyl)-α-D-mannopyranoside (7c)
Compound 7c was obtained as colorless syrups (126.1 mg, 95% yield) from the reac-
tion between 1 (60.0 mg, 0.18 mmol) and 6c (100.3 mg, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz,
CDCl3) δ 1.81 (dt, J = 9.0, 3.0 Hz, 1 H), 2.00 (s, 3 H), 2.02 (s, 3 H), 2.09 (s, 3 H),
2.39 (dd, J = 5.0, 12.5 Hz, 1 H), 3.35 (s, 3 H), 3.72–3.76 (m, 3 H), 3.86–3.92 (m
containing dd, J = 12.0, 3.0 Hz, 2 H), 3.95 (d, J = 2.0 Hz, 1 H), 4.06 (dd, J = 2.0,
12.5 Hz, 1 H), 4.18 (ddd, J = 2.0, 5.0, 10.0 Hz, 1 H), 4.27 (dd, J = 5.0, 12.0 Hz, 1 H),
4.51 (d, J = 11.0 Hz, 1 H), 4.60–4.71 (m, 4 H), 4.78 (d, J = 1.5 Hz, 1 H), 4.82 (d, J
= 10.5 Hz, 1 H), 4.99 (t, J = 10.5 Hz, 1 H), 5.12 (d, J = 3.0 Hz, 1 H), 5.39 (ddd, J =
5.5, 2.0, 9.5 Hz, 1 H), 7.16–7.18 (m, 2 H), 7.25–7.39 (m, 13 H); 13C NMR (125 MHz,
CDCl3) δ 20.6, 20.7, 20.9, 29.6, 35.0, 54.6, 62.5, 68.0, 68.8, 69.1, 69.5, 71.5, 72.2, 73.1,
74.7, 75.0, 75.2, 79.7, 98.7, 99.6, 127.2, 127.3, 127.5, 127.6,127.7, 127.8, 128.2, 128,3,
128.3, 138.2, 138.3, 169.9, 170.6; ESI-MS: Calcd for C40H52O13N [M+NH4]+: 754.3,
found 754.2.

JOURNAL OF CARBOHYDRATE CHEMISTRY
21
methyl 3,4,6-tri-O-benzyl-2-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-
galactopyranosyl)-α-D-mannopyranoside (8c)
Compound 8c was obtained as colorless syrups (130.1 mg, 98% yield) from the reac-
tion between 4 (60.0 mg, 0.18 mmol) and 6c (100.3 mg, 0.22 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz,
CDCl3) δ 2.00 (s, 3 H), 2.02–2.07 (m, 2 H), 2.06 (s, 3 H), 2.14 (s, 3 H), 3.37 (s, 3 H),
3.72–3.77 (m, 3 H), 3.86 (dd, J = 4.0, 9.3 Hz, 1 H), 3.92 (dd, J = 2.8, 9.3 Hz, 1 H), 4.00
(s, 1 H), 4.09 (dd, J = 2.7, 4.6 Hz, 2 H), 4.31 (t, J = 6.3 Hz, 1 H), 4.52 (d, J = 10.8 Hz,
1 H), 4.59 (d, J = 12.0 Hz, 1 H), 4.66 (d, J = 11.8 Hz, 1 H), 4.67 (d, J = 12.0 Hz, 1
H), 4.70 (d, J = 11.8 Hz, 1 H), 4.80 (d, J = 0.3 Hz, 1 H), 4.84 (d, J = 10.8 Hz, 1 H),
5.23 (d, J = 2.4 Hz, 1 H), 5.34 (s, 1 H), 5.30–5.33 (ddd, J = 2.4, 5.5, 9.0 Hz, 1 H),
7.12–7.19 (m, 2 H), 7.26–7.38 (m, 13 H); 13C NMR (125 MHz, CDCl3) δ 20.6, 20.7,
20.8, 30.1, 54.7, 62.7, 66.0, 66.7, 67.0 69.1, 71.6, 72.2, 73.2, 74.6, 74.8, 75.0, 79.8, 99.1,
99.7, 127.3, 127.5, 127.5, 127.6, 127.8, 128.2, 128.3, 138.2, 138.3, 138.3, 169.8, 170.0,
170.4; ESI-MS: Calcd for C40H52O13N [M+NH4]+: 754.3, found 754.2.
Methyl 2,3,6-tri-O-benzyl-4-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-
glucopyranosyl)-α-D-glucopyranoside (7d)
Compound 7d was obtained as colorless syrups (57.7 mg, 87% yield) from the reac-
tion between 1 (30.0 mg, 0.09 mmol) and 6d (51.1 mg, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz,
CDCl3) δ 1.62 (dd, J = 3.7, 12.1 Hz, 1 H), 1.98 (s, 3 H), 2.02 (s, 6 H), 2.02–2.04 (m, 1
H), 3.41 (m, 3 H), 3.53 (dd, J = 3.4, 9.6 Hz, 1 H), 3.64–3.68 (m, 3 H), 3.76–3.78 (m,
2 H), 3.84 (d, J = 10.0 Hz, 1 H), 3.93 (t, J = 9.2 Hz, 1 H), 4.13 (dd, J = 4.0, 12.2 Hz,
1 H), 4.51 (d, J = 12.2 Hz, 1 H), 4.61–4.66 (m, 4 H), 4.72 (d, J = 12.0 Hz, 1 H), 4.90
(t, J = 9.7 Hz, 1 H), 5.03 (d, J = 11.3 Hz, 1 H), 5.21 (ddd, J = 1.9, 4.9, 11.3 Hz, 1 H),
5.41 (d, J = 3.0 Hz, 1 H), 7.27–7.33 (m, 15 H); 13C NMR (125 MHz, CDCl3) δ 14.0,
20.6, 20.9, 22.6, 29.3, 29.6, 29.7, 31.8, 35.1, 55.2, 62.1,68.5, 68.7, 69.1, 69.2, 69.5, 73.1,
73.3, 75.3, 76.3, 80.0, 81.7, 97.7, 98.5, 127.4, 127.4, 127.4, 127.5, 127.9, 128.0, 128.3,
128.4, 128.4, 137.8, 138.0, 138.5, 169.9, 170.1, 170.5; ESI-MS: Calcd for C40H52O13N
[M+NH4]+: 754.3, found 754.2.
Methyl 2,3,6-tri-O-benzyl-4-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-
galactopyranosyl)-α-D-glucopyranoside (8d)
Compound 8d was obtained as colorless syrups (60.3 mg, 91% yield) from the reac-
tion between 4 (30.0 mg, 0.09 mmol) and 6d (51.1 mg, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz,
CDCl3) δ 1.72 (dd, J = 4.8, 12.3 Hz, 1 H), 1.91 (dt, J = 3.6, 12.3 Hz, 1 H), 1.96 (s, 3
H), 1.97 (s, 3 H), 2.09 (s, 3 H), 3.41 (s, 3 H), 3.52 (dd, J = 3.4, 9.7 Hz, 1 H), 3.64–3.68
(m, 3 H), 3.76–3.78 (m, 1 H), 3.88–3.94 (m, 3 H), 3.98 (t, J = 6.5 Hz, 1 H), 4.52 (d,

22
G. YANG ET AL.
J = 12.2 Hz, 1 H), 4.62 (dd, J = 3.5, 11.6 Hz, 4 H), 4.72 (d, J = 12.0 Hz, 1 H), 5.04
(d, J = 11.2 Hz, 1 H), 5.16 (dd, J = 4.7, 11.1 Hz, 1 H), 5.20 (s, 1 H), 5.47 (d, J =
2.7 Hz, 1 H), 7.27–7.35 (m, 15 H); 13C NMR (125 MHz, CDCl3) δ 14.0, 20.6, 20.8,
22.6, 29.3, 29.6, 29.7, 30.3, 31.8, 55.2, 62.2, 65.8, 66.4, 67.2, 69.1, 69.5, 73.0, 73.1, 75.3,
76.1, 80.6, 81.7, 97.6, 99.1, 127.4, 127.5, 127.6, 127.9, 128.1, 128.3, 128.4, 128.4, 137.8,
138.0, 138.4, 169.9, 170.2; ESI-MS: Calcd for C40H52O13N [M+NH4]+: 754.3, found
754.2.
Phenyl 2,3,4-tri-O-benzoyl-6-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-
glucopyranosyl)-1-thio-β-D-glucopyranoside (7e)
Compound 7e was obtained as colorless syrups (76.3 mg, 99% yield) from the reac-
tion between 1 (30.0 mg, 0.09 mmol) and 6e (64.3 mg, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 7.95 (4H, m), 7.82 (2H, m), 7.57–7.51 (4H, m), 7.46–7.33 (8H, m), 7.29
(2H, m), 5.92 (1H, t, J = 9.5 Hz), 5.54 (1H, t, J = 9.5 Hz), 5.53 (1H, t, J = 9.5 Hz),
5.37–5.32 (1H, m), 5.00 (1H, t, J = 10 Hz), 4.97 (1H, d, J = 3 Hz), 4.24 (1H, dd, J =
12.5, 4.5 Hz), 4.12–4.06 (2H, m), 3.97 (1H, dd, J = 12, 1.5 Hz), 3.93 (1H, dd, J = 11,
6 Hz), 3.67 (1H, dd, J = 11, 2 Hz), 2.24 (1H, dd, J = 12.5, 5.5 Hz), 2.07 (3H, s), 2.05
(3H, s), 1.98 (3H, s), 1.82 (1H, dt, J = 12.5, 4 Hz); 13C NMR (125 MHz; CDCl3)
δ 170.69, 170.02, 169.89, 165.78, 165.16, 165.07, 133.55, 133.32, 133.22, 132.54,
132.27, 129.89, 129.85, 129.76, 129.18, 129.00, 128.79, 128.50, 128.40, 128.29, 128.15,
97.05, 86.53, 77.17, 74.21, 70.54, 69.56, 69.15, 69.05, 67.92, 66.66, 62.13, 34.71,
21.00, 20.74, 20.69. ESI-MS: Calcd for C45H44O15SNa [M+Na]+: 879.23, found
879.17.
Phenyl 2,3,4-tri-O-benzoyl-6-O-(3,4,6-tri-O-acetyl-2-deoxy-α-D-
galactopyranosyl)-1-thio-β-D-glucopyranoside (8e)
Compound 8e was obtained as colorless syrups (69.3 mg, 90% yield) from the reac-
tion between 4 (30.0 mg, 0.09 mmol) and 6e (64.3 mg, 0.11 mmol, 1.2 equiv.) under
the same conditions described above for the synthesis of 3a. 1H NMR (500 MHz;
CDCl3) δ 7.97 (4H, m), 7.81 (2H, m), 7.53 (4H, m), 7.40 (8H, m), 7.29 (2H, m),
5.92 (1H, t, J = 4.5 Hz), 5.59 (1H, t, J = 4.5 Hz), 5.51 (1H, t, J = 4.5 Hz), 5.25
(1H, s), 5.24–5.20 (1H, m), 5.11 (1H, d, J = 10 Hz), 5.04 (1H, d, J = 3 Hz), 4.101
(1H, t, J = 6 Hz), 4.07–4.03 (1H, m), 3.99 (2H, d, J = 6.5 Hz), 3.92 (1H, dd, J = 11,
5.5 Hz), 3.70 (1H, dd, J = 11, 2.5 Hz), 2.13 (3H, s), 2.06 (1H, dd, J = 8.5, 3.5 Hz), 2.02
(3H, s), 1.95 (3H, s), 1.82 (1H, dd, J = 12.5, 5.5 Hz); 13C NMR (125 MHz; CDCl3)
δ 170.44, 170.28, 169.77, 165.80, 165.16, 165.06, 133.47, 133.32, 133.22, 132.46,
132.08, 129.89, 129.82, 129.76, 129.22, 129.10, 128.88, 128.80, 128.49, 128.40, 128.28,
97.57, 86.07, 77.18, 74.23, 70.60, 69.55, 66.84, 66.63, 66.51, 66.39, 66.07, 62.45, 29.83,
20.87, 20.70, 20.64. ESI-MS: Calcd for C45H44O15SNa [M+Na]+: 879.23, found
879.17.

JOURNAL OF CARBOHYDRATE CHEMISTRY
23
In vitro antitumor test
Human carcinoma cell line (SMMC-7721) was cultured in RPMI-1640 medium
supplemented with 10% fetal bovine serum under an atmosphere of 5% carbon diox-
ide at 37°C. Cells were subcultured in the same medium under the same conditions
after reaching 70–80% confluency and were maintained in the log phase for fur-
ther experiments. The cell suspensions were dispensed (200 lL) in triplicate into
96-well culture plates at optimized concentrations of 1 × 104 cells/well in a com-
plete medium. The tested samples at final concentrations of 10, 50 and 100 µg/ml in
well. In control wells, only culture medium with vehicle was added. After an addi-
tional 72 h incubation period, the medium in each well was aspirated and replaced
with 100 µL MTT working solution. The cells were incubated at 37°C for 4 h, and
then the medium was aspirated and replaced with 100 µL DMSO to dissolve the
formazan crystals that are formed. The culture plates were shaken for 5 min, and
the absorbance of each well was read at 540 nm. The results were expressed as the
inhibition ratio of tumor cell proliferation calculated as (A-B)/A × 100%. A and
B are the average numbers of viable tumor cells of the control and the samples,
respectively.
Acknowledgements
We thank the analytic center of East China Normal University for data measurement. The project
was supported by Natural Science Foundation of Shanghai (11ZR1410400), “DAXIA” Foundation
of East China Normal University (2011DX-084) and large instruments Open Foundation of East
China Normal University (20151043&20162015).
Funding
Natural Science Foundation of Shanghai [11ZR1410400]; “DAXIA” Foundation of East China
Normal University [2011DX-084]; large instruments Open Foundation of East China Normal
University [20151043, 20162015].
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