An Unexpected FeCl 3/C-Catalyzed β-Stereoselective Glycosylation in the Presence of the C(2)-Benzyl Group

Article abstract of DOI:10.1055/s-0037-1611801

An efficient and completely β-stereoselective glycosylation that did not rely on neighboring group participation is described using 2-20 molpercent FeCl ₃ /C as the catalyst and benzylated propargyl glycosides as the donors to reach yields up to 96percent under mild condition. With an octatomic-ring intermediate at the α-face of FeCl ₃ /C with alkyne of propargyl glycosides, a panel of aglycones comprising aliphatic, alicyclic, unsaturated alcohols, halogenated alcohols, and phenols with different substitution were examined successfully for the exclusive β-stereoselective glycosylation reaction.

Full text of DOI:10.1055/s-0037-1611801

SYNTHESIS
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
© Georg Thieme Verlag Stuttgart · New York
2019, 51, A–Q
paper
A
en
H. Guo et al.
Paper
Synthesis
An Unexpected FeCl3/C-Catalyzed -Stereoselective Glycosylation
in the Presence of the C(2)-Benzyl Group
Hong Guoa
Wenshuai Sia
Juan Lia
Guofang Yanga
Tianjun Tanga
Zhongfu Wangb
Jie Tanga
R2
R2
R1
R1
FeCl3/C (2–20 mol%)
CH3CN, 60 °C
O
R3
O
R3
BnO
ROH/ArOH
(1.2 equiv)
OR/Ar
BnO
OBn
OBn
O
(1.0 equiv)
66 examples
up to 96% yield
β-anomer only
Glucose: R1 = CH2OBn, R2 = H, R3 = OBn
Galactose: R1 = CH2OBn, R2 = OBn, R3 = H
Xylose: R1 = H, R2 = H, R3 = OBn
Jianbo Zhang*a
0
0
0
0-0
0
0
3-3
7
2
6-
4
2
3
X
a School of Chemistry and Molecular Engineering, East China
Normal University, Shanghai, 200241, P. R. of China
Jbzhang@chem.ecnu.edu.cn
b School of Life Sciences, Northwest University, Xi’an, 710069,
P. R. of China
Received: 11.11.2018
Accepted after revision: 25.03.2019
Published online:
sylations.6 However, a mixture of - and -glycoside prod-
ucts are usually detected in the reactions because the do-
nors appear to go through an oxocarbenium intermediate
lacking the face selectivity. To avoid such difficulty, novel
neighboring group participations by C(2)-ether functions in
glycosylation have been developed.7 Boons et al. used
neighboring group participation by an R-auxiliary at C(2)
leading to 1,2-trans glycosides.8 Demchenko and co-work-
ers have recently reported the stereoselective synthesis of
-glycosides utilizing C(2)-picolyl moiety as a novel neigh-
boring participating group.9 Nguyen’s strategy for -glyco-
sylation was to exploit the ability of cationic palladium cat-
alyst to direct -glycosylation through coordination to both
the imidate nitrogen and C(2)-oxygen of glycosyl trichloro-
acetimidate donors.10 Mlynarski et al. used 2-O-(2-nitro-
benzyl) and 2-O-(2-cyanobenzyl) groups to control stereo-
selective formation of 1, 2-trans glycosidic linkages via the
arming participation effect.11 Schmidt et al. used -O-glyco-
pyranosyl trichloroacetimidates and dibenzylphosphoric
acid leading to 1,2-trans glycosides.12 There were also some
reports on the use of nitrile solvent to improve the -selec-
tivity.5e,13
These explorations showed C(2)-ether functionality of
glycosyl donors could also construct -glycoside products
in appropriate cases. Then how to improve -selectivity and
what kind of new donors could influence -glycosylation
were worth further research. In the past decade, propargyl
glycosides have shown great potential in glycosylations,
compared to conventional glycosyl donors.14 However, most
of the methods for the activation of propargyl glycosides
were limited to the use of toxic or noble catalysts such as
Hg(OTf)2, AuCl3, AuBr3, or AuCl3 with AgSbF6, which made
them difficult to be widely used in the synthesis of glyco-
sides. It should be noted that a few of these reports were re-
ported to yield 1,2-trans -glycosides.14b Nevertheless, it
need to be converted to orthoester, as a new intermediate.
DOI: 10.1055/s-0037-1611801; Art ID: ss-2018-h0756-op
Abstract An efficient and completely -stereoselective glycosylation
that did not rely on neighboring group participation is described using
2–20 mol% FeCl3/C as the catalyst and benzylated propargyl glycosides
as the donors to reach yields up to 96% under mild condition. With an
octatomic-ring intermediate at the -face of FeCl3/C with alkyne of
propargyl glycosides, a panel of aglycones comprising aliphatic, alicy-
clic, unsaturated alcohols, halogenated alcohols, and phenols with dif-
ferent substitution were examined successfully for the exclusive -ste-
reoselective glycosylation reaction.
Key words propargyl glycosides, glycosylation, -stereoselective,
C(2)-benzyl group, FeCl3/C
Naturally occurring carbohydrates carrying 1,2-trans--
glycosidic bonds such as -(1→6)-glucan, machilusides A
and B, and sulfated holostane glycosides from sea cucumber
Holothurian leucospilota are important biomolecules.1
Chemically, stereocontrol on the basis of neighboring group
participation (NGP) by a C(2)-ester group has often fulfilled
expectations to furnish 1,2-trans--glycosidic linkages.2
However, reactivities of glycosyl donors incorporating C(2)-
ester functionality are often decreased in many methodolo-
gies due to disarmed effect.3 This popular approach could
also suffer from the competitive formation of orthoesters
and acyl migration problems.4 An alternative approach to
settle this problem is to avoid C(2)-ester functions; howev-
er, the reaction conditions providing high 1,2-trans -selec-
tivity are limited.5 Therefore a general, high-yielding and
operationally easy 1,2-trans -selective glycosylation that
does not invoke C(2)-ester neighboring group participation
is highly desired.
Recently, C(2)-ether functionality of glycosyl donors
have been explored because they are recognized as ‘armed’
donors, which could enhance the reactivity in many glyco-
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

B
H. Guo et al.
Paper
Synthesis
Recently, we reported that FeCl315 as an efficient and afford-
able catalyst could activate propargyl glycosides leading to
disaccharides effectively.15g However, a mixture of - and -
glycoside products were still detected in the reactions and
the synthesis with exclusive -selectivity with propargyl
donor still remains a challenge. Very recently, our group has
made many attempts and occasionally found that when al-
cohol acceptors were applied, less equivalents of FeCl3 were
required and -stereoselectivity was exclusive. Whether
this was accidental or regular, it was worthy of further re-
search.
In this article, our novel strategy for -glycosylation was
to exploit the ability of iron catalysts to direct -glycosyla-
tion through coordination to both the alkynyl and C(2)-ox-
ygen of complete benzyl protecting propargyl glycosides16
(Scheme 1).
Table 1 Screening of Ferric Salts for the Catalysta
OBn
OBn
O
catalyst
O
BnO
BnO
BnO
BnO
OBn
BnOH
+
solvent
BnO
BnO
O
2
1
Entry
Catalyst
FeCl3
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
9
3
81
72
70
65
ND
67
80
73
96
FeCl3·6H2O
Fe2(SO4)3
4
15
10
24
24
15
20
3
Fe(NO3)3·9H2O
FeCl2
FeCl3/SiO2
FeCl3/4Å MS
FeCl3/Al2O3
FeCl3/C
Present work
R2
R2
R1
R1
O
R3
BnO
FeCl3/C, CH3CN
60 °C
O
R3
BnO
OR/Ar
+
ROH/ArOH
a Catalyst (3 mol%), ROH (1.2 equiv), CH3CN.
b Isolated yields. ND: Not detected.
BnO
BnO
O
β-anomer only
Glucose: R1 = CH2OBn, R2 = H, R3 = OBn
Galactose: R1 = CH2OBn, R2 = OBn, R3 = H
Xylose: R1 = H, R2 = H, R3 = OBn
ence of 0.02 equivalent of FeCl3/C in CH3CN (Table 2, entries
5–8 and entries 14–16). Toluene, 1,4-dioxane, acetone, nitro-
methane, DMF, and dichloroethane, which are also widely
used in glycosylation, were not suitable in this case (Table 2,
entries 9–13). In the end, the preferable result was achieved
Previous work
OP
OP
O
Hg(II), Ga(III), Au(I)
or Au(III) salts
O
PO
PO
ROH
PO
PO
+
OR
PO
LG
OP
Table 2 Optimizing the Reaction Conditions
P = Bn
LG = OAc, OC(NH)CCl3, STol or propargyl
Entry Catalyst
(equiv)
Acceptor Solvent
(equiv)
Temp
(°C)
Time (h) Yield
(%)a
Scheme 1 Metal-catalyzed glycosylation
1
0.01
0.02
0.04
0.10
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
1.2
1.2
1.2
1.2
1
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
toluene
60
60
60
60
60
60
60
60
60
5
92
96
92
95
64
90
95
95
ND
ND
ND
ND
ND
ND
80
82
87
Initial studies were performed with propargyl 2,3,4,6-
tetra-O-benzyl--D-glucoside 1 as the glycosyl donor and
benzyl alcohol as the nucleophilic acceptor. Upon treatment
of both coupling partners 1 and benzyl alcohol with 3 mol%
of commercially available metal chlorides like AlCl3, PdCl2,
CuCl2, ZnCl2, CoCl2·6H2O, and NiCl2·6H2O as the catalyst in
CH3CN at 60 °C for 24 hours; unfortunately, no desired
product appeared in the reaction, regardless of the amount
of catalyst used.
2
3
3
2.5
1.5
24
9
4
5
6
1.1
1.3
1.5
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
7
2.8
2.4
24
24
24
24
24
24
12
9
8
9
In recent years, iron salts7e,15g,17 have been widely used
in organic chemistry as efficient catalysts, so we tried to
catalyze the reaction with them (Table 1). As a result, all
Fe(III) salts could promote this reaction among which FeCl3
(3 mol%) is the best; the desired product 2 was isolated in
81% yield with completely -stereoselectivity after 3 hours
(Table 1, entry 1). This result was fairly encouraging be-
cause it clearly showed that FeCl3 (3 mol%) could direct -
glycosylation with the C(2)-benzyl protected donor to pro-
vide the desired glycoside. We found that the reactions af-
forded the products in moderate to good yields in the pres-
10
11
12
13
14
15
16
17
1,4-dioxane 60
acetone
CH3NO2
DMF
60
60
60
60
20
40
80
DCE
CH3CN
CH3CN
CH3CN
2
a Isolated yields, complete -selectivity. ND: Not detected.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

C
H. Guo et al.
Paper
Synthesis
when the reaction was carried out with 2 mol% of FeCl3/C in
CH3CN at 60 °C and the desired product 3 was isolated in
96% yield with complete -stereoselectivity.
smoothly under the specified conditions, as well as com-
plex alcohols such as menthol. All reactions afforded excel-
lent yields (81–96%) with complete -selectivity.
Having established the optimal reaction conditions, we
decided to survey its scope with a variety of acceptors. As
shown in Scheme 2, glycosidation between propargyl
2,3,4,6-tetra-O-benzyl-D-glucopyranosyl glycoside and pri-
mary, secondary, benzyl and allyl alcohols proceeded
Since a wide range of important organic reactions can
be efficiently catalyzed by solid acids, which often show
improved efficiency and recyclability,18 different iron salts
with and without a carrier were tried. It showed that acti-
R2
R1
R1
R3
BnO
O
R3
O
FeCl3/C (2–10 mol%)
CH3CN, 60 °C
OR
+
ROH
BnO
OBn
OBn
O
(1.2 equiv)
(1.0 equiv)
1 Glucose: R1 = CH2OBn, R2 = H, R3 = OBn a
16 Galactose: R1 = CH2OBn, R2 = OBn, R3 = H b
31 Xylose: R1 = H, R2 = H, R3 = OBn a
OBn
OBn
OBn
OBn
OBn
O
O
O
O
O
BnO
BnO
BnO
BnO
BnO
BnO
BnO
BnO
BnO
BnO
O
O
O
O
CF3
O
Cl
OBn
OBn
OBn
OBn
OBn
2
3
4
5
6
96% yield, 3 h
93% yield, 4 h
91% yield, 5 h
92% yield, 7 h
86% yield, 6 h
OBn
OBn
OBn
O
OBn
O
OBn
O
O
O
O
BnO
BnO
BnO
BnO
BnO
BnO
BnO
BnO
BnO
BnO
O
O
O
O
OBn
OBn
OBn
10
OBn
OBn
2
3
2
8
9
11
7
95% yield, 5 h
90% yield, 4 h
94% yield, 4 h
95% yield, 8 h
91% yield, 4 h
OBn
O
BnO
OBn
OBn
OBn
O
OBn
O
O
O
O
BnO
BnO
BnO
BnO
BnO
BnO
BnO
BnO
O
O
O
O
BnO
OBn
15
OBn
OBn
OBn
14
7
3
OBn
12
13
17
OH
83% yield, 5 h
81% yield, 6 h
82% yield, 6 h
88% yield, 4 h
92% yield, 5 h
BnO
BnO
OBn
BnO
BnO
BnO
BnO
BnO
OBn
OBn
OBn
OBn
OBn
O
O
O
O
O
O
O
O
O
O
CF3
O
O
BnO
BnO
BnO
BnO
BnO
Cl
OBn
22
OBn
OBn
OBn
OBn
21
OBn
18
19
20
23
92% yield, 5 h
90% yield, 6 h
89% yield, 8 h
83% yield, 6 h
92% yield, 8 h
89% yield, 6 h
BnO
BnO
OBn
BnO
BnO
BnO
OBn
BnO
BnO
BnO
OBn
OBn
OBn
O
O
O
O
O
O
O
O
O
O
BnO
OBn
BnO
OBn
2
OBn
OBn
3
OBn
2
24
25
26
27
28
OH
88% yield, 6 h
92% yield, 10 h
87% yield, 6 h
81% yield, 8 h
80% yield, 8 h
BnO
BnO
OBn
OBn
O
O
O
O
BnO
BnO
BnO
BnO
BnO
BnO
O
O
O
O
Cl
O
O
OBn
OBn
OBn
BnO
BnO
OBn
3
OBn
7
29
30
32
33
34
80% yield, 8 h
85% yield, 6 h
94% yield, 3 h
89% yield, 5 h
93% yield, 5 h
O
O
O
O
O
O
BnO
BnO
BnO
BnO
BnO
BnO
BnO
BnO
O
O
O
O
BnO
BnO
OBn
OBn
OBn
OBn
2
3
OBn
35
36
37
38
39
OH
90% yield, 4 h
90% yield, 4 h
82% yield, 6 h
81% yield, 6 h
81% yield, 6 h
Scheme 2 Alcohol substrate scope via FeCl3/C catalyst. a FeCl3/C (0.02 equiv). b FeCl3/C (0.10 equiv). Isolated yields are shown.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

D
H. Guo et al.
Paper
Synthesis
vated carbon was the best carrier for the iron catalyst FeCl3
(Table 1, entry 9). Then we optimized the reaction condi-
tions like solvent, catalyst amounts, and acceptor (Table 2).
The stereochemistry and structure of all the glycosylat-
ed products were elucidated by NMR and mass spectral
data and also by comparison with the reported data.15g,16,19
Furthermore, galactosyl 16 and xylosyl 31 propargyl
glycosides can be also reacted with various alcohols to ob-
tain the corresponding products in good yields and single -
selectivity (Scheme 2). The results showed that good yields
and single -stereoselectivity could be obtained using vari-
ous alcohols as acceptors. Then the method was extended
to phenolic acceptors. To our delight, the desired single -
O-glycosides were obtained with higher dosage of catalyst.
Meanwhile the reaction between propargyl glycosides of 1
and glycosyl acceptors was attempted. When methyl 2,3,4-
used, unfortunately, no product was detected, even under
0.5 equivalent of FeCl3/C after 12 hours of reaction time.
Only traces of the product could be detected, when methyl
2,3,4-tri-O-benzoyl-6-O-hydroxyl--D-glucopyranoside
was applied as acceptor. Notably, a variety of phenols were
also able to tolerate this iron(III) salt condition. From
Scheme 3, we can conclude that not only the phenols with
electron-donating substituents (→ 41, 42, 51, 52, 61, 62)
but also the elcctron-withdrawing (→ 46, 47, 56, 57, 66, 67)
and steric hindered phenols (→ 43, 44, 45, 53, 54, 55, 63, 64,
65) could give excellent results. All the reactions provided
the corresponding -aryl-O-glycosides as the only detect-
able glycosylation products in good to excellent yields (79–
95%). Additionally, the undesired C-arylglycosides were not
observed in the reaction. Comparing the reactivity between
alcohols and phenols, benzyl alcohol and phenol were em-
ployed to reactions with propargyl 2,3,4,6-tetra-O-benzyl-
tri-O-benzyl-6-O-hydroxyl--D-glucopyranoside
and
1,2:3,4-acetonide-6-hydroxyl--D-galactopyranoside were
R2
R1
R2
R1
R3
O
R3
O
FeCl3/C (10–20 mol%)
CH3CN, 60 °C
ArOH
BnO
OAr
BnO
OBn
O
OBn
(1.5 equiv)
(1.0 equiv)
1 Glucose: R1 = CH2OBn, R2 = H, R3 = OBn a
16 Galactose: R1 = CH2OBn, R2 = OBn, R3 = H b
31 Xylose: R1 = H, R2 = H, R3 = OBn a
OBn
OBn
OBn
OBn
OBn
H3C
O
H3C
O
O
O
O
O
BnO
BnO
BnO
BnO
BnO
BnO
BnO
BnO
BnO
BnO
O
CH3
O
CH3
O
O
OBn
40
OBn
OBn
OBn
OBn
43
80% yield, 9 h
41
42
44
88% yield, 6 h
89% yield, 6 h
91% yield, 6 h
81% yield, 9 h
OBn
O
OBn
OBn
O
OBn
OBn
H3C
O
O
O
BnO
BnO
BnO
BnO
O
BnO
BnO
BnO
BnO
BnO
BnO
O
O
O
Cl
O
Br
OBn
OBn
OBn
OBn
46
OBn
H3C
45
47
48
49
78% yield, 12 h
86% yield, 5 h
86% yield, 5 h
87% yield, 6 h
88% yield, 6 h
OBn
OBn
OBn
OBn
OBn
BnO
BnO
BnO
BnO
BnO
BnO
H3C
BnO
H3C
O
O
O
O
O
O
O
O
O
CH3
O
CH3
BnO
BnO
BnO
OBn
OBn
OBn
OBn
OBn
50
51
52
53
54
88% yield, 7 h
89% yield, 6 h
89% yield, 6 h
80% yield, 10 h
81% yield, 9 h
OBn
OBn
OBn
OBn
OBn
BnO
BnO
BnO
BnO
H3C
BnO
BnO
O
O
O
O
O
O
O
O
O
Br
O
Cl
BnO
BnO
BnO
BnO
OBn
OBn
OBn
OBn
OBn
H3C
55
56
57
58
59
79% yield, 12 h
86% yield, 6 h
86% yield, 6 h
87% yield, 6 h
87% yield, 6 h
H3C
O
H3C
O
O
O
O
O
O
BnO
BnO
BnO
BnO
BnO
BnO
BnO
BnO
O
O
CH3
BnO
BnO
O
CH3
O
OBn
61
OBn
64
OBn
OBn
63
80% yield, 8 h
OBn
60
89% yield, 6 h
62
88% yield, 6 h
90% yield, 6 h
84% yield, 9 h
H3C
O
O
O
O
O
O
O
BnO
BnO
BnO
BnO
BnO
BnO
Cl
Br
O
BnO
BnO
BnO
O
BnO
OBn
66
OBn
OBn
OBn
OBn
H3C
65
78% yield, 12 h
67
68
88% yield, 6 h
69
88% yield, 5 h
87% yield, 5 h
88% yield, 6 h
Scheme 3 Phenol substrate scope via FeCl3/C catalyst. a FeCl3/C (0.10 equiv). b FeCl3/C (0.20 equiv). Isolated yields are shown.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

E
H. Guo et al.
Paper
Synthesis
-D-glucoside 1 as the glycosyl donor. Based on these find-
ings, the alcoholic hydroxyl group was shown to have sig-
nificantly higher reactivity.
Table 3 Mechanistic Studies with Various Donorsa
Entry Donors
1
Productb Time (h)
Yield (%)c
96
Encouraged by the above excellent results, the catalyzed
FeCl3/C reaction was further explored in the synthesis of -
stereoselective glycosylation between more glycosyl donors
and benzyl alcohol as shown in Table 3. When compound
70 was applied, the expected product could be obtained in
85% yield under FeCl3/C condition (Table 3, entry 2). We
tried the reaction between propargyl 3,4,6-tri-O-benzyl-2-
O-methyl--D-glucopyranoside and benzyl alcohol. Unfor-
tunately, no product was detected under 0.5 equivalent of
FeCl3/C after 12 hours of reaction time. This result indicates
that the applicability of the donors needs further explora-
tion (entry 3). However, when compound 72 was applied,
the product could be obtained in a low yield of 35% (entry
4). It can be seen from entries 1–4 in Table 3 that the impor-
tance of the substituent and the activation of the donor by
the benzyl group increase the reactivity, and if the benzyl
group is not protected or the number of benzyl substituent
was less, the corresponding reactivity was also reduced. Un-
expectedly, when propargyl 2,3,4,6-tetra-O-benzyl-D-man-
nopyranosyl glycoside, another common donor was ap-
plied, the expected product could not be detected in the re-
action (entry 5). This did not match with the mechanism
we had proposed earlier.15 We also found that the reaction
between benzylated L-fucose derived propargyl glycosyl
donor and benzyl alcohol afforded the product 82 in 63%
yield with complete -stereoselectivity in the presence of
0.02 equivalent of FeCl3/C after 16 hours (entry 6). To ex-
plore this new mechanism, other glyco donors were further
employed. In the absence of the C(2)-substituent group,
there was no reaction, thus indicating that the product is
the result of C(2)-group participation (entry 7). It has been
reported that compound 76 could be activated by Lewis ac-
id,20 however, no product was detected when FeCl3/C was
used to activate 76. Similarly, the donor of allyl glycoside
could not be activated either. These results indicate that the
FeCl3/C and anomeric propargyl were the key to the reac-
tion (entry 8).
OBn
2
3
O
BnO
BnO
OBn
O
O
O
1
2
80
5
85
OBn
O
BnO
BnO
OH
70
3
–
12
ND
OBn
O
BnO
BnO
MeO
71
4
81
5
35
ND
63
OH
O
HO
HO
OH
72
O
5
–
24
16
OBn
OBn
O
BnO
BnO
O
73
6
82
O
O
OBn
OBn
OBn
74
7
–
–
24
24
ND
ND
OBn
O
BnO
BnO
O
75
8
OBn
When the 1,2-O-protecting group were changed from
cis to trans (Table 3, entries 1 and 9), there was no reaction.
These results indicate that 1,2-cis configuration is crucial in
the donor structure. Besides, it should be noted that the re-
action system was also not suitable to the donors of 2-acyl
group due to the disarmed effect (entries 10 and 11). Taken
together, these results support our hypothesis that the
combination of the propargyl on O-1 and the demanding
Bn group on O-2 and 1,2-cis favors the formation of -gly-
cosides by -selective attack of alcohol on an electrophilic
intermediate.
O
BnO
BnO
OBn
OMe
76
9
–
24
ND
OBn
O
BnO
BnO
O
OBn
77
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

F
H. Guo et al.
Paper
Synthesis
Table 3 (continued)
Entry Donors
10
In summary, a novel method for FeCl3/C-catalyzed -se-
lective glycosylation in the absence of the C(2)-ester partic-
ipating group has been developed. The reaction was com-
pletely -selective and proceeded with low catalyst loading
(2–20 mol%).
Productb Time (h)
Yield (%)c
ND
–
–
24
OBn
O
BnO
BnO
Furthermore, as an effective, economical, and environ-
mentally beneficial heterogeneous catalyst, FeCl3/C can be
simply filtered after the completion of the reaction which
entails the simple procedure. Exclusive -stereoselective
glycoside products could be obtained from aliphatic, alicy-
clic, unsaturated alcohols, halogenated alcohols, and phe-
nols with different substitution. Mechanistic studies with
varying propargyl glycosidic donors for an octatomic-ring
intermediate at the -face of FeCl3/C with alkyne of propar-
gyl glycosides were performed. Lastly, as a number of natu-
ral products are glycosylated with -O-glycosides, this nov-
el -glycosylation method should be useful for their prepa-
ration as well.
OAc
O
O
78
11
24
ND
OAc
O
AcO
AcO
OAc
79
a Reaction conditions: FeCl3/C (0.02 equiv), BnOH (1.2 equiv).
b See experimental for product description.
c Isolated yields. ND: Not detected.
According to the above results, the proposed reaction
mechanism may be explained as follows (Scheme 4).16,17d,21
An octatomic-ring intermediate B at the -face of FeCl3
with alkyne is formed first. Intermediate B is attacked by
nucleophile ROH leading to glycoside C. Intermediate C gen-
erates glycosylation product D and alkenyl iron complex E.
Subsequent deferrization of anion E provides volatile cyclo-
propanone G and meanwhile regenerates the catalyst. In
addition, carbon as the carrier of Lewis catalyst plays an im-
portant role in this reaction and its mechanism of action is
still in the research stage. It has been reported that carriers
often played important roles in heterogeneous reactions.22
It is also believed that there were collaborative effect and
support effect between the carrier and the catalyst, so good
reactivity and high stereoselectivity were obtained.18d,23
Unless otherwise noted, materials were obtained from commercial
suppliers and were used without further purification. Unless other-
wise reported, all reactions were performed under argon atmosphere.
Removal of solvent in vacuo refers to distillation using a rotary evapo-
rator attached to an efficient vacuum pump. 1H NMR and 13C NMR
spectra were recorded on Bruker DRX-500 NMR spectrometer in solu-
tions of CDCl3 using TMS as the internal standard. Mass spectra were
determined on LTQ-XL (Thermo scientific, USA) with an (ESI) ion trap
mass spectrometer.
Catalyst FeCl3/C
Activated charcoal-supported FeCl3 was prepared by the following
method: To a mixture of FeCl3 (0.1 g) and activated charcoal (0.5 g,
200–300 mesh) was added anhyd EtOH (5 mL) and the slurry was re-
fluxed for 30 min. The solvent was evaporated under reduced pres-
sure resulting in free flowing FeCl3/activated charcoal, which was
dried at 120 °C for 2 h and used for the reactions directly.
O
O
R
O
G
F
BnO
O
FeCl3
Reaction of 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside with Al-
cohols and Phenols in the Presence of FeCl3/C; General Procedure
A
A suspension of the FeCl3/C catalyst (2 mg, 0.002 mmol) in anhyd
CH3CN (6 mL) was prepared in a round-bottomed flask. A portion of
this preparation (1.5 mL) was added to a mixture of required 2,3,4,6-
tetra-O-benzyl--D-glucopyranoside (58 mg, 0.1 mmol) and the re-
spective acceptor (0.12 mmol) in a round-bottomed flask (5 mL) un-
der N2 atmosphere and the reaction mixture was stirred at 60 °C. Af-
ter completion of the reaction (monitored by TLC), the organic phase
was condensed under vacuum to obtain the crude product, which
was purified by silica gel column chromatography (PE/EtOAc 40:1).
ROH
O
O
-
R
FeCl3
E
BnO
O
Fe
O
R
OR
B
BnO
D
O
R
OR
BnO
Fe
All new compounds were fully characterized by 1H NMR, 13C NMR,
and MS. Spectral and analytical data were in good agreement with
the desired structures.
O
C
Propargyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (1)15g
Scheme 4 The possible mechanism for the glycosylation
Compound 1 was prepared according to the general procedure and
isolated as a white solid (8.22 g, 95% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 83–84 °C.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

G
H. Guo et al.
Paper
Synthesis
1H NMR (500 MHz, CDCl3):  = 2.46 (1 H, t, J = 2.4 Hz), 3.47–3.50 (2 H,
m), 3.61–3.73 (4 H, m), 4.42–4.46 (2 H, m), 4.46 (1 H, d, J = 12.2 Hz),
4.48 (1 H, d, J = 10.9 Hz), 4.60 (1 H, d, J = 11.9 Hz), 4.71 (1 H, d, J = 10.9
Hz), 4.76 (1 H, d, J = 10.9 Hz), 4.81 (1 H, d, J = 10.9 Hz), 4.83 (1 H, d, J =
10.9 Hz), 4.98 (1 H, d, J = 10.9 Hz), 5.08 (1 H, d, J = 3.6 Hz), 7.14–7.16
(2 H, m), 7.26–7.39 (18 H, m).
ESI-MS: m/z calcd for C36H40O6Na [M + Na]+: 591.28; found: 591.33.
Isopropyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (6)24q
Compound 6 was prepared according to the general procedure and
isolated as a white solid (50 mg, 86% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 107–108 °C.
1H NMR (500 MHz, CDCl3):  = 3.45–3.49 (2 H, m), 3.57–3.61 (1 H, m),
3.63–3.73 (5 H, m), 3.80–3.85 (1 H, m), 4.15–4.20 (1 H, m), 4.44 (1 H,
d, J = 7.7 Hz), 4.52 (1 H, d, J = 10.8 Hz), 4.54 (1 H, d, J = 12.1 Hz), 4.60 (1
H, d, J = 12.2 Hz), 4.71 (1 H, d, J = 10.7 Hz), 4.78 (1 H, d, J = 11.1 Hz),
4.81 (1 H, d, J = 11.0 Hz), 4.93 (1 H, d, J = 10.9 Hz), 4.99 (1 H, d, J = 10.9
Hz), 7.14–7.16 (2 H, m), 7.26–7.38 (19 H, m).
ESI-MS: m/z calcd for C37H38O6Na [M + Na]+: 601.27; found: 601.33.
Benzyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (2)16
Compound 2 was prepared according to the general procedure and
isolated as a white solid (60.5 mg, 96% yield ) after column chroma-
tography on silica gel (PE/EtOAc 40:1); mp 81–82 °C.
1H NMR (500 MHz, CDCl3):  = 3.46–3.49 (1 H, m), 3.51–3.55 (1 H, m),
3.60–3.65 (2 H, m), 3.69–3.78 (2 H, m), 4.51 (1 H, d, J = 7.8 Hz), 4.54 (1
H, d, J = 11.0 Hz), 4.57 (1 H, d, J = 12.3 Hz), 4.64 (1 H, d, J = 12.1 Hz),
4.67 (1 H, d, J = 11.9 Hz), 4.72 (1 H, d, J = 10.9 Hz), 4.78 (1 H, d, J = 10.9
Hz), 4.82 (1 H, d, J = 10.8 Hz), 4.92 (1 H, d, J = 11.0 Hz), 4.95 (1 H, d, J =
11.2 Hz), 4.98 (1 H, d, J = 12.4 Hz), 7.16–7.18 (2 H, m), 7.26–7.39 (22
H, m).
ESI-MS: m/z calcd for C36H39ClO6Na [M + Na]+: 625.24; found: 625.25.
Allyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (7)24c
Compound 7 was prepared according to the general procedure and
isolated as a white solid (55 mg, 95% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 76–77 °C
1H NMR (500 MHz, CDCl3):  = 3.44–3.50 (2 H, m), 3.57–3.70 (4 H, m),
3.74 (1 H, d, J = 9.4 Hz), 4.13–4.17 (1 H, m), 4.42 (1 H, d, J = 5.2 Hz),
4.45 (1 H, d, J = 7.8 Hz), 4.52 (1 H, d, J = 10.9 Hz), 4.54 (1 H, d, J = 12.2
Hz), 4.59 (1 H, d, J = 10.9 Hz), 4.72 (1 H, d, J = 11.0 Hz), 4.78 (1 H, d, J =
11.0 Hz), 4.81 (1 H, d, J = 10.9 Hz), 4.96 (1 H, d, J = 11.0 Hz), 4.98 (1 H,
d, J = 9.7 Hz), 5.21 (1 H, d, J = 10.6 Hz), 5.34 (1 H, d, J = 17.3 Hz), 5.97 (1
H, m), 7.15–7.17 (2 H, m), 7.26–7.35 (20 H, m).
ESI-MS: m/z calcd for C41H42O6Na [M + Na]+: 653.30; found: 653.33.
Ethyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (3)24i
Compound 3 was prepared according to the general procedure and
isolated as a white solid (53.0 mg, 93% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1); mp 94–95 °C
1H NMR (500 MHz, CDCl3):  = 3.44–3.50 (2 H, m), 3.57–3.70 (4 H, m),
3.74 (1 H, d, J = 9.4 Hz), 4.13–4.17 (1 H, m), 4.42 (1 H, d, J = 5.2 Hz),
4.45 (1 H, d, J = 7.8 Hz), 4.52 (1 H, d, J = 10.9 Hz), 4.54 (1 H, d, J = 12.2
Hz), 4.59 (1 H, d, J = 10.9 Hz), 4.72 (1 H, d, J = 11.0 Hz), 4.78 (1 H, d, J =
11.0 Hz), 4.81 (1 H, d, J = 10.9 Hz), 4.96 (1 H, d, J = 11.0 Hz), 4.98 (1 H,
d, J = 9.7 Hz), 5.21 (1 H, d, J = 10.6 Hz), 5.34 (1 H, d, J = 17.3 Hz), 5.97 (1
H, m), 7.15–7.17 (2 H, m), 7.26–7.35 (20 H, m).
ESI-MS: m/z calcd for C37H40O6Na [M + Na]+: 603.28; found: 603.25.
Butyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (8)19c
Compound 8 was prepared according to the general procedure and
isolated as a white solid (54 mg, 90% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 59–60 °C.
1H NMR (500 MHz, CDCl3):  = 0.92 (3 H, t, J = 7.5 Hz), 1.40–1.46 (2 H,
m), 1.62–1.66 (2 H, m), 3.42–3.46 (2 H, m), 3.51–3.58 (2 H, m), 3.62–
3.68 (2 H, m), 3.73 (1 H, d, J = 9.5 Hz), 3.96 (1 H, m), 4.38 (1 H, d, J = 8.0
Hz), 4.51 (1 H, d, J = 10.5 Hz), 4.55 (1 H, d, J = 12.5 Hz), 4.61 (1 H, d, J =
12.0 Hz), 4.70 (1 H, d, J = 11.0 Hz), 4.77 (1 H, d, J = 11.0 Hz), 4.80 (1 H,
d, J = 10.5 Hz), 4.92 (1 H, d, J = 12.0 Hz), 4.94 (1 H, d, J = 11.5 Hz), 7.14–
7.16 (2 H, m), 7.25–7.34 (18 H, m).
ESI-MS: m/z calcd for C37H40O6Na [M + Na]+: 603.28; found: 603.25.
2-Chloroethyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (4)24b
Compound 4 was prepared according to the general procedure and
isolated as a colorless oil (55 mg, 91% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 1.75–1.79 (2 H, m), 2.17–2.18 (2 H, m),
3.44–3.47 (2 H, m), 3.55–3.69 (4 H, m), 3.75 (1 H, m), 3.98 (1 H, m),
4.39 (1 H, d, J = 7.8 Hz), 4.53 (1 H, d, J = 10.9 Hz), 4.56 (1 H, d, J = 12.5
Hz), 4.62 (1 H, d, J = 12.3 Hz), 4.73 (1 H, d, J = 11.0 Hz), 4.79 (1 H, d, J =
11.0 Hz), 4.82 (1 H, d, J = 10.8 Hz), 4.93 (1 H, d, J = 12.0 Hz), 4.95 (1 H,
d, J = 11.0 Hz), 4.98 (1 H, d, J = 9.9 Hz), 5.01–5.05 (1 H, m), 5.75–5.86
(1 H, m), 7.15–7.17 (2 H, m), 7.26–7.35 (18 H, m).
ESI-MS: m/z calcd for C38H44O6Na [M + Na]+: 619.31; found: 619.33.
Pentyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (9)19c
Compound 9 was prepared according to the general procedure and
isolated as a colorless oil (57 mg, 94% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 0.88 (3 H, t, J = 7.0 Hz), 1.31–1.38 (4 H,
m), 1.64–1.67 (2 H, m), 3.42–3.47 (2 H, m), 3.50–3.59 (2 H, m), 3.61–
3.68 (2 H, m), 3.73 (1 H, d, J = 10.5 Hz), 3.96 (1 H, m), 4.38 (1 H, d, J =
8.0 Hz), 4.51 (1 H, d, J = 11.0 Hz), 4.55 (1 H, d, J = 12.5 Hz), 4.61 (1 H, d,
J = 12.5 Hz), 4.71 (1 H, d, J = 11.0 Hz), 4.78 (1 H, d, J = 11.0 Hz), 4.82 (1
H, d, J = 10.5 Hz), 4.92 (1 H, d, J = 11.0 Hz), 4.95 (1 H, d, J = 11.5 Hz),
7.14–7.16 (2 H, m), 7.25–7.35 (20 H, m).
ESI-MS: m/z calcd for C39H44O6Na [M + Na]+: 631.31; found: 631.33.
2,2,2-Trifluoroethyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside
(5)24c
Compound 5 was prepared according to the general procedure and
isolated as a white solid (57 mg, 92% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 90–91 °C.
ESI-MS: m/z calcd for C39H46O6Na [M + Na]+: 633.33; found: 633.33.
1H NMR (500 MHz, CDCl3):  = 1.29 (3 H, t, J = 7.0 Hz), 3.43–3.46 (2 H,
m), 3.55–3.59 (1 H, m), 3.62–3.75 (4 H, m), 3.98–4.03 (1 H, m), 4.40 (1
H, d, J = 7.9 Hz), 4.52 (1 H, d, J = 11.8 Hz), 4.54 (1 H, d, J = 14.2 Hz), 4.61
(1 H, d, J = 12.4 Hz), 4.72 (1 H, d, J = 11.1 Hz), 4.78 (1 H, d, J = 11.1 Hz),
4.81 (1 H, d, J = 11.5 Hz), 4.92 (1 H, d, J = 13.5 Hz), 4.95 (1 H, d, J = 11.7
Hz), 7.14–7.16 (2 H, m), 7.26–7.33 (19 H, m).
4-Pentenyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (10)16
Compound 10 was prepared according to the general procedure and
isolated as a white solid (58 mg, 95% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 69–70 °C
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

H
H. Guo et al.
Paper
Synthesis
1H NMR (500 MHz, CDCl3):  = 1.75–1.79 (2 H, m), 2.17–2.18 (2 H, m),
3.44–3.47 (2 H, m), 3.55–3.69 (4 H, m), 3.75 (1 H, m), 3.98 (1 H, m),
4.39 (1 H, d, J = 7.8 Hz), 4.53 (1 H, d, J = 10.9 Hz), 4.56 (1 H, d, J = 12.5
Hz), 4.62 (1 H, d, J = 12.3 Hz), 4.73 (1 H, d, J = 11.0 Hz), 4.79 (1 H, d, J =
11.0 Hz), 4.82 (1 H, d, J = 10.8 Hz), 4.93 (1 H, d, J = 12.0 Hz), 4.95 (1 H,
d, J = 11.0 Hz), 4.98 (1 H, d, J = 9.9 Hz), 5.01–5.05 (1 H, m), 5.75–5.86
(1 H, m), 7.15–7.17 (2 H, m), 7.26–7.35 (18 H, m).
d, J = 11.0 Hz), 4.78 (1 H, d, J = 11.0 Hz), 4.82 (1 H, d, J = 10.5 Hz), 4.93
(1 H, d, J = 11.0 Hz), 4.95 (1 H, d, J = 11.0 Hz), 7.15–7.17 (2 H, m), 7.25–
7.34 (18 H, m).
13C NMR (125 MHz, CDCl3):  = 10.9, 11.2, 14.1, 23.1, 23.8, 29.0, 29.2,
29.7, 30.5, 30.6, 39.7, 39.8, 69.0, 72.4, 72.5, 73.5, 74.8, 74.9, 75.0, 75.7,
76.8, 78.0, 82.3, 84.8, 103.8, 103.9, 127.5, 127.6, 127.7, 127.8, 128.0,
128.1, 128.3, 128.4, 138.2, 138.3, 138.5, 138.7.
ESI-MS: m/z calcd for C39H44O6Na [M + Na]+: 631.31; found: 631.33.
HRMS (ESI): m/z calcd for C42H52O6Na [M + Na]+: 675.3656; found:
675.3646.
Hexyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (11)19c
Decyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (15)24o
Compound 11 was prepared according to the general procedure and
isolated as a colorless oil (54 mg, 91% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 0.88 (3 H, t, J = 7.0 Hz), 1.29–1.31 (4 H,
m), 1.39–1.41 (2 H, m), 1.64–1.67 (2 H, m), 3.43–3.47 (2 H, m), 3.51–
3.59 (2 H, m), 3.62–3.69 (2 H, m), 3.74 (1 H, d, J = 9.5 Hz), 3.94–3.99 (1
H, m), 4.39 (1 H, d, J = 7.5 Hz), 4.52 (1 H, d, J = 11.0 Hz), 4.55 (1 H, d, J =
12.5 Hz), 4.61 (1 H, d, J = 12.5 Hz), 4.71 (1 H, d, J = 11.0 Hz), 4.78 (1 H,
d, J = 11.0 Hz), 4.82 (1 H, d, J = 11.0 Hz), 4.93 (1 H, d, J = 11.0 Hz), 4.95
(1 H, d, J = 11.0 Hz), 7.15–7.17 (2 H, m), 7.26–7.35 (18 H, m).
Compound 15 was prepared according to the general procedure and
isolated as a colorless oil (60 mg, 88% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 0.88 (3 H, t, J = 6.7 Hz), 1.26–1.34 (15
H, m), 1.59–1.63 (3 H, m), 3.42–3.44 (1 H, m), 3.54–3.57 (1 H, m),
3.59–3.65 (3 H, m), 3.71– 3.79 (1 H, m), 3.99 (1 H, t, J = 9.2 Hz), 4.47 (2
H, d, J = 11.6 Hz), 4.61 (1 H, d, J = 12.2 Hz), 4.75 (2 H, m), 4.77 (1 H, d,
J = 11.0 Hz), 4.81 (1 H, d, J = 10.7 Hz), 4.82 (1 H, d, J = 10.5 Hz), 4.99 (1
H, d, J = 10.9 Hz), 7.15–7.17 (2 H, m), 7.25–7.34 (18 H, m).
ESI-MS: m/z calcd for C40H48O6Na [M + Na]+: 647.35; found: 647.33.
ESI-MS: m/z calcd for C44H56O6Na [M + Na]+: 703.41; found: 703.42.
Cyclohexyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (12)19c
Propargyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (16)15g
Compound 12 was prepared according to the general procedure and
isolated as a colorless oil (52 mg, 83% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
Compound 16 was prepared according to the general procedure and
isolated as a colorless oil (8.22 g, 95% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 1.23–1.30 (3 H, m), 1.33–1.52 (3 H, m),
1.75–1.76 (2 H, m), 1.97–2.01 (2 H, m), 3.43–3.47 (2 H, m), 3.53–3.57
(1 H, m), 3.62–3.68 (2 H, m), 3.70–3.75 (2 H, m), 4.51 (1 H, d, J = 7.8
Hz), 4.53 (1 H, d, J = 11.3 Hz), 4.56 (1 H, d, J = 12.9 Hz), 4.61 (1 H, d, J =
12.2 Hz), 4.71 (1 H, d, J = 10.8 Hz), 4.78 (1 H, d, J = 10.9 Hz), 4.82 (1 H,
d, J = 10.9 Hz), 4.92 (1 H, d, J = 10.9 Hz), 4.99 (1 H, d, J = 10.9 Hz), 7.15–
7.17 (2 H, m), 7.26–7.35 (18 H, m).
1H NMR (500 MHz, CDCl3):  = 2.42 (1 H, t, J = 2.4 Hz), 3.53–3.59 (4 H,
m), 3.82–3.86 (1 H, m), 3.89 (1 H, d, J = 3.0 Hz), 4.37–4.45 (4 H, m),
4.60 (1 H, d, J = 10.9 Hz), 4.61 (1 H, d, J = 11.0 Hz), 4.70 (1 H, d, J = 12.0
Hz), 4.72 (1 H, d, J = 11.5 Hz), 4.77 (1 H, d, J = 12.0 Hz), 4.94 (1 H, d, J =
11.5 Hz), 4.95 (1 H, d, J = 11.0 Hz), 7.26–7.34 (21 H, m).
ESI-MS: m/z calcd for C37H38O6Na [M + Na]+: 601.27; found: 601.33.
ESI-MS: m/z calcd for C40H46O6Na [M + Na]+: 645.33; found: 645.33.
Benzyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (17)24k
Compound 17 was prepared according to the general procedure and
isolated as a white solid (58 mg, 92% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 86–87 °C.
1H NMR (500 MHz, CDCl3):  = 3.51–3.55 (2 H, m), 3.58–3.63 (2 H, m),
3.87–3.90 (2 H, m), 3.69–3.78 (2 H, m), 4.42 (1 H, d, J = 12.0 Hz), 4. 45
(1 H, d, J = 11.0 Hz), 4.47 (1 H, d, J = 8.0 Hz), 4.63 (2 H, d, J = 12.1 Hz),
4.70 (1 H, d, J = 11.7 Hz), 4.75 (1 H, d, J = 11.2 Hz), 4.77 (1 H, d, J = 9.9
Hz), 4.92 (2 H, d, J = 10.9 Hz), 4.95 (1 H, d, J = 12.0 Hz), 7.25–7.35 (25
H, m).
Menthyl 2,3,4,6-etra-O-benzyl--D-glucopyranoside (13)24o
Compound 13 was prepared according to the general procedure and
isolated as a white solid (55 mg, 81% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 80–82 °C.
1H NMR (500 MHz, CDCl3):  = 0.83 (3 H, d, J = 6.9 Hz), 0.90 (6 H, d, J =
6.6 Hz), 0.92–0.99 (2 H, m), 1.24–1.39 (3 H, m), 1.66 (2 H, d, J = 11.9
Hz), 2.12–2.40 (2 H, m), 3.40–3.43 (2 H, m), 3.48–3.52 (1 H, m), 3.58–
3.66 (2 H, m), 3.70 (2 H, d, J = 3.2 Hz), 4.48 (1 H, d, J = 7.8 Hz), 4.54 (1
H, d, J = 12.1 Hz), 4.56 (1 H, d, J = 9.9 Hz), 4.61 (1 H, d, J = 12.4 Hz), 4.69
(1 H, d, J = 10.9 Hz), 4.79 (1 H, d, J = 11.3 Hz), 4.82 (1 H, d, J = 10.9 Hz),
4.93 (1 H, d, J = 11.1 Hz), 4.95 (1 H, d, J = 10.9 Hz), 7.15–7.17 (2 H, m),
7.26–7.35 (18 H, m).
ESI-MS: m/z calcd for C41H42O6Na [M + Na]+: 653.30; found: 653.33.
Ethyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (18)24n
Compound 18 was prepared according to the general procedure and
isolated as a colorless oil (52 mg, 92% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 1.27 (3 H, t, J = 7.0 Hz), 3.51–3.55 (2 H,
m), 3.58–3.61 (3 H, m), 3.81–3.84 (1 H, m), 3.90 (1 H, d, J = 2.5 Hz),
3.97–4.01 (1 H, m), 4.37 (1 H, d, J = 7.7 Hz), 4.41 (1 H, d, J = 11.8 Hz),
4.46 (1 H, d, J = 11.8 Hz), 4.63 (1 H, d, J = 11.7 Hz), 4.72 (1 H, d, J = 11.9
Hz), 4.74 (1 H, d, J = 12.5 Hz), 4.77 (1 H, d, J = 11.0 Hz), 4.94 (1 H, d, J =
10.9 Hz), 4.95 (1 H, d, J = 11.8 Hz), 7.26–7.39 (20 H, m).
ESI-MS: m/z calcd for C44H54O6Na [M + Na]+: 701.39; found: 701.42.
Isooctyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (14)
Compound 14 was prepared according to the general procedure and
isolated as a colorless oil (53 mg, 82% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 0.87–0.91 (6 H, m), 0.92–0.99 (2 H, m),
1.26–1.33 (7 H, m), 1.39–1.43 (3 H, m), 3.37–3.41 (1 H, m), 3.42–3.47
(2 H, m), 3.58 (1 H, t, J = 9.0 Hz), 3.63–3.69 (2 H, m), 3.75 (1 H, d, J =
10.0 Hz), 3.88–3.93 (1 H, m), 4.37 (1 H, d, J = 8.0 Hz), 4.53 (1 H, d, J =
10.5 Hz), 4.57 (1 H, d, J = 12.5 Hz), 4.62 (1 H, d, J = 12.0 Hz), 4.71 (1 H,
ESI-MS: m/z calcd for C36H40O6Na [M + Na]+: 591.28; found: 591.33.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

I
H. Guo et al.
Paper
Synthesis
2-Chloroethyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (19)
Butyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (23)24g
Compound 19 was prepared according to the general procedure and
isolated as a colorless oil (54 mg, 90% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
Compound 23 was prepared according to the general procedure and
isolated as a white solid (53 mg, 89% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 74–75 °C.
1H NMR (500 MHz, CDCl3):  = 3.50–3.58 (4 H, m), 3.67 (2 H, t, J = 6.0
Hz), 3.75–3.85 (2 H, m), 3.88 (1 H, d, J = 2.6 Hz), 4.12–4.16 (1 H, m),
4.40 (1 H, d, J = 9.3 Hz), 4.42 (1 H, d, J = 7.8 Hz), 4.43 (1 H, d, J = 11.7
Hz), 4.62 (1 H, d, J = 11.7 Hz), 4.71 (1 H, d, J = 11.9 Hz), 4.75 (1 H, d, J =
10.6 Hz), 4.77 (1 H, d, J = 11.8 Hz), 4.94 (1 H, d, J = 11.6 Hz), 4.98 (1 H,
d, J = 10.7 Hz), 7.26–7.39 (20 H, m).
13C NMR (125 MHz, CDCl3):  = 29.7, 42.7, 68.9, 69.7, 73.1, 73.4, 73.5,
73.6, 74.5, 75.2, 76.8, 79.3, 82.0, 104.1, 127.5, 127.6, 127.8, 127.9,
128.1, 128.2, 128.3, 128.4, 137.8, 138.4, 138.5, 138.6.
1H NMR (500 MHz, CDCl3):  = 0.92 (3 H, t, J = 7.4 Hz), 1.40–1.45 (2 H,
m), 1.62–1.66 (2 H, m), 3.50–3.55 (3 H, m), 3.59–3.61 (2 H, m), 3.80–
3.84 (1 H, m), 3.89 (1 H, d, J = 2.5 Hz), 3.92–3.97 (1 H, m), 4.36 (1 H, d,
J = 7.6 Hz), 4.41 (1 H, d, J = 11.8 Hz), 4.46 (1 H, d, J = 11.8 Hz), 4.63 (1 H,
d, J = 11.7 Hz), 4.72 (1 H, d, J = 11.9 Hz), 4.74 (1 H, d, J = 12.1 Hz), 4.76
(1 H, d, J = 10.7 Hz), 4.94 (1 H, d, J = 10.8 Hz), 4.95 (1 H, d, J = 11.7 Hz),
7.26–7.38 (20 H, m).
ESI-MS: m/z calcd for C38H44O6Na [M + Na]+: 619.31; found: 619.33.
HRMS (ESI): m/z calcd for C36H39ClO6Na [M + Na]+: 625.2327; found:
Pentyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (24)
625.2316.
Compound 24 was prepared according to the general procedure and
isolated as a colorless oil (54 mg, 88% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 0.88 (3 H, t, J = 7.1 Hz), 1.32–1.36 (4 H,
m), 1.62–1.66 (2 H, m), 3.47–3.54 (3 H, m), 3.58–3.60 (2 H, m), 3.80–
3.84 (1 H, m), 3.89 (1 H, d, J = 2.5 Hz), 3.92–3.96 (1 H, m), 4.35 (1 H, d,
J = 7.7 Hz), 4.41 (1 H, d, J = 11.8 Hz), 4.46 (1 H, d, J = 11.8 Hz), 4.63 (1 H,
d, J = 11.7 Hz), 4.71 (1 H, d, J = 11.7 Hz), 4.74 (1 H, d, J = 11.9 Hz), 4.76
(1 H, d, J = 12.2 Hz), 4.94 (1 H, d, J = 10.9 Hz), 4.95 (1 H, d, J = 11.8 Hz),
7.25–7.38 (19 H, m).
2,2,2-Trifluoroethyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside
(20)24c
Compound 20 was prepared according to the general procedure and
isolated as a colorless oil (55 mg, 89% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 3.50–3.56 (4 H, m), 3.84–3.87 (2 H, m),
3.91–3.95 (1 H, m), 4.15–4.19 (1 H, m), 4.40 (1 H, d, J = 12.0 Hz), 4.43
(1 H, d, J = 12.1 Hz), 4.47 (1 H, d, J = 7.6 Hz), 4.62 (1 H, d, J = 11.6 Hz),
4.71 (1 H, d, J = 11.7 Hz), 4.75 (1 H, d, J = 10.6 Hz), 4.77 (1 H, d, J = 11.9
Hz), 4.90 (1 H, d, J = 10.6 Hz), 4.94 (1 H, d, J = 11.6 Hz), 7.26–7.37 (20
H, m).
13C NMR (125 MHz, CDCl3):  = 14.0, 22.5, 28.3, 29.4, 68.9, 70.0, 73.1,
73.4, 73.5, 74.5, 75.2, 76.8, 79.6, 82.2, 82.3, 104.0, 127.5, 127.8, 127.9,
128.1, 128.2, 128.3, 128.4, 138.0, 138.6, 138.7, 138.8.
ESI-MS: m/z calcd for C36H37F3O6Na [M + Na]+: 645.25; found: 645.33.
HRMS (ESI): m/z calcd for C39H46O6Na [M + Na]+: 633.3187; found:
633.3201.
Isopropyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (21)24o
4-Pentenyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (25)24l
Compound 21 was prepared according to the general procedure and
isolated as a colorless oil (48 mg, 83% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 1.21 (3 H, d, J = 6.1 Hz), 1.27 (3 H, d, J =
6.2 Hz), 3.49–3.52 (2 H, m), 3.57 (2 H, d, J = 6.2 Hz), 3.77–3.80 (1 H,
m), 3.87 (1 H, d, J = 2.4 Hz), 3.96–4.01 (1 H, m), 4.40 (1 H, d, J = 11.9
Hz), 4.41 (1 H, d, J = 7.6 Hz), 4.44 (1 H, d, J = 11.8 Hz), 4.61 (1 H, d, J =
11.7 Hz), 4.69 (1 H, d, J = 11.9 Hz), 4.74 (1 H, d, J = 10.8 Hz), 4.75 (1 H,
d, J = 11.8 Hz), 4.92 (1 H, d, J = 11.7 Hz), 4.93 (1 H, d, J = 10.8 Hz), 7.23–
7.37 (20 H, m).
Compound 25 was prepared according to the general procedure and
isolated as a colorless oil (56 mg, 92% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 1.71–1.75 (2 H, m), 2.13–2.16 (2 H, m),
3.49–3.52 (3 H, m), 3.56–3.58 (2 H, m), 3.79–3.82 (1 H, m), 3.88 (1 H,
d, J = 2.5 Hz), 3.92–3.94 (1 H, m), 4.34 (1 H, d, J = 7.7 Hz), 4.39 (1 H, d,
J = 11.8 Hz), 4.44 (1 H, d, J = 11.8 Hz), 4.63 (1 H, d, J = 11.7 Hz), 4.70 (1
H, d, J = 11.9 Hz), 4.74 (1 H, d, J = 11.8 Hz), 4.76 (1 H, d, J = 10.9 Hz),
4.91 (1 H, d, J = 11.1 Hz), 4.94 (1 H, d, J = 11.6 Hz), 4.97–5.01 (1 H, m),
5.77–5.81 (1 H, m), 7.25–7.36 (20 H, m).
ESI-MS: m/z calcd for C37H42O6Na [M + Na]+: 605.30; found: 605.33.
ESI-MS: m/z calcd for C39H44O6Na [M + Na]+: 631.31; found: 631.33.
Allyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (22)24q
Hexyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (26)
Compound 22 was prepared according to the general procedure and
isolated as a colorless oil (53 mg, 92% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 3.49–3.52 (2 H, m), 3.57 (2 H, d, J = 6.2
Hz), 3.77–3.80 (1 H, m), 3.87 (1 H, d, J = 2.4 Hz), 3.96–4.01 (1 H, m),
4.39 (1 H, d, J = 8.0 Hz), 4.40 (1 H, d, J = 10.1 Hz), 4.41 (1 H, d, J = 11.5
Hz), 4.43 (1 H, d, J = 11.8 Hz), 4.59 (1 H, d, J = 11.7 Hz), 4.68 (1 H, d, J =
11.9 Hz), 4.71 (1 H, d, J = 12.8 Hz), 4.74 (1 H, d, J = 10.9 Hz), 4.91 (1 H,
d, J = 10.8 Hz), 4.93 (1 H, d, J = 11.7 Hz), 5.14–5.16 (1 H, m), 5.28–5.31
(1 H, m), 5.88–5.96 (1 H, m), 7.23–7.35 (20 H, m).
Compound 26 was prepared according to the general procedure and
isolated as a colorless oil (54 mg, 87% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 0.88 (3 H, t, J = 7.0 Hz), 1.26–1.28 (4 H,
m), 1.34–1.38 (2 H, m), 1.60–1.64 (2 H, m), 3.48–3.53 (3 H, m), 3.58–
3.60 (2 H, m), 3.80–3.83 (1 H, m), 3.89 (1 H, d, J = 2.5 Hz), 3.91–3.94 (1
H, m), 4.35 (1 H, d, J = 7.6 Hz), 4.41 (1 H, d, J = 11.9 Hz), 4.46 (1 H, d, J =
11.7 Hz), 4.62 (1 H, d, J = 11.7 Hz), 4.71 (1 H, d, J = 11.8 Hz), 4.74 (1 H,
d, J = 12.4 Hz), 4.76 (1 H, d, J = 11.4 Hz), 4.93 (1 H, d, J = 10.9 Hz), 4.95
(1 H, d, J = 11.8 Hz), 7.26–7.36 (20 H, m).
ESI-MS: m/z calcd for C37H40O6Na [M + Na]+: 603.28; found: 603.25.
13C NMR (125 MHz, CDCl3):  = 14.0, 22.6, 25.9, 29.7, 31.7, 68.9, 70.0,
73.1, 73.4, 73.5, 73.6, 74.5, 75.2, 76.8, 79.6, 82.3, 104.0, 127.5, 127.8,
127.9, 128.1, 128.2, 128.3, 128.4, 138.0, 138.6, 138.7, 138.8.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

J
H. Guo et al.
Paper
Synthesis
HRMS (ESI): m/z calcd for C40H48O6Na [M + Na]+: 647.3343; found:
647.3338.
ESI-MS: m/z calcd for [M + Na]+: 647.35; found: 647.33.
ESI-MS: m/z calcd for C44H56O6Na [M + Na]+: 703.41; found: 703.42.
Propargyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (31)15g
Compound 31 was prepared according to the general procedure and
isolated as a colorless oil (6.5 g, 95% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 2.46 (1 H, t, J = 2.3 Hz), 3.49–3.63 (4 H,
m), 3.89–3.93 (1 H, m), 4.23–4.32 (2 H, m), 4.63 (1 H, d, J = 11.7 Hz),
4.71 (1 H, d, J = 12.0 Hz), 4.75 (1 H, d, J = 11.6 Hz), 4.77 (1 H, d, J = 11.9
Hz), 4.86 (1 H, d, J = 10.9 Hz), 4.94 (1 H, d, J = 10.9 Hz), 5.00 (1 H, d, J =
3.6 Hz), 7.26–7.39 (15 H, m).
Cyclohexyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (27)19c
Compound 27 was prepared according to the general procedure and
isolated as a colorless oil (51 mg, 81% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 0.88–0.93 (3 H, m), 1.37–1.55 (3 H, m),
1.68–1.76 (2 H, m), 1.94–2.01 (2 H, m), 3.52–3.54 (2 H, m), 3.60–3.61
(2 H, m), 3.68–3.72 (1 H, m), 3.82–3.85 (1 H, m), 3.88–3.92 (1 H, m),
4.43 (1 H, d, J = 11.8 Hz), 4.47 (1 H, d, J = 10.0 Hz), 4.49 (1 H, d, J = 7.5
Hz), 4.65 (1 H, d, J = 11.7 Hz), 4.71 (1 H, d, J = 11.9 Hz), 4.74 (1 H, d, J =
12.5 Hz), 4.78 (1 H, d, J = 11.6 Hz), 4.96 (1 H, d, J = 11.9 Hz), 4.99 (1 H,
d, J = 10.8 Hz), 7.26–7.40 (20 H, m).
ESI-MS: m/z calcd for C29H30O5Na [M + Na]+: 481.21; found: 481.25.
Benzyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (32)24f
Compound 32 was prepared according to the general procedure and
isolated as a white solid (48 mg, 94% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 73–74 °C.
1H NMR (500 MHz, CDCl3):  = 3.21–3.26 (1 H, m), 3.43–3.46 (1 H, m),
3.57–3.65 (2 H, m), 3.96 (1 H, dd, J = 5.1 Hz, J = 11.6 Hz), 4.48 (1 H, d,
J = 7.6 Hz), 4.63 (1 H, d, J = 11.6 Hz), 4.65 (1 H, d, J = 11.9 Hz), 4.72 (1 H,
d, J = 10.6 Hz), 4.74 (1 H, d, J = 12.0 Hz), 4.84 (1 H, d, J = 11.0 Hz), 4.86
(1 H, d, J = 11.0 Hz), 4.87 (1 H, d, J = 11.1 Hz), 4.91 (1 H, d, J = 10.8 Hz),
7.26–7.38 (20 H, m).
ESI-MS: m/z calcd for C40H46O6Na [M + Na]+: 645.33; found: 645.33.
Menthyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (28)16
Compound 28 was prepared according to the general procedure and
isolated as a colorless oil (54 mg, 80% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 0.78 (3 H, d, J = 6.9 Hz), 0.90 (6 H, d, J =
6.6 Hz), 0.92–0.99 (2 H, m), 1.29–1.39 (3 H, m), 1.66 (2 H, d, J = 11.9
Hz), 2.12–2.40 (2 H, m), 3.44–3.48 (1 H, m), 3.52–3.58 (4 H, m), 3.77–
3.80 (1 H, m), 3.88 (1 H, d, J = 2.5 Hz), 4.41 (1 H, d, J = 11.4 Hz), 4.43 (1
H, d, J = 7.5 Hz), 4.46 (1 H, d, J = 11.7 Hz), 4.65 (1 H, d, J = 11.8 Hz), 4.72
(1 H, d, J = 12.1 Hz), 4.75 (1 H, d, J = 12.5 Hz), 4.79 (1 H, d, J = 11.8 Hz),
4.95 (1 H, d, J = 10.9 Hz), 4.97 (1 H, d, J = 11.6 Hz), 7.26–7.40 (20 H, m).
ESI-MS: m/z calcd for C33H34O5Na [M + Na]+: 533.24; found: 533.25.
2-Chloroethyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (33)
Compound 33 was prepared according to the general procedure and
isolated as a colorless oil (43 mg, 89% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
ESI-MS: m/z calcd for C44H54O6Na [M + Na]+: 701.39; found: 701.42.
1H NMR (500 MHz, CDCl3):  = 3.19–3.23 (1 H, m), 3.38–3.41 (1 H, m),
3.56–3.64 (1 H, m), 3.66–3.68 (2 H, m), 3.78–3.83 (1 H, m), 3.92 (1 H,
dd, J = 4.6 Hz, J = 11.5 Hz), 4.08–4.12 (1 H, m), 4.39 (1 H, d, J = 7.6 Hz),
4.63 (1 H, d, J = 11.6 Hz), 4.72 (1 H, d, J = 10.8 Hz), 4.73 (1 H, d, J = 11.6
Hz), 4.84 (1 H, d, J = 11.5 Hz), 4.88 (1 H, d, J = 11.0 Hz), 4.96 (1 H, d, J =
10.9 Hz), 7.26–7.37 (15 H, m).
13C NMR (125 MHz, CDCl3):  = 42.8, 63.9, 69.8, 73.4, 74.9, 75.6, 76.8,
77.7, 81.7, 83.6, 104.3, 127.6, 127.7, 127.8, 127.9, 128.0, 128.2, 128.3,
128.5, 138.0, 138.4, 138.6.
Isoctyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (29)
Compound 29 was prepared according to the general procedure and
isolated as a colorless oil (52 mg, 80% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 0.86–0.88 (6 H, m), 1.20–1.40 (9 H, m),
1.55–1.57 (4 H, m), 3.30–3.36 (1 H, m), 3.50–3.53 (2 H, m), 3.58–3.60
(2 H, m), 3.80–3.83 (1 H, m), 3.85–3.88 (2 H, m), 4.32 (1 H, d, J = 7.7
Hz), 4.41 (1 H, d, J = 11.8 Hz), 4.45 (1 H, d, J = 11.8 Hz), 4.62 (1 H, d, J =
11.7 Hz), 4.70 (1 H, d, J = 11.9 Hz), 4.73 (1 H, d, J = 12.5 Hz), 4.75 (1 H,
d, J = 11.0 Hz), 4.93 (2 H, d, J = 11.4 Hz), 7.26–7.39 (20 H, m).
HRMS (ESI): m/z calcd for C28H31ClO5Na [M + Na]+: 505.1752; found:
505.1757.
13C NMR (125 MHz, CDCl3):  = 10.9, 11.1, 14.1, 22.9, 23.0, 23.6, 29.0,
29.1, 29.7, 30.3, 30.5, 39.6, 39.7, 68.9, 72.4, 72.5, 73.0, 73.4, 73.5, 74.4,
75.1, 76.8, 79.5, 82.2, 104.2, 127.4, 127.5, 127.7, 127.8, 128.0, 128.1,
128.2, 128.3, 128.4, 138.0, 138.5, 138.6, 138.7.
Allyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (34)24d
Compound 34 was prepared according to the general procedure and
isolated as a colorless oil (43 mg, 93% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
HRMS (ESI): m/z calcd for C42H52O6Na [M + Na]+: 675.3656; found:
675.3644.
1H NMR (500 MHz, CDCl3):  = 3.21–3.25 (1 H, m), 3.42–3.45 (1 H, m),
3.59–3.67 (2 H, m), 3.95 (1 H, dd, J = 4.8 Hz, J = 11.5 Hz), 4.14–4.17 (1
H, m), 4.37–4.41 (1 H, m), 4.43 (1 H, d, J = 7.6 Hz), 4.65 (1 H, d, J = 11.7
Hz), 4.72 (1 H, d, J = 10.8 Hz), 4.76 (1 H, d, J = 11.6 Hz), 4.87 (1 H, d, J =
11.0 Hz), 4.91 (1 H, d, J = 11.0 Hz), 4.95 (1 H, d, J = 10.9 Hz), 5.23 (1 H,
d, J = 10.4 Hz), 5.36 (1 H, d, J = 15.9 Hz), 5.93–6.01 (1 H, m), 7.26–7.39
(15 H, m).
Decyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (30)24o
Compound 30 was prepared according to the general procedure and
isolated as a colorless oil (58 mg, 85% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 0.89 (3 H, t, J = 6.7 Hz), 1.27–1.30 (15
H, m), 1.63–1.67 (3 H, m), 3.49–3.55 (3 H, m), 3.60–3.61 (2 H, m),
3.81–3.85 (1 H, m), 3.90 (1 H, d, J = 2.5 Hz), 3.93–3.96 (1 H, m), 4.37 (1
H, d, J = 7.7 Hz), 4.43 (1 H, d, J = 11.8 Hz), 4.47 (1 H, d, J = 11.8 Hz), 4.63
(1 H, d, J = 11.7 Hz), 4.72 (1 H, d, J = 11.9 Hz), 4.75 (1 H, d, J = 12.9 Hz),
4.77 (1 H, d, J = 11.4 Hz), 4.94 (1 H, d, J = 10.9 Hz), 4.95 (1 H, d, J = 11.8
Hz), 7.26–7.39 (20 H, m).
ESI-MS: m/z calcd for C29H32O5Na [M + Na]+: 483.22; found: 483.17.
Butyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (35)
Compound 35 was prepared according to the general procedure and
isolated as a colorless oil (43 mg, 90% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

K
H. Guo et al.
Paper
Synthesis
1H NMR (500 MHz, CDCl3):  = 0.97 (3 H, t, J = 7.4 Hz), 1.45–1.48 (2 H,
m), 1.63–1.67 (2 H, m), 3.22–3.26 (1 H, m), 3.39–3.42 (1 H, m), 3.57–
3.67 (3 H, m), 3.92–3.99 (2 H, m), 4.38 (1 H, d, J = 7.7 Hz), 4.67 (1 H, d,
J = 11.6 Hz), 4.76 (1 H, d, J = 10.8 Hz), 4.78 (1 H, d, J = 11.6 Hz), 4.90 (1
H, d, J = 11.5 Hz), 4.92 (1 H, d, J = 11.0 Hz), 4.96 (1 H, d, J = 10.9 Hz),
7.26–7.37 (15 H, m).
13C NMR (125 MHz, CDCl3):  = 13.8, 19.3, 29.7, 31.9, 63.9, 69.7, 73.4,
74.9, 75.6, 76.8, 77.9, 82.0, 83.8, 104.2, 127.5, 127.6, 127.8, 127.9,
128.0, 128.3, 128.4, 138.2, 138.5, 138.7.
13C NMR (125 MHz, CDCl3):  = 15.7, 21.0, 22.2, 23.2, 25.4, 29.7, 31.4,
34.4, 40.8, 48.0, 63.9, 73.2, 74.9, 75.6, 76.8, 77.7, 78.0, 81.8, 84.1,
101.2, 127.5, 127.6, 127.8, 127.9, 128.2, 128.3, 128.4, 138.3, 138.6,
138.8.
HRMS (ESI): m/z calcd for C36H46O5Na [M + Na]+: 581.3237; found:
581.3225.
Isooctyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (39)
Compound 39 was prepared according to the general procedure and
isolated as a colorless oil (43 mg, 81% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
HRMS (ESI): m/z calcd for C30H36O5Na [M + Na]+: 499.2455; found:
499.2462.
1H NMR (500 MHz, CDCl3):  = 0.90–0.93 (6 H, m), 1.28–1.42 (10 H,
m), 1.56–1.58 (2 H, m), 3.20–3.24 (1 H, m), 3.37–3.43 (2 H, m), 3.58–
3.66 (2 H, m), 3.81–3.86 (1 H, m), 3.95 (1 H, dd, J = 5.0 Hz, J = 11.5 Hz),
4.34 (1 H, d, J = 7.7 Hz), 4.64 (1 H, d, J = 11.5 Hz), 4.73 (1 H, d, J = 11.0
Hz), 4.75 (1 H, d, J = 11.5 Hz), 4.87 (1 H, d, J = 11.0 Hz), 4.90 (1 H, d, J =
11.0 Hz), 4.94 (1 H, d, J = 11.0 Hz), 7.26–7.39 (15 H, m).
13C NMR (125 MHz, CDCl3):  = 31.5, 35.2, 68.8, 73.4, 74.9, 75.0, 75.7,
76.7, 77.7, 82.0, 84.7, 101.8, 116.4, 126.3, 127.5, 127.6, 127.7, 127.8,
127.9, 128.2, 128.3, 128.4, 138.0, 138.1, 138.2, 138.5, 145.3, 155.1.
Pentyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (36)
Compound 36 was prepared according to the general procedure and
isolated as a colorless oil (44 mg, 90% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 0.89 (3 H, t, J = 6.9 Hz), 1.29–1.37 (4 H,
m), 1.63–1.65 (2 H, m), 3.18–3.22 (1 H, m), 3.35–3.38 (1 H, m), 3.51–
3.62 (3 H, m), 3.87–3.94 (2 H, m), 4.33 (1 H, d, J = 7.7 Hz), 4.62 (1 H, d,
J = 11.6 Hz), 4.72 (1 H, d, J = 10.8 Hz), 4.73 (1 H, d, J = 11.6 Hz), 4.85 (1
H, d, J = 11.0 Hz), 4.88 (1 H, d, J = 11.0 Hz), 4.92 (1 H, d, J = 10.9 Hz),
7.24–7.36 (15 H, m).
13C NMR (125 MHz, CDCl3):  = 14.0, 22.5, 28.3, 29.5, 29.7, 63.9, 70.1,
73.4, 74.9, 75.6, 77.9, 82.0, 83.8, 104.2, 127.5, 127.6, 127.8, 127.9,
128.0, 128.3, 128.4, 138.2, 138.5, 138.7.
HRMS (ESI): m/z calcd for C31H38O5Na [M + Na]+: 513.2611; found:
513.2615.
HRMS (ESI): m/z calcd for C34H44O5Na [M + Na]+: 555.3081; found:
555.3086.
Phenyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (40)24c
Compound 40 was prepared according to the general procedure and
isolated as a white solid (54 mg, 88% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 77–78 °C.
1H NMR (500 MHz, CDCl3):  = 3.64–3.73 (3 H, m), 3.76–3.83 (3 H, m),
4.53 (1 H, d, J = 12.0 Hz), 4.55 (1 H, d, J = 12.0 Hz), 4.57 (1 H, d, J = 10.7
Hz), 4.84 (1 H, d, J = 11.2 Hz), 4.86 (2 H, d, J = 12.8 Hz), 4.97 (1 H, d, J =
10.9 Hz), 5.03 (1 H, d, J = 7.0 Hz), 5.07 (1 H, d, J = 11.0 Hz), 7.06–7.11 (3
H, m), 7.20 (2 H, d, J = 6.0 Hz), 7.27–7.37 (20 H, m).
Cyclohexyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (37)
Compound 37 was prepared according to the general procedure and
isolated as a colorless oil (41 mg, 82% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 1.26–1.34 (3 H, m), 1.41–1.56 (3 H, m),
1.75–1.76 (2 H, m), 1.96–2.01 (2 H, m), 3.19–3.23 (1 H, m), 3.37–3.40
(1 H, m), 3.56–3.70 (3 H, m), 3.92 (1 H, dd, J = 5.0 Hz, J = 11.5 Hz), 4.47
(1 H, d, J = 7.7 Hz), 4.64 (1 H, d, J = 11.6 Hz), 4.73 (1 H, d, J = 12.8 Hz),
4.75 (1 H, d, J = 12.0 Hz), 4.86 (1 H, d, J = 11.1 Hz), 4.89 (1 H, d, J = 10.9
Hz), 4.98 (1 H, d, J = 10.9 Hz), 7.28–7.38 (15 H, m).
13C NMR (125 MHz, CDCl3):  = 23.9, 24.0, 25.6, 32.0, 33.8, 63.9, 73.4,
74.9, 75.6, 76.8, 77.6, 77.9, 82.0, 84.0, 102.4, 127.5, 127.6, 127.8,
127.9, 128.0, 128.1, 128.3, 128.4, 138.2, 138.5, 138.7.
ESI-MS: m/z calcd for C40H40O6Na [M + Na]+: 639.28; found: 639.33.
4-Methylphenyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside
(41)24j
Compound 41 was prepared according to the general procedure and
isolated as a white solid (56 mg, 89% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 82–83 °C.
1H NMR (500 MHz, CDCl3):  = 2.33 (3 H, s), 3.59–3.62 (1 H, m), 3.69–
3.75 (4 H, m), 3.79 (1 H, d, J = 10.8 Hz), 4.54 (1 H, d, J = 12.1 Hz), 4.58
(1 H, d, J = 12.3 Hz), 4.61 (1 H, d, J = 12.5 Hz), 4.81 (1 H, d, J = 10.5 Hz),
4.83 (1 H, d, J = 11.0 Hz), 4.86 (1 H, d, J = 11.1 Hz), 4.95 (1 H, d, J = 10.8
Hz), 4.98 (1 H, d, J = 7.3 Hz), 5.06 (1 H, d, J = 10.9 Hz), 7.00 (2 H, d, J =
8.3 Hz), 7.10 (2 H, d, J = 8.2 Hz), 7.20 (2 H, d, J = 7.1 Hz), 7.27–7.37 (18
H, m).
HRMS (ESI): m/z calcd for C32H38O5Na [M + Na]+: 525.2611; found:
525.2613.
Menthyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (38)
Compound 38 was prepared according to the general procedure and
isolated as a colorless oil (45 mg, 81% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
ESI-MS: m/z calcd for C41H42O6Na [M + Na]+: 653.30; found: 653.33.
1H NMR (500 MHz, CDCl3):  = 0.81 (3 H, d, J = 6.9 Hz), 0.93 (6 H, d, J =
6.2 Hz), 0.94–0.98 (2 H, m), 1.24–1.39 (3 H, m), 1.68 (2 H, d, J = 11.9
Hz), 2.15–2.40 (2 H, m), 3.20–3.24 (1 H, m), 3.35–3.39 (1 H, m), 3.45–
3.50 (1 H, m), 3.58–3.62 (1 H, m), 3.64–3.68 (1 H, m), 3.96 (1 H, dd, J =
5.0 Hz, J = 11.5 Hz), 4.47 (1 H, d, J = 7.7 Hz), 4.65 (1 H, d, J = 11.7 Hz),
4.72 (1 H, d, J = 12.4 Hz), 4.75 (1 H, d, J = 12.0 Hz), 4.86 (1 H, d, J = 11.5
Hz), 4.90 (1 H, d, J = 10.9 Hz), 4.95 (1 H, d, J = 10.9 Hz), 7.24–7.36 (15
H, m).
4-tert-Butylphenyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside
(42)
Compound 42 was prepared according to the general procedure and
isolated as a colorless oil (61 mg, 91% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1)
1H NMR (500 MHz, CDCl3):  = 1.30 (9 H, s), 3.60–3.62 (1 H, m), 3.66–
3.71 (2 H, m), 3.72–3.74 (2 H, m), 3.79 (1 H, d, J = 10.8 Hz), 4.53 (1 H,
d, J = 12.0 Hz), 4.56 (1 H, d, J = 11.5 Hz), 4.59 (1 H, d, J = 12.2 Hz), 4.81
(1 H, d, J = 10.5 Hz), 4.83 (1 H, d, J = 11.0 Hz), 4.85 (1 H, d, J = 10.8 Hz),
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

L
H. Guo et al.
Paper
Synthesis
4.95 (1 H, d, J = 11.0 Hz), 4.98 (1 H, d, J = 7.3 Hz), 5.05 (1 H, d, J = 11.0
Hz), 7.02 (2 H, d, J = 8.8 Hz), 7.19 (2 H, d, J = 8.0 Hz), 7.28–7.36 (20 H,
4-Chlorophenyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside
(46)24a
m).
Compound 46 was prepared according to the general procedure and
isolated as a colorless oil (56 mg, 86% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 3.59–3.61 (1 H, m), 3.65–3.68 (2 H, m),
3.72–3.74 (2 H, m), 3.76–3.79 (1 H, m), 4.51 (1 H, d, J = 12.0 Hz), 4.56
(1 H, d, J = 10.7 Hz), 4.58 (1 H, d, J = 12.0 Hz), 4.80 (1 H, d, J = 11.0 Hz),
4.82 (1 H, d, J = 11.0 Hz), 4.84 (1 H, d, J = 10.5 Hz), 4.93 (1 H, d, J = 10.6
Hz), 4.94 (1 H, d, J = 7.4 Hz), 4.99 (1 H, d, J = 11.0 Hz), 6.99 (2 H, d, J =
8.7 Hz), 7.18 (2 H, d, J = 7.5 Hz), 7.22 (2 H, d, J = 8.8 Hz), 7.25–7.31 (17
H, m).
13C NMR (125 MHz, CDCl3):  = 10.5, 10.7, 13.6, 22.5, 22.6, 23.3, 23.4,
28.6, 28.8, 30.0, 30.1, 39.3, 63.5, 71.9, 72.0, 72.9, 74.4, 75.1, 76.3, 76.6,
76.8, 77.5, 81.5, 83.4, 103.9, 104.0, 127.0, 127.1, 127.3, 127.4, 127.5,
127.6, 127.8, 128.0, 137.8, 138.1, 138.3.
HRMS (ESI): m/z calcd for C44H48O6Na [M + Na]+: 695.3343; found:
695.3341.
2-Methylphenyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside
(43)24j
ESI-MS: m/z calcd for C40H39ClO6Na [M + Na]+: 673.24; found: 673.17.
Compound 43 was prepared according to the general procedure and
isolated as a colorless oil (50 mg, 80% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 2.31 (3 H, s), 3.60–3.63 (1 H, m), 3.68–
3.72 (2 H, m), 3.75–3.82 (3 H, m), 4.53 (1 H, d, J = 12.0 Hz), 4.59 (2 H,
d, J = 11.2 Hz), 4.84 (1 H, d, J = 10.5 Hz), 4.85 (1 H, d, J = 11.0 Hz), 4.86
(1 H, d, J = 10.0 Hz), 4.95 (1 H, d, J = 11.0 Hz), 5.03 (1 H, d, J = 7.0 Hz),
5.08 (1 H, d, J = 10.5 Hz), 6.95 (1 H, t, J = 7.0 Hz), 7.16 (1 H, d, J = 7.5
Hz), 7.17–7.21 (4 H, m), 7.26–7.34 (20 H, m).
4-Bromophenyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside
(47)24e
Compound 47 was prepared according to the general procedure and
isolated as a colorless oil (60 mg, 86% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 3.62–3.64 (1 H, m), 3.67–3.71 (2 H, m),
3.74–3.76 (2 H, m), 3.78–3.81 (1 H, m), 4.54 (1 H, d, J = 12.0 Hz), 4.58
(1 H, d, J = 10.5 Hz), 4.60 (1 H, d, J = 11.9 Hz), 4.83 (1 H, d, J = 10.9 Hz),
4.85 (1 H, d, J = 10.6 Hz), 4.87 (1 H, d, J = 10.4 Hz), 4.95 (1 H, d, J = 10.9
Hz), 4.97 (1 H, d, J = 6.8 Hz), 5.01 (1 H, d, J = 10.9 Hz), 6.96 (2 H, d, J =
9.2 Hz), 7.21 (2 H, d, J = 6.9 Hz), 7.27–7.33 (18 H, m), 7.39 (2 H, d, J =
8.7 Hz).
ESI-MS: m/z calcd for C41H42O6Na [M + Na]+: 653.30; found: 653.25.
2,4-Dimethylphenyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside
(44)
Compound 44 was prepared according to the general procedure and
isolated as a white solid (52 mg, 81% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 93–94 °C.
1H NMR (500 MHz, CDCl3):  = 2.28 (6 H, s), 3.59–3.60 (1 H, m), 3.69–
3.72 (2 H, m), 3.74–3.78 (3 H, m), 4.53 (1 H, d, J = 11.9 Hz), 4.58 (1 H,
d, J = 12.3 Hz), 4.60 (1 H, d, J = 10.5 Hz), 4.82 (1 H, d, J = 10.5 Hz), 4.84
(1 H, d, J = 11.0 Hz), 4.86 (1 H, d, J = 10.1Hz), 4.95 (1 H, d, J = 11.8 Hz),
4.97 (1 H, d, J = 7.2 Hz), 5.07 (1 H, d, J = 10.8 Hz), 6.92 (1 H, d, J = 8.2
Hz), 6.97 (2 H, d, J = 8.1 Hz), 7.20 (2 H, d, J = 7.1 Hz), 7.27–7.37 (18 H,
m).
13C NMR (125 MHz, CDCl3):  = 16.6, 20.5, 29.7, 68.8, 73.5, 75.0, 75.1,
75.8, 76.7, 77.0, 77.3, 77.8, 82.1, 84.8, 101.7, 115.2, 127.2, 127.4,
127.5, 127.6, 127.7, 127.8, 127.9, 128.0, 128.2, 128.3, 128.4, 131.5,
131.7, 138.1, 138.2, 138.5, 153.4.
ESI-MS: m/z calcd for C40H39BrO6Na [M + Na]+: 719.19; found: 719.17.
-Naphthyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (48)24e
Compound 48 was prepared according to the general procedure and
isolated as a colorless oil (58 mg, 87% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 3.69–3.84 (5 H, m), 3.96–3.99 (1 H, m),
4.53 (1 H, d, J = 11.8 Hz), 4.58 (1 H, d, J = 12.8 Hz), 4.61 (1 H, d, J = 11.1
Hz), 4.86 (1 H, d, J = 10.9 Hz), 4.88 (1 H, d, J = 10.4 Hz), 4.95 (1 H, d, J =
10.5 Hz), 4.99 (1 H, d, J = 10.9 Hz), 5.18 (1 H, d, J = 10.6 Hz), 5.24 (1 H,
d, J = 7.3 Hz), 7.15 (1 H, d, J = 7.2 Hz), 7.21–7.37 (23 H, m), 7.44–7.50
(2 H, m), 7.56 (1 H, d, J = 8.2 Hz), 7.83 (1 H, d, J = 7.9 Hz), 8.31 (1 H, d,
J = 8.1 Hz).
ESI-MS: m/z calcd for C44H42O6Na [M + Na]+: 689.30; found: 689.17.
HRMS (ESI): m/z calcd for C42H44O6Na [M + Na]+: 667.3030; found:
667.3037.
-Naphthyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside (49)24e
2,6-Dimethylphenyl 2,3,4,6-Tetra-O-benzyl--D-glucopyranoside
Compound 49 was prepared according to the general procedure and
isolated as a white solid (59 mg, 88% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 107–108 °C.
1H NMR (500 MHz, CDCl3):  = 3.70–3.74 (3 H, m), 3.78–3.85 (3 H, m),
4.54 (1 H, d, J = 12.0 Hz), 4.58 (1 H, d, J = 10.5 Hz), 4.60 (1 H, d, J = 11.9
Hz), 4.84 (1 H, d, J = 12.9 Hz), 4.87 (1 H, d, J = 12.2 Hz), 4.97 (1 H, d, J =
10.7 Hz), 4.98 (1 H, d, J = 10.9 Hz), 5.10 (1 H, d, J = 10.5 Hz), 5.16 (1 H,
d, J = 6.3 Hz), 7.21–7.45 (24 H, m), 7.66 (1 H, d, J = 8.1 Hz), 7.77–7.80
(2 H, m).
(45)24e
Compound 45 was prepared according to the general procedure and
isolated as a white solid (50 mg, 78% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 135–136 °C.
1H NMR (500 MHz, CDCl3):  = 2.38 (6 H, s), 3.30–3.32 (1 H, m), 3.63–
3.69 (2 H, m), 3.71–3.78 (3 H, m), 4.46 (1 H, d, J = 12.0 Hz), 4.53 (1 H,
d, J = 12.0 Hz), 4.61 (1 H, d, J = 11.0 Hz), 4.79 (1 H, d, J = 7.5 Hz), 4.84 (1
H, d, J = 11.0 Hz), 4.86 (1 H, d, J = 10.5 Hz), 4.87 (1 H, d, J = 11.0 Hz),
4.99 (1 H, d, J = 11.0 Hz), 5.15 (1 H, d, J = 11.0 Hz), 6.99–7.04 (3 H, m),
7.20 (2 H, d, J = 7.5 Hz), 7.25–7.32 (17 H, m), 7.38 (2 H, d, J = 6.5 Hz).
ESI-MS: m/z calcd for C44H42O6Na [M + Na]+: 689.30; found: 689.25.
ESI-MS: m/z calcd for C42H44O6Na [M + Na]+: 667.31; found: 667.25.
Phenyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (50)24p
Compound 50 was prepared according to the general procedure and
isolated as a colorless oil (54 mg, 88% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

M
H. Guo et al.
Paper
Synthesis
1H NMR (500 MHz, CDCl3):  = 3.63–3.69 (3 H, m), 3.70–3.73 (1 H, m),
3.98 (1 H, d, J = 2.5 Hz), 4.14–4.18 (1 H, m), 4.43 (1 H, d, J = 11.6 Hz),
4.48 (1 H, d, J = 11.6 Hz), 4.68 (1 H, d, J = 11.8 Hz), 4.77 (1 H, d, J = 11.8
Hz), 4.82 (1 H, d, J = 11.8 Hz), 4.89 (1 H, d, J = 10.8 Hz), 5.01 (1 H, d, J =
11.0 Hz), 5.02 (1 H, d, J = 7.8 Hz), 5.04 (1 H, d, J = 10.9 Hz), 7.05–7.07 (1
H, m), 7.10 (2 H, d, J = 8.5 Hz), 7.26–7.41 (22 H, m).
1H NMR (500 MHz, CDCl3):  = 2.25 (6 H, s), 3.62–3.67 (4 H, m), 3.95
(1 H, d, J = 2.5 Hz), 4.11–4.15 (1 H, m), 4.40 (1 H, d, J = 11.8 Hz), 4.45 (1
H, d, J = 11.5 Hz), 4.65 (1 H, d, J = 11.7 Hz), 4.75 (1 H, d, J = 11.8 Hz),
4.77 (1 H, d, J = 11.8 Hz), 4.87 (1 H, d, J = 10.9 Hz), 4.94 (1 H, d, J = 8.3
Hz), 4.98 (1 H, d, J = 11.7 Hz), 5.02 (1 H, d, J = 10.7 Hz), 6.87 (1 H, d, J =
8.4 Hz), 6.92–6.94 (2 H, m), 7.25–7.35 (20 H, m).
ESI-MS: m/z calcd for C40H40O6Na [M + Na]+: 639.28; found: 639.25.
13C NMR (125 MHz, CDCl3):  = 16.5, 20.5, 68.9, 73.1, 73.4, 73.6, 73.7,
74.5, 75.4, 76.8, 77.0, 77.3, 79.3, 82.4, 101.8, 114.8, 127.0, 127.2,
127.5, 127.6, 127.7, 127.8, 128.0, 128.2, 128.3, 128.4, 131.3, 131.5,
137.9, 138.4, 138.5, 138.6, 153.5.
HRMS (ESI): m/z calcd for C42H44O6Na [M + Na]+: 667.3030; found:
667.3042.
4-Methylphenyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside
(51)24p
Compound 51 was prepared according to the general procedure and
isolated as a white solid (56 mg, 89% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 106–107 °C.
1H NMR (500 MHz, CDCl3):  = 2.29 (3 H, s), 3.59–3.66 (4 H, m), 3.94
(1 H, d, J = 2.5 Hz), 4.08–4.12 (1 H, m), 4.40 (1 H, d, J = 11.7 Hz), 4.44 (1
H, d, J = 11.6 Hz), 4.65 (1 H, d, J = 11.6 Hz), 4.74 (1 H, d, J = 11.8 Hz),
4.78 (1 H, d, J = 11.8 Hz), 4.85 (1 H, d, J = 10.9 Hz), 4.93 (1 H, d, J = 7.7
Hz), 4.98 (1 H, d, J = 11.7 Hz), 5.01 (1 H, d, J = 10.9 Hz), 6.97 (2 H, d, J =
8.5 Hz), 7.05 (2 H, d, J = 8.4 Hz), 7.25–7.38 (18 H, m).
2,6-Dimethylphenyl2,3,4,6-Tetra-O-benzyl--D-galactopyranoside
(55)24e
Compound 55 was prepared according to the general procedure and
isolated as a white solid (51 mg, 79% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 120–121 °C.
1H NMR (500 MHz, CDCl3):  = 2.35 (6 H, s), 3.41–3.44 (1 H, m), 3.48–
3.51 (1 H, m), 3.59–3.64 (2 H, m), 3.93 (1 H, d, J = 2.5 Hz), 4.09–4.12 (1
H, m), 4.32 (1 H, d, J = 11.7 Hz), 4.36 (1 H, d, J = 12.1 Hz), 4.64 (1 H, d,
J = 11.7 Hz), 4.75 (1 H, d, J = 10.6 Hz), 4.77 (1 H, d, J = 11.8 Hz), 4.79 (1
H, d, J = 11.7 Hz), 4.89 (1 H, d, J = 10.9 Hz), 4.99 (1 H, d, J = 11.8 Hz),
5.09 (1 H, d, J = 10.9 Hz), 6.87 (1 H, d, J = 8.4 Hz), 7.16–7.18 (4 H, m),
7.26–7.40 (18 H, m).
ESI-MS: m/z calcd for C41H42O6Na [M + Na]+: 653.30; found: 653.25.
4-tert-Butylphenyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside
(52)
Compound 52 was prepared according to the general procedure and
isolated as a white solid (60 mg, 89% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 111–112 °C.
ESI-MS: m/z calcd for C42H44O6Na [M + Na]+: 667.31; found: 667.25.
1H NMR (500 MHz, CDCl3):  = 1.31 (9 H, s), 3.61–3.68 (4 H, m), 3.96
(1 H, d, J = 2.5 Hz), 4.10–4.14 (1 H, m), 4.42 (1 H, d, J = 11.8 Hz), 4.47 (1
H, d, J = 11.8 Hz), 4.66 (1 H, d, J = 11.8 Hz), 4.76 (1 H, d, J = 11.8 Hz),
4.80 (1 H, d, J = 11.8 Hz), 4.86 (1 H, d, J = 10.9 Hz), 4.96 (1 H, d, J = 7.7
Hz), 4.99 (1 H, d, J = 11.7 Hz), 5.03 (1 H, d, J = 10.9 Hz), 7.02 (2 H, d, J =
8.8 Hz), 7.27–7.39 (22 H, m).
4-Chlorophenyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside
(56)24a
Compound 56 was prepared according to the general procedure and
isolated as a white solid (56 mg, 86% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 108–109 °C.
13C NMR (125 MHz, CDCl3):  = 31.5, 34.2, 68.9, 73.1, 73.5, 73.6, 73.8,
74.5, 75.3, 76.8, 77.0, 77.3, 79.3, 82.2, 102.3, 116.6, 126.2, 127.5,
127.6, 127.7, 127.8, 128.1, 128.2, 128.3, 128.4, 138.0, 138.5, 138.6,
138.7, 145.2, 155.2.
HRMS (ESI): m/z calcd for C44H48O6Na [M + Na]+: 695.3343; found:
695.3352.
1H NMR (500 MHz, CDCl3):  = 3.56–3.67 (4 H, m), 3.94 (1 H, d, J = 2.5
Hz), 4.08–4.12 (1 H, m), 4.40 (1 H, d, J = 11.8 Hz), 4.44 (1 H, d, J = 11.5
Hz), 4.65 (1 H, d, J = 11.6 Hz), 4.75 (1 H, d, J = 11.8 Hz), 4.78 (1 H, d, J =
11.9 Hz), 4.85 (1 H, d, J = 10.9 Hz), 4.92 (1 H, d, J = 7.7 Hz), 4.96 (1 H, d,
J = 10.4 Hz), 4.97 (1 H, d, J = 11.6 Hz), 6.98 (2 H, d, J = 8.8 Hz), 7.19 (2 H,
d, J = 8.8 Hz), 7.25–7.38 (20 H, m).
ESI-MS: m/z calcd for C40H39ClO6Na [M + Na]+: 673.24; found: 673.17.
2-Methylphenyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside
(53)24e
4-Bromophenyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside
(57)24e
Compound 53 was prepared according to the general procedure and
isolated as a white solid (50 mg, 80% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 98–99 °C.
1H NMR (500 MHz, CDCl3):  = 2.30 (3 H, s), 3.59–3.66 (4 H, m), 3.94
(1 H, d, J = 2.5 Hz), 4.08–4.12 (1 H, m), 4.41 (1 H, d, J = 11.5 Hz), 4.47 (1
H, d, J = 11.6 Hz), 4.66 (1 H, d, J = 11.7 Hz), 4.74 (1 H, d, J = 11.8 Hz),
4.78 (1 H, d, J = 11.8 Hz), 4.89 (1 H, d, J = 10.9 Hz), 4.99 (1 H, d, J = 10.8
Hz), 5.01 (1 H, d, J = 7.7 Hz), 5.03 (1 H, d, J = 11.2 Hz), 6.93 (1 H, t, J =
7.0 Hz), 7.05 (1 H, d, J = 8.2 Hz), 7.08–7.10 (1 H, m), 7.14 (1 H, d, J = 7.5
Hz), 7.27–7.38 (20 H, m).
Compound 57 was prepared according to the general procedure and
isolated as a colorless oil (60 mg, 86% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 3.56–3.67 (4 H, m), 3.93 (1 H, d, J = 2.5
Hz), 4.08–4.12 (1 H, m), 4.40 (1 H, d, J = 11.8 Hz), 4.44 (1 H, d, J = 11.5
Hz), 4.64 (1 H, d, J = 11.6 Hz), 4.74 (1 H, d, J = 11.8 Hz), 4.78 (1 H, d, J =
11.9 Hz), 4.85 (1 H, d, J = 10.9 Hz), 4.92 (1 H, d, J = 7.7 Hz), 4.95 (1 H, d,
J = 10.4 Hz), 4.97 (1 H, d, J = 11.5 Hz), 6.93 (2 H, d, J = 8.8 Hz), 7.24–
7.38 (22 H, m).
ESI-MS: m/z calcd for C41H42O6Na [M + Na]+: 653.30; found: 653.25.
ESI-MS: m/z calcd for C40H39BrO6Na [M + Na]+: 717.19; found: 717.08.
2,4-Dimethylphenyl2,3,4,6-Tetra-O-benzyl--D-galactopyranoside
-Naphthyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (58)24e
(54)
Compound 58 was prepared according to the general procedure and
isolated as a colorless oil (58 mg, 87% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
Compound 54 was prepared according to the general procedure and
isolated as a white solid (52 mg, 81% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 87–88 °C.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

N
H. Guo et al.
Paper
Synthesis
1H NMR (500 MHz, CDCl3):  = 3.64–3.71 (3 H, m), 3.74–3.77 (1 H, m),
3.99 (1 H, d, J = 2.5 Hz), 4.30–4.34 (1 H, m), 4.40 (1 H, d, J = 11.6 Hz),
4.46 (1 H, d, J = 11.6 Hz), 4.69 (1 H, d, J = 11.7 Hz), 4.78 (1 H, d, J = 11.8
Hz), 4.80 (1 H, d, J = 11.9 Hz), 4.94 (1 H, d, J = 10.6 Hz), 5.02 (1 H, d, J =
11.7 Hz), 5.12 (1 H, d, J = 10.5 Hz), 5.19 (1 H, d, J = 7.7 Hz), 7.12 (1 H, d,
J = 7.6 Hz), 7.25–7.52 (24 H, m), 7.80 (1 H, d, J = 8.3 Hz), 8.31 (1 H, d,
J = 8.4 Hz).
1H NMR (500 MHz, CDCl3):  = 1.35 (9 H, s), 3.34–3.39 (1 H, m), 3.70–
3.75 (3 H, m), 4.01–4.04 (1 H, m), 4.68 (1 H, d, J = 11.5 Hz), 4.79 (1 H,
d, J = 11.5 Hz), 4.84 (1 H, d, J = 11.0 Hz), 4.91 (1 H, d, J = 11.0 Hz), 4.94
(1 H, d, J = 11.0 Hz), 5.02 (1 H, d, J = 7.7 Hz), 5.04 (1 H, d, J = 11.0 Hz),
7.02 (2 H, d, J = 8.5 Hz), 7.26–7.39 (17 H, m).
13C NMR (125 MHz, CDCl3):  = 31.0, 33.8, 63.5, 72.9, 74.6, 75.2, 76.3,
76.6, 76.8, 77.3, 81.1, 83.2, 101.9, 116.1, 125.9, 127.2, 127.4, 127.5,
127.6, 127.7, 127.9, 128.0, 137.7, 137.9, 138.2, 145.1, 154.4.
ESI-MS: m/z calcd for C44H42O6Na [M + Na]+: 689.30; found: 689.25.
HRMS (ESI): m/z calcd for C36H40O5Na [M + Na]+: 575.2768; found:
575.2786.
-Naphthyl 2,3,4,6-Tetra-O-benzyl--D-galactopyranoside (59)24e
Compound 59 was prepared according to the general procedure and
isolated as a white solid (58 mg, 87% yield) after column chromatogra-
phy on silica gel (PE/EtOAc 40:1); mp 111–112 °C.
1H NMR (500 MHz, CDCl3):  = 3.62–3.71 (3 H, m), 3.75–3.78 (1 H, m),
3.97 (1 H, d, J = 2.5 Hz), 4.17–4.21 (1 H, m), 4.41 (1 H, d, J = 11.6 Hz),
4.48 (1 H, d, J = 11.6 Hz), 4.67 (1 H, d, J = 11.6 Hz), 4.77 (1 H, d, J = 11.8
Hz), 4.81 (1 H, d, J = 11.9 Hz), 4.89 (1 H, d, J = 10.9 Hz), 5.00 (1 H, d, J =
11.7 Hz), 5.05 (1 H, d, J = 10.9 Hz), 5.13 (1 H, d, J = 7.7 Hz), 7.26–7.42
(24 H, m), 7.64 (1 H, d, J = 8.3 Hz), 7.74–7.78 (2 H, m).
2-Methylphenyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (63)24e
Compound 63 was prepared according to the general procedure and
isolated as a colorless oil (41 mg, 80% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 2.28 (3 H, s), 3.32–3.35 (1 H, m), 3.69–
3.71 (3 H, m), 3.97–4.00 (1 H, m), 4.65 (1 H, d, J = 11.6 Hz), 4.76 (1 H,
d, J = 11.8 Hz), 4.83 (1 H, d, J = 10.9 Hz), 4.88 (1 H, d, J = 11.1 Hz), 4.90
(1 H, d, J = 11.1 Hz), 4.99 (1 H, d, J = 11.3 Hz), 5.02 (1 H, d, J = 7.8 Hz),
6.94–7.00 (2 H, m), 7.14–7.17 (2 H, m), 7.26–7.33 (15 H, m).
ESI-MS: m/z calcd for C44H42O6Na [M + Na]+: 689.30; found: 689.33.
ESI-MS: m/z calcd for C33H34O5Na [M + Na]+: 533.24; found: 533.17.
Phenyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (60)
Compound 60 was prepared according to the general procedure and
isolated as a colorless oil (44 mg, 89% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 3.33–3.37 (1 H, m), 3.67–3.72 (3 H, m),
3.99–4.02 (1 H, m), 4.65 (1 H, d, J = 11.5 Hz), 4.76 (1 H, d, J = 11.5 Hz),
4.82 (1 H, d, J = 11.0 Hz), 4.90 (1 H, d, J = 11.0 Hz), 4.93 (1 H, d, J = 11.0
Hz), 4.99 (1 H, d, J = 7.7 Hz), 5.01 (1 H, d, J = 11.0 Hz), 7.04–7.07 (3 H,
m), 7.26–7.35 (17 H, m).
13C NMR (125 MHz, CDCl3):  = 63.9, 73.4, 75.1, 75.6, 76.7, 77.0, 77.3,
77.7, 81.5, 83.6, 102.1, 116.8, 122.7, 127.6, 127.7, 127.8, 127.9, 128.2,
128.4, 128.5, 129.5, 138.0, 138.2, 138.5, 157.1.
HRMS (ESI): m/z calcd for C32H32O5Na [M + Na]+: 519.2142; found:
519.2155.
2,4-Dimethylphenyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (64)
Compound 64 was prepared according to the general procedure and
isolated as a colorless oil (44 mg, 84% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 2.29 (6 H, s), 3.32–3.36 (1 H, m), 3.71–
3.75 (3 H, m), 3.99–4.02 (1 H, m), 4.67 (1 H, d, J = 11.8 Hz), 4.78 (1 H,
d, J = 11.8 Hz), 4.86 (1 H, d, J = 10.9 Hz), 4.89 (1 H, d, J = 11.1 Hz), 4.93
(1 H, d, J = 11.1 Hz), 4.99 (1 H, d, J = 6.8 Hz), 5.03 (1 H, d, J = 10.9 Hz),
6.92–7.00 (3 H, m), 7.26–7.38 (15 H, m).
13C NMR (125 MHz, CDCl3):  = 16.4, 20.5, 63.9, 73.3, 75.2, 75.6, 76.7,
77.0, 77.3, 77.7, 81.6, 83.7, 102.0, 115.0, 127.1, 127.5, 127.6, 127.7,
127.8, 127.9, 128.0, 128.3, 128.5, 131.6, 131.8, 132.2, 138.0, 138.2,
138.6, 153.1.
HRMS (ESI): m/z calcd for C34H36O5Na [M + Na]+: 547.2455; found:
547.2471.
4-Methylphenyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (61)
Compound 61 was prepared according to the general procedure and
isolated as a colorless oil (45 mg, 88% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 2.33 (3 H, s), 3.33–3.37 (1 H, m), 3.68–
3.73 (3 H, m), 4.00–4.03 (1 H, m), 4.68 (1 H, d, J = 11.8 Hz), 4.78 (1 H,
d, J = 11.8 Hz), 4.84 (1 H, d, J = 11.0 Hz), 4.91 (1 H, d, J = 11.1 Hz), 4.93
(1 H, d, J = 11.1 Hz), 4.98 (1 H, d, J = 6.9 Hz), 5.02 (1 H, d, J = 10.9 Hz),
6.98 (2 H, d, J = 8.5 Hz), 7.13 (2 H, d, J = 8.3 Hz), 7.25–7.37 (15 H, m).
2,6-Dimethylphenyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (65)24e
Compound 65 was prepared according to the general procedure and
isolated as a colorless oil (41 mg, 78% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 2.33 (6 H, s), 3.06–3.11 (1 H, m), 3.65–
3.70 (3 H, m), 3.88–3.91 (1 H, m), 4.63 (1 H, d, J = 11.8 Hz), 4.73 (1 H,
d, J = 11.7 Hz), 4.76 (1 H, d, J = 6.9 Hz), 4.86 (1 H, d, J = 10.9 Hz), 4.90 (1
H, d, J = 11.2 Hz), 4.93 (1 H, d, J = 11.2 Hz), 5.10 (1 H, d, J = 11.0 Hz),
6.96–7.03 (3 H, m), 7.26–7.38 (15 H, m).
13C NMR (125 MHz, CDCl3):  = 20.6, 63.9, 73.4, 75.0, 75.6, 76.7, 77.0,
77.3, 77.7, 81.5, 83.6, 102.5, 116.9, 122.7, 127.6, 127.7, 127.8, 127.9,
128.2, 128.3, 128.4, 129.9, 132.2, 138.0, 138.2, 138.6, 155.0.
ESI-MS: m/z calcd for C34H36O5Na [M + Na]+: 547.26; found: 547.25.
HRMS (ESI): m/z calcd for C33H34O5Na [M + Na]+: 533.2298; found:
533.2316.
4-Chlorophenyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (66)
Compound 66 was prepared according to the general procedure and
isolated as a colorless oil (47 mg, 88% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 3.32–3.36 (1 H, m), 3.65–3.70 (3 H, m),
3.97–4.01 (1 H, m), 4.65 (1 H, d, J = 11.9 Hz), 4.76 (1 H, d, J = 11.6 Hz),
4.81 (1 H, d, J = 10.9 Hz), 4.87 (1 H, d, J = 10.9 Hz), 4.89 (1 H, d, J = 11.2
Hz), 4.93 (1 H, d, J = 7.0 Hz), 4.95 (1 H, d, J = 11.0 Hz), 6.95–6.97 (3 H,
m), 7.24–7.26 (3 H, m), 7.30–7.35 (15 H, m).
4-tert-Butylphenyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (62)
Compound 62 was prepared according to the general procedure and
isolated as a colorless oil (50 mg, 90% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

O
H. Guo et al.
Paper
Synthesis
13C NMR (125 MHz, CDCl3):  = 63.9, 73.4, 75.1, 75.6, 76.7, 77.0, 77.3,
77.6, 81.4, 83.4, 102.2, 118.2, 127.6, 127.7, 127.8, 127.9, 128.0, 128.1,
128.3, 128.4, 128.5, 129.5, 138.0, 138.1, 138.5, 155.7.
1H NMR (500 MHz, CD3OD):  = 3.17–3.30 (4 H, m), 3.63 (1 H, dd, J =
11.8, 5.2 Hz ), 3.83 (1 H, d, J = 11.7 Hz), 4.29 (1 H, d, J = 7.7 Hz), 4.59 (1
H, d, J = 11.8 Hz), 4.86 (1 H, d, J = 11.8 Hz), 7.18–7.36 (5 H, m).
HRMS (ESI): m/z calcd for C32H31ClO5Na [M + Na]+: 553.1752; found:
ESI-MS: m/z calcd for C13H18O6Na [M + Na]+: 270.11; found: 270.08.
553.1772.
Benzyl 2,3,4-Tri-O-benzyl--L-fucoside (82)24f
4-Bromophenyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (67)24e
Compound 82 was prepared according to the general procedure and
isolated as a colorless oil (41 mg, 63% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 7.43–7.26 (20 H, m), 4.98 (1 H, d, J =
11.6 Hz), 4.89 (2 H, d, J = 11.9 Hz), 4.74 (2 H, dd, J = 11.8, 5.8 Hz), 4.66
(2 H, t, J = 11.5 Hz), 4.58 (2 H, dd, J = 12.1, 6.5 Hz), 4.04 (1 H, dd, J =
10.1, 3.5 Hz), 3.99 (1 H, dd, J = 10.2, 2.0 Hz) 3.88 (1 H, q, J = 6.4 Hz),
3.66 (1 H, s), 1.08 (3 H, d, J = 6.5 Hz).
Compound 67 was prepared according to the general procedure and
isolated as a colorless oil (50 mg, 87% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 3.31–3.36 (1 H, m), 3.64–3.70 (3 H, m),
3.97–4.00 (1 H, m), 4.64 (1 H, d, J = 11.9 Hz), 4.75 (1 H, d, J = 11.7 Hz),
4.80 (1 H, d, J = 10.9 Hz), 4.87 (1 H, d, J = 10.9 Hz), 4.89 (1 H, d, J = 11.2
Hz), 4.92 (1 H, d, J = 7.0 Hz), 4.94 (1 H, d, J = 11.5 Hz), 6.90 (2 H, d, J =
8.8 Hz), 7.26–7.35 (15 H, m), 7.40 (2 H, d, J = 8.8 Hz).
ESI-MS: m/z calcd for C32H31BrO5Na [M + Na]+: 597.14; found: 597.04.
Funding Information
-Naphthyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (68)24e
The project was financially supported by Natural Science Foundation
of Shanghai (11ZR1410400) and Open Foundation of East China Nor-
mal University (20151043 & 20162015).
Compound 68 was prepared according to the general procedure and
isolated as a colorless oil (48 mg, 88% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
N
aturalS
c
i
e
n
c
e
F
o
u
n
d
ati
o
n
of
S
h
a
n
g
h
a
i(1
1
Z
R
1
4
1
0
4
0
0)
1H NMR (500 MHz, CDCl3):  = 3.38–3.42 (1 H, m), 3.75–3.78 (2 H, m),
3.86–3.89 (1 H, m), 4.02–4.05 (1 H, m), 4.67 (1 H, d, J = 11.7 Hz), 4.77
(1 H, d, J = 11.7 Hz), 4.89 (1 H, d, J = 11.2 Hz), 4.92 (1 H, d, J = 7.0 Hz),
5.09 (1 H, d, J = 10.8 Hz), 5.24 (1 H, d, J = 7.2 Hz), 7.08 (1 H, d, J = 7.7
Hz), 7.26–7.56 (19 H, m), 7.82 (1 H, d, J = 8.1 Hz), 8.27 (1 H, d, J = 8.4
Hz).
Acknowledgment
We are thankful to the analytic center of East China Normal Universi-
ty for data measurement. The authors express sincere gratitude for
helpful discussions with Prof. Qiang Li (ECNU) and kind suggestions
from the reviewers of Synthesis.
ESI-MS: m/z calcd for C36H34O5Na [M + Na]+: 569.24; found: 569.25.
-Naphthyl 2,3,4-Tri-O-benzyl--D-xylopyranoside (69)24e
Supporting Information
Compound 69 was prepared according to the general procedure and
isolated as a colorless oil (48 mg, 88% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
Supporting information for this article is available online at
https://doi.org/10.1055/s-0037-1611801.
S
u
p
p
orti
n
gInformati
o
n
S
u
p
p
orti
n
gInformati
o
n
1H NMR (500 MHz, CDCl3):  = 3.44–3.48 (1 H, m), 3.75–3.78 (3 H, m),
4.07–4.10 (1 H, m), 4.70 (1 H, d, J = 11.7 Hz), 4.80 (1 H, d, J = 11.7 Hz),
4.89 (1 H, d, J = 11.0 Hz), 4.92 (1 H, d, J = 11.0 Hz), 4.94 (1 H, d, J = 10.8
Hz), 5.07 (1 H, d, J = 11.0 Hz), 5.19 (1 H, d, J = 7.0 Hz), 7.08 (1 H, d, J =
7.7 Hz), 7.26–7.38 (19 H, m), 7.40–7.43 (1 H, m), 7.77–7.83 (3 H, m).
References
(1) (a) Tanaka, H.; Amaya, T.; Takahashi, T. Tetrahedron Lett. 2003,
44, 3053. (b) Han, H.; Zhang, W.; Yi, Y. H.; Liu, B. S.; Pan, M. X.;
Wang, X. H. Chem. Biodiversity 2010, 7, 1764. (c) Liu, M.; Gan,
M.; Lin, S.; Zhang, Y.; Zi, J.; Song, W.; Fan, X.; Liu, Y.; Yang, Y.;
Shi, J. Org. Lett. 2011, 13, 2856. (d) Mulani, S. K.; Guh, J.-H.;
Mong, K.-K. T. Org. Biomol. Chem. 2014, 12, 2926.
(2) (a) Toshima, K.; Tatsuta, K. Chem. Rev. 1993, 93, 1503. (b) Jensen,
K. J. J. Chem. Soc., Perkin Trans. 1 2002, 2219. (c) Demchenko, A.
V. Synlett 2003, 1225. (d) Zhu, X.; Schmidt, R. R. Angew. Chem.
Int. Ed. 2009, 48, 1900. (e) Arihara, R.; Kakita, K.; Suzuki, N.;
Nakamura, S.; Hashimoto, S. J. Org. Chem. 2015, 80, 4259.
(3) (a) Fraser-Reid, B.; Wu, Z.; Udodong, U. E.; Ottosson, H. J. Org.
Chem. 1990, 55, 6068. (b) Tomono, S.; Kusumi, S.; Takahashi, D.;
Toshima, K. Tetrahedron Lett. 2011, 52, 2399. (c) Yang, G.; Luo,
X.; Guo, H.; Wang, Q.; Zhou, J.; Huang, T.; Tang, J.; Shan, J.;
Zhang, J. J. Carbohydr. Chem. 2018, 37, 128.
ESI-MS: m/z calcd for C36H34O5Na [M + Na]+: 569.24; found: 569.25.
Benzyl 3,4,6-Tri-O-benzyl--D-glucopyranoside (80)24h
Compound 80 was prepared according to the general procedure and
isolated as a colorless oil (46 mg, 85% yield) after column chromatog-
raphy on silica gel (PE/EtOAc 40:1).
1H NMR (500 MHz, CDCl3):  = 2.24 (1 H, t, J = 2.3 Hz), 2.46 (1 H, s),
3.64–3.69 (2 H, m), 3.74–3.77 (2 H, m), 3.80–3.84 (2 H, m), 4.36–4.42
(2 H, m), 4.45 (1 H, d, J = 12.2 Hz), 4.49 (1 H, d, J = 12.2 Hz), 4.53 (1 H,
d, J = 10.3 Hz), 4.61 (1 H, d, J = 12.2 Hz), 4.82 (1 H, d, J = 10.8 Hz), 4.84
(1 H, d, J = 11.9 Hz), 4.94 (1 H, d, J = 11.3 Hz), 7.15–7.17 (2 H, m), 7.25–
7.38 (13 H, m).
ESI-MS: m/z calcd for C34H36O6Na [M + Na]+: 563.25; found: 563.25.
(4) (a) Seeberger, P. H.; Eckhardt, M.; Gutteridge, C. E.; Danishefsky,
S. J. J. Am. Chem. Soc. 1997, 119, 10064. (b) Crich, D.; Dai, Z.;
Gastaldi, S. J. Org. Chem. 1999, 64, 5224. (c) Chen, L.; Zhao, X.-E.;
Lai, D.; Song, Z.; Kong, F. Carbohydr. Res. 2006, 341, 1174.
(d) Zhao, G.; Wang, T. Angew. Chem. Int. Ed. 2018, 57, 6120.
Benzyl -D-Glucopyranoside (81)24m
Compound 81 was prepared according to the general procedure and
isolated as a colorless oil (9.5 mg, 35% yield) after column chromatog-
raphy on silica gel (CH2Cl2/MeOH 15:1).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

P
H. Guo et al.
Paper
Synthesis
(5) (a) Schmidt, R. R.; Michel, J. Angew. Chem. Int. Ed. 1980, 19, 731.
(b) Hashimoto, S.; Hayashi, M.; Noyori, R. Tetrahedron Lett. 1984,
25, 1379. (c) Ito, Y.; Ogawa, T. Tetrahedron Lett. 1987, 28, 4701.
(d) Schmidt, R. R.; Behrendt, M.; Toepfer, A. Synlett 1990, 694.
(e) Vankar, Y. D.; Vankar, P. S.; Behrendt, M.; Schmidt, R. R. Tet-
rahedron 1991, 47, 9985. (f) Hashimoto, S.; Umeo, K.; Sano, A.;
Watanabe, N.; Nakajima, M.; Ikegami, S. Tetrahedron Lett. 1995,
63, 2251. (g) Hashihayata, T.; Mandai, H.; Mukaiyama, T. Bull.
Chem. Soc. Jpn. 2004, 77, 169. (h) Yang, D.-M.; Chen, Y.;
Sweeney, R. P.; Lowary, T. L.; Liang, X.-Y. Org. Lett. 2018, 20,
2287.
(6) (a) Wever, W. J.; Cinelli, M. A.; Bowers, A. A. Org. Lett. 2013, 15,
30. (b) Vibhute, A. M.; Dhaka, A.; Athiyarath, V.; Sureshan, K. M.
Chem. Sci. 2016, 7, 4259. (c) Goswami, M.; Ashley, D. C.; Baik,
M.-H.; Pohl, N. L. B. J. Org. Chem. 2016, 81, 5949. (d) Park, Y.;
Harper, K. C.; Kuhl, N.; Kwan, E. E.; Liu, R. Y.; Jacobsen, E. N.
Science 2017, 35(6321), 162.
(7) (a) Chao, C. S.; Lin, C. Y.; Mulani, S.; Hung, W. C.; Mong, K. K.
Chem. Eur. J. 2011, 17, 12193. (b) Buda, S.; Golebiowska, P.;
Mlynarski, J. Eur. J. Org. Chem. 2013, 3988. (c) Cox, D. J.; Singh, G.
P.; Watson, A. J. A.; Fairbanks, A. J. Eur. J. Org. Chem. 2014, 4624.
(d) Somasundaram, D.; Balasubramanian, K. K.; Bhagavathy, S.
Carbohydr. Res. 2017, 449, 95. (e) Mukherjee, M. M.; Basu, N.;
Ghosh, R. RSC Adv. 2016, 6, 105589.
5732. (f) Boddien, A.; Mellmann, D.; Gartner, F.; Jackstell, R.;
Junge, H.; Dyson, P. J.; Laurenczy, G.; Ludwig, R.; Beller, M.
Science 2011, 333,6050 : 1733. (g) Speranca, A.; Godoi, B.;
Pinton, S.; Back, D. F.; Menezes, P. H.; Zeni, G. J. Org. Chem. 2011,
76, 6789. (h) Patil, N. T.; Shinde, V. S.; Thakare, M. S.; Hemant,
Kumar. P.; Bangal, P. R.; Barui, A. K.; Patra, C. R. Chem. Commun.
2012, 48, 11229. (i) Vidhani, D. V.; Cran, J. W.; Krafft, M. E.;
Alabugin, I. V. Org. Biomol. Chem. 2013, 11, 1624. (j) Su, Y.;
Zhang, Y.; Akhmedov, N. G.; Petersen, J. L.; Shi, X. Org. Lett. 2014,
16, 2478. (k) Kepp, K. P. Inorg. Chem. 2016, 55, 9461. (l) Ren, B.;
Ramstrom, O.; Zhang, Q.; Ge, J.; Dong, H. Chemistry 2016, 22,
2481. (m) Bleith, T.; Gade, L. H. J. Am. Chem. Soc. 2016, 138,
4972. (n) Okamura, M.; Kondo, M.; Kuga, R.; Kurashige, Y.;
Yanai, T.; Hayami, S.; Praneeth, V. K.; Yoshida, M.; Yoneda, K.;
Kawata, S.; Masaoka, S. Nature 2016, 530(7591), 465. (o) Ford, C.
L.; Park, Y. J.; Matson, E. M.; Gordon, Z.; Fout, A. R. Science 2016,
354(6313), 741. (p) Brenna, D.; Villa, M.; Gieshoff, T. N.; Fischer,
F.; Hapke, M.; Jacobi von Wangelin, A. Angew. Chem. Int. Ed.
2017, 56, 8451.
(18) (a) Zhou, J. F.; Chen, X.; Wang, Q. B.; Zhang, B.; Zhang, L. Y.;
Yusulf, A.; Wang, Z. F.; Zhang, J. B.; Tang, J. Chin. Chem. Lett.
2010, 21, 922. (b) Torres Galvis, H. M.; Bitter, J. H.; Khare, C. B.;
Ruitenbeek, M.; Dugulan, A. I.; de Jong, K. P. Science 2012,
335,6070 : 835. (c) Mazzotta, M. G.; Gupta, D.; Saha, B.; Patra, A.
K.; Bhaumik, A.; Abu-Omar, M. M. ChemSusChem 2014, 7, 2342.
(d) Zhou, J.; Chen, H.; Shan, J.; Li, J.; Yang, G.; Chen, X.; Xin, K.;
Zhang, J.; Tang, J. J. Carbohydr. Chem. 2014, 33, 313. (e) Zhang, T.;
Li, W.; Xu, Z.; Liu, Q.; Ma, Q.; Jameel, H.; Chang, H. M.; Ma, L.
Bioresour. Technol. 2016, 209, 108. (f) Sun, G.; Qiu, S.; Ding, Z.;
Chen, H.; Zhou, J.; Wang, Z.; Zhang, J. Synlett 2017, 28, 347.
(g) Ding, Z.; Luo, X.; Ma, Y.; Chen, H.; Qiu, S.; Sun, G.; Zhang, W.;
Yu, C.; Zhang, J. J. Carbohydr. Chem. 2018, 37, 81.
(8) Kim, J. H.; Yang, H.; Boons, G. J. Angew. Chem. Int. Ed. 2005, 44,
947.
(9) Smoot, J. T.; Pornsuriyasak, P.; Demchenko, A. V. Angew. Chem.
Int. Ed. 2005, 44, 7123.
(10) Mensah, E. A.; Azzarelli, J. M.; Nguyen, H. M. J. Org. Chem. 2009,
74, 1650.
(11) Buda, S.; Nawoj, M.; Golebiowska, P.; Dyduch, K.; Michalak, A.;
Mlynarski, J. J. Org. Chem. 2015, 80, 770.
(12) Peng, P.; Schmidt, R. R. Acc. Chem. Res. 2017, 50, 1171.
(13) (a) Marra, A.; Esnault, J.; Veyrieres, A.; Sinay, P. J. Am. Chem. Soc.
1992, 114, 6354. (b) Crich, D.; Patel, M. Carbohydr. Res. 2006,
341, 1467. (c) Chao, C. S.; Lin, C. Y.; Mulani, S.; Hung, W. C.;
Mong, K. T. Chem. Eur. J. 2011, 17, 12193. (d) Chu, A.-H. A.;
Minciunescu, A.; Bennett, C. S. Org. Lett. 2015, 17, 6262.
(14) (a) Imagawa, H.; Kinoshita, A.; Fukuyama, T.; Yamamoto, H.;
(19) (a) Kayastha, A. K.; Hotha, S. Chem. Commun. 2012, 48, 7161.
(b) Adhikari, S.; Baryal, K. N.; Zhu, D.; Li, X.; Zhu, J. ACS Catal.
2012, 3, 57. (c) Yadav, J. S.; Yadav, N. N.; Gupta, M. K.; Srivastava,
N.; Subba Reddy, B. V. Monatsh. Chem. 2014, 145, 517.
(20) Vidadala, S. R.; Hotha, S. Chem. Commun. 2009, 2505.
(21) (a) Shamim, A.; Vasconcelos, S. N. S.; Ali, B.; Madureira, L. S.;
Zukerman-Schpector, J.; Stefani, H. A. Tetrahedron Lett. 2015, 56,
5836. (b) Whitfield, D. M. Carbohydr. Res. 2015, 403, 69.
(c) Adero, P. O.; Amarasekara, H.; Wen, P.; Bohe, L.; Crich, D.
Chem. Rev. 2018, 118, 8242.
(22) (a) Afsaneh, F.; Hassan, H. M. J. Catal. 2017, 352, 229. (b) Saeed,
R.; Fatemeh, N. C. R. Chimie 2017, 20, 967. (c) Kayhaneh, B.;
Afsaneh, F.; Hassan, H. M.; Christoph, J. Tetrahedron 2018, 74,
2202. (d) Kayhaneh, B.; Hassan, H. M. Inorg. Chim. Acta 2018,
471, 113.
Nishizawa,
M.
Tetrahedron
Lett.
2006,
47,
4729.
(b) Sureshkumar, G.; Hotha, S. Chem. Commun. 2008, 4282.
(c) Yang, F.; Wang, Q.; Yu, B. Tetrahedron Lett. 2012, 53, 5231.
(d) Ramana, K. N.; Rengarajan, B. Org. Biomol. Chem. 2015, 13,
5094.
(15) (a) Cornil, J.; Guerinot, A.; Reymond, S.; Cossy, J. J. Org. Chem.
2013, 78, 10273. (b) Zhu, Y.; Li, C.; Zhang, J.; She, M.; Sun, W.;
Wan, K.; Wang, Y.; Yin, B.; Liu, P.; Li, J. Org. Lett. 2015, 17, 3872.
(c) Shi, J. L.; Zhang, J. C.; Wang, B. Q.; Hu, P.; Zhao, K. Q.; Shi, J.
Org. Lett. 2016, 18, 1238. (d) Zhao, J.; Xu, Z.; Oniwa, K.; Asao, N.;
Yamamoto, Y.; Jin, T. Angew. Chem. Int. Ed. 2016, 55, 259.
(e) Jang, S. S.; Youn, S. W. Org. Biomol. Chem. 2016, 14, 2200.
(f) Shiva Kumar, K.; Siddi Ramulu, M.; Rajesham, B.; Kumar, N.
P.; Voora, V.; Kancha, R. K. Org. Biomol. Chem. 2017, 15, 4468.
(g) Sun, G.; Wu, Y.; Liu, A.; Qiu, S.; Zhang, W.; Zhang, J. Synlett
2018, 29, 668.
(16) Hotha, S.; Kashyap, S. J. Am. Chem. Soc. 2006, 128, 9620.
(17) (a) Jana, U.; Biswas, S.; Maiti, S. Eur. J. Org. Chem. 2008, 5798.
(b) Wu, X. F.; Bezier, D.; Darcel, C. Adv. Synth. Catal. 2009, 351,
367. (c) Shahzad, S. A.; Vivant, C.; Wirth, T. Org. Lett. 2010, 12,
1364. (d) Gay, R. M.; Manarin, F.; Schneider, C. C.; Barancelli, D.
A.; Costa, M. D.; Zeni, G. J. Org. Chem. 2010, 75, 5701. (e) Huang,
L.; Cheng, K.; Yao, B.; Xie, Y.; Zhang, Y. J. Org. Chem. 2011, 76,
(23) Qiu, S.; Sun, G.; Ding, Z.; Chen, H.; Zhang, J. Synlett 2017, 28,
2024.
(24) (a) Tsutsumi, H.; Ishido, Y. Carbohydr. Res. 1981, 88, 61. (b) Qiu,
D.-X.; Wang, Y.-F.; Caj, H. S. Synth. Commun. 1989, 19, 3453.
(c) Gueyrard, D.; Rollin, P.; Nga, T. T. T.; Ourevitch, M. O.; Bégué,
J.-P.; Bonnet-Delpon, D. Carbohydr. Res. 1999, 318, 171.
(d) Hadad, C.; Bouquillon, S.; Harakat, D.; Muzart, J. Appl.
Organomet. Chem. 2009, 23, 161. (e) McKay, M. J.; Naab, B. D.;
Mercer, G. J.; Nguyen, H. M. J. Org. Chem. 2009, 74, 4705.
(f) Jalsa, N. K. Tetrahedron Lett. 2011, 52, 6587. (g) Mattson, A. L.;
Michel, A. K.; Cloninger, M. J. Carbohydr. Res. 2012, 347, 142.
(h) Padungros, P.; Alberch, L.; Wei, A. J. Org. Chem. 2014, 79,
2611. (i) Liu, X.; Zhang, B.; Gu, X.; Chen, G.; Chen, L.; Wang, X.;
Xiong, B.; You, Q.-D.; Chen, Y.-L.; Shen, J. Carbohydr. Res. 2014,
398, 45. (j) Roy, R.; Rajasekaran, P.; Mallick, A.; Vankar, Y. D. Eur.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q

Q
H. Guo et al.
Paper
Synthesis
J. Org. Chem. 2014, 5564. (k) Tambie, M. S.; Jalsa, N. K. J. Carbo-
hydr. Chem. 2015, 34, 545. (l) Palanivel, A.; Chennaiah, A.;
Dubbu, S.; Mallick, A.; Vankar, Y. D. Carbohydr. Res. 2017, 437,
43. (m) Yang, J.; Meng, X.; Shi, Y.;. Faming Zhuanli Shenqing CN
107936070 A, 2018. (n) Chatterjee, S.; Moon, S.; Hentschel, F.;
Gilmore, K.; Seeberger, P. H. J. Am. Chem. Soc. 2018, 140, 11942.
(o) Mishra, K. B.; Singh, A. K.; Kandasamy, J. J. Org. Chem. 2018,
83, 4204. (p) Ye, H.; Xiao, C.; Zhou, Q.-Q.; Wang, P. G.; Xiao, W.-J.
J. Org. Chem. 2018, 83, 13325. (q) Shaw, M.; Thakur, R.; Kumar,
A. J. Org. Chem. 2019, 84, 589.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–Q