Collective syntheses of phenylethanoid glycosides by interrupted Pummerer reaction mediated glycosylations

Article abstract of DOI:10.1080/07328303.2018.1541997

The collective total syntheses of nine natural phenylethanoid glycosides (PhEGs) together with proposed Incanoside B in a divergent mode were described. By using a core disaccharide as common intermediate, our developed interrupted Pummerer reaction media

Full text of DOI:10.1080/07328303.2018.1541997

Journal of Carbohydrate Chemistry
ISSN: 0732-8303 (Print) 1532-2327 (Online) Journal homepage: https://www.tandfonline.com/loi/lcar20
Collective syntheses of phenylethanoid glycosides
by interrupted Pummerer reaction mediated
glycosylations
Yueqi Zhao, Jing Zeng, Yan Liu, Xiong Xiao, Guangfei Sun, Jiuchang Sun,
Penghua Shu, Dengxian Fu, Lingkui Meng & Qian Wan
To cite this article: Yueqi Zhao, Jing Zeng, Yan Liu, Xiong Xiao, Guangfei Sun, Jiuchang
Sun, Penghua Shu, Dengxian Fu, Lingkui Meng & Qian Wan (2019): Collective syntheses of
phenylethanoid glycosides by interrupted Pummerer reaction mediated glycosylations, Journal of
Carbohydrate Chemistry, DOI: 10.1080/07328303.2018.1541997
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JOURNAL OF CARBOHYDRATE CHEMISTRY
https://doi.org/10.1080/07328303.2018.1541997
Collective syntheses of phenylethanoid glycosides by
interrupted Pummerer reaction mediated glycosylations
a
a
a
a
a
Yueqi Zhao , Jing Zeng , Yan Liu , Xiong Xiao , Guangfei Sun , Jiuchang
a
a
a
a
a,b
Sun , Penghua Shu , Dengxian Fu , Lingkui Meng , and Qian Wan
a
Hubei Key Laboratory of Natural Medicinal Chemistry and Resource Evaluation, School of
b
Pharmacy, Huazhong University of Science and Technology, Wuhan, China; Institute of Brain
Research, Huazhong University of Science and Technology, Wuhan, China
ABSTRACT
KEYWORDS
Phenylethanoid glycosides;
collective synthesis;
structure revision;
interrupted
The collective total syntheses of nine natural phenylethanoid
glycosides (PhEGs) together with proposed Incanoside B in a
divergent mode were described. By using a core disaccharide
as common intermediate, our developed interrupted
Pummerer reaction mediated (IPRm) glycosylations adopting
latent-active strategy enables the efficient, concise and diver-
gent syntheses of these bioactive PhEGs. Among them, five
natural PhEGs, Darendoside B (1), Cistanoside G (3), Decaffeoyl
Pummerer reaction
0
00
acteoside (4), Kankanoside F (5) and 4 -epi-Leonoside F (7)
were the first time being synthesized. According to the syn-
0
00
thesis of 4 -epi-Leonoside F (7), we also elucidated the real
structure of carbohydrate component of the PhEG isolated
from Rehmannia glutinosa which was misled as “Leonoside F”.
GRAPHICAL ABSTRACT
Introduction
Phenylethanoid glycosides (PhEGs) are common components of many
[
1]
medicinal plants, which usually present noteworthy bioactivities.
Structurally, PhEGs are glycosides bearing a substituted phenylethanoid
aglycon attached to various carbohydrates (Figure 1a). Hundreds of PhEGs
have been isolated and identified to date, among which the different
CONTACT Qian Wan
wanqian@hust.edu.cn
Hubei Key Laboratory of Natural Medicinal Chemistry and
Resource Evaluation, School of Pharmacy, Huazhong University of Science and Technology, 7 Hangkong Road,
Wuhan, Hubei, 430030, China; Institute of Brain Research, Huazhong University of Science and Technology, 7
Hangkong Road, Wuhan, Hubei, 430030, China
Supplemental data for this article can be accessed on the publisher’s website.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lcar
ß 2019 Taylor & Francis Group, LLC

2
Y. ZHAO ET AL.
(
a)
(
b)
Figure 1. Common structure of PhEGs and targeted PhEGs.
linkage of glycosides and the variation of the aromatic aglycons or residues
[
2]
account for their structural diversity. Updating reviews introduced the
[
3]
isolation and bioactivities of new PhEGs and the chemical synthesis of
[
4]
some PhEGs have also been reported. However, despite inherent struc-
ture similarity of these PhEGs, the collective synthesis of PhEGs in a diver-
gent way was rare.
Recently, we have developed two interrupted Pummerer reaction medi-
[
5]
ated (IPRm) glycosylations. These methods are convenient and efficient
in synthesizing complex glycosides due to the allowance of employing
latent-active glycosylation strategy. In the IPRm glycosylations, O/S-2-(2-
propylthio)benzyl (O/S-PTB) glycosides were introduced as “latent” glycosyl
donors, which are quite stable under most of glycosylation and many pro-
tection/deprotection conditions. The latent O/S-PTB glycosides can be con-
veniently
oxidized
to
their
“active”
counterparts,
O/S-2-(2-
propylsulfinyl)benzyl (O/S-PSB) glycosides, to perform satisfying reactivity
in the glycosylation process via an interrupted Pummerer reaction mechan-
[
6]
ism (Scheme 1a). With the newly developed IPRm glycosylations, we

JOURNAL OF CARBOHYDRATE CHEMISTRY
3
a)
b)
Scheme 1. Interrupted Pummerer reaction mediated (IPRm) glycosylations and synthetic plan
to PhEGs.
have accomplished the total syntheses as well as the structural revisions of
[
5a,5c]
several PhEGs including Leonoside E, F and Leonuriside B.
Taking account of the important bioactivities and the structure similarity
of PhEGs as well as the efficiency of our newly developed IPRm glycosyla-
tion method, here we report the collective total syntheses of a series of
[
7]
[8]
PhEGs, including Darendoside B (1), Cistanoside E (2), Cistanoside G
[
9]
[10]
[11]
(
(
3),
6),
Decaffeoyl acteoside (4),
Kankanoside F (5),
4 -epi-Leonoside F (7), Leonoside E (8),
Leonoside F
[
12] 000
[12]
[13]
Leonuriside B (9)
[
14]
and Incanoside B (10)
(Figure 1b). Most of them have been reported to
present interesting bioactivities. For example, Darendoside B (1),
Cistanoside G (3), and Leonuriside B (9) present antioxidative activi-
[
2b,4,15g]
[2b]
ty,
5) showed vasorelaxant activity,
protective activity against D-galactosamine-induced toxicity in HL-7702 cells
Decaffeoyl acteoside (4) has antitumor effect,
Kankanoside F
[
11]
(
Leonoside E (8) exhibit potent hepato-
ꢁ5
[12]
at concentration of 1 ꢀ 10 M.
From structure point of view, 1–4 are

4
Y. ZHAO ET AL.
Scheme 2. Synthesis of core disaccharide 11.
disaccharide PhEGs, 5–7 belong to branched trisaccharide PhEGs, 8–10 are
linear trisaccharide PhEGs. Most importantly, all these PhEGs possess the
same a-L-rhamnopyranosyl-(1!3)-b-D-glucopyranosyl core disaccharide
moiety. This intrinsic structural character promoted us to synthesize these
PhEGs from a common disaccharide intermediate 11 incorporating the
interrupted Pummerer reaction mediated glycosylations. We envisaged that
compound 11 bearing the cleavable acetyl and benzylidene groups could be
easily converted to corresponding glycosyl acceptors to link with the third
glycosides. More importantly, the latent 1-SPTB group of 11 could be oxi-
dized to its active 1-SPSB pattern whenever needed, and act as glycosyl
donors to link with various aglycons (Scheme 1b).
Results and discussion
Our collective syntheses of PhEGs commenced from the preparation of the
core disaccharide 11 (Scheme 2). Treatment of 2,3-dihydroxyl SPTB glyco-
[
5c]
side 12
with Ag O (1.5 equiv), BzCl (1.1 equiv) and catalytic amount of
2
[
16]
KI (0.2 equiv) selectively afforded the mono-benzoylated acceptor 13.
The regioselectivity was confirmed by the downfield shift of H-2 signal
1
from d 3.41 of 12 to d 5.19 of 13 in H NMR spectrum. Further glycosyla-
tion of the latent SPTB glycoside 13 with 1.2 equiv of OPSB donor 14 in
the presence of 1.2 equiv of Tf O and 2.0 equiv DTBMP furnished the core
2
disaccharide 11 in 80% yield with absolute stereo-control.
With the core disaccharide intermediate 11 in hand, we started to synthe-
size the disaccharide PhEGs 1–4 following the route showed in Scheme 3.
After oxidation of 11 to its active pattern, the obtained donor 15 was
coupled with four different phenylethanol aglycons 16a–d respectively in the
presence of 1.2 equiv of Tf O and 1.6 equiv of DTBMP, which provided
2
17a–d in yields ranging from 85% to 89%. Deprotection of benzylidene
groups of 17a–d with our recently reported 1,4-dithiotretol (DTT) mediated
[
17]
acetal groups deprotection method provided 18a–d efficiently.
Further
deacylations and debenzylations successfully afforded the disaccharide PhEGs
Darendoside B (1), Cistanoside E (2), Cistanoside G (3) and Decaffeoyl
acteoside (4) respectively in excellent yields. The spectral data of 1–4 were in
[
7–10]
good agreement with those reported for isolated natural products.
The obtaining of 18a–d possessing free hydroxy groups during the syn-
thesis of PhEGs 1–4 allowed the quick access to branched PhEGs 5–6 by

JOURNAL OF CARBOHYDRATE CHEMISTRY
5
Scheme 3. Syntheses of disaccharide PhEGs 1–4.
Scheme 4. Syntheses of branched PhEGs 5 and 6.
selective attaching the third carbohydrate moieties to the primary hydroxy
group. The coupling reaction between SPSB glycoside 19 and disaccharide
18a or 18d under the standard activation conditions proceeded smoothly,
which offered trisaccharide 20a or 20d regioselectively. Further deprotec-
[
5a]
tion reactions provided Leonoside F (6, revised structure)
Kankanoside F (5) successfully (Scheme 4).
and
[
5a]
We have recently reported the structure revision of Leonoside F
which was originally isolated from Chinese motherwort (Leonurus japonicus
Houtt) . Following this isolation, it was reported that Leonoside F was
[
12]
[
18]
also isolated from Chinese foxglove (Rehmannia glutinosa).
However, it
1
3
was found that the C-NMR spectra of the latter Leonoside F is different
from that of the revised Leonoside F in the region d 69.0–79.0 ppm which
were assigned to the branched glucose component. By carefully analyzing
the spectra, we suspected that the branched glucose of “Leonoside F” iso-
lated from Chinese foxglove was incorrectly elucidated; most possibly it
0
00
would be galactose. To verify this hypothesis, we synthesized 4 -epi-
Leonoside F containing galactose moiety followed the procedure depicted

6
Y. ZHAO ET AL.
0
00
Scheme 5. Synthesis of 4 -epi-Leonoside F (7).
Table 1. Selective removal of acetyl group of 11.
Entry
Conditions
Yield (%)
1
2
3
4
K
2
CO
3
, DCM/MeOH, rt, 10 h
65
71
0
NaOMe, DCM/MeOH, rt, 29 h
N
N
2
H
4
-H
-H
2
O (10 eq), THF, rt, 12 h
ꢂ
2
H
4
2
O(100 eq), THF, 60 C, 30 h
78
in Scheme 5. As predicted, the NMR data of the trisaccharide moiety of
0
00
4
-epi-Leonoside F is perfectly matched with the isolated one, which sug-
gested the real structure of the carbohydrate component of “Leonoside F”
isolated from Chinese foxglove. However, slightly difference still exist in
1
3
the aromatic part (Dd ± 0.4 ppm in C-NMR) possibly due to the different
[
19]
chemical environment in NMR test.
The successful synthesis of the disaccharide and branched PhEGs encour-
aged us to further apply this strategy to the synthesis of linear PhEGs
8–10. The structure difference of these PhEGs lies not only on the aglycon
moiety but also on the terminal sugar components. We planned to install
the terminal sugars to the core disaccharide 11 first which required the
selective removal of the acetyl group of 11 in the presence of the benzoyl
group. As shown in Table 1, when treatment of 11 with NaOMe in dry
[
20]
DCM/MeOH,
the desired product 23 was obtained in 71% yield,
together with some debenzoylation by-product. The utilization of K CO
2
3
gave a similar result. Then N H -H O was employed as deacetylation
2
4
2
[
21]
reagent.
However, the starting material 11 is quite stable when applying
1
0 equiv of N H -H O at room temperature, after increasing N H -H O to
2
4
2
2
4
2

JOURNAL OF CARBOHYDRATE CHEMISTRY
7
Scheme 6. Syntheses of linear PhEGs 8 and 9.
Scheme 7. Synthesis of proposed Incanoside B (10).
ꢂ
1
00 equiv and elevating reaction temperature to 60 C, 23 was finally
obtained in 78% yield.
We then moved on synthesizing Leonoside E (8) and Leonuriside B (9)
bearing the same trisaccharide glycan (Scheme 6). The latent trisaccharide
25 was obtained as single isomer by coupling of donor 24 with disacchar-
ide acceptor 23. Further oxidation and glycosylation with 16a or 16d pro-
vided 27a or 27d in high efficiency. Final global deprotection of
benzylidene group, acyl group and benzyl group offered Leonoside E (8)
and Leonuriside B (9) in 86% and 78% yield respectively.
However, when application of above mentioned glycosylation condi-
tions to the synthesis of trisaccharide moiety 28, only 13% of desired
product was obtained, accompanied with 69% of ortho-ester by-product
2
9, possibly resulting from the over basicity reaction conditions by
using 2.0 equiv of DTBMP. Thus, we decreased the dosage of DTBMP
to 0.5 equiv, and to our delight, the ortho-ester by-product decreased
effectively and 28 was obtained in 68% yield. Following the subsequent
glycosylation and deprotection reactions as described in Scheme 7,
finally, we successfully obtained the proposed structure of Incanoside B
(
10). However, it was found that the chemical shifts of the proposed
structure were inconsistent with those of isolated one at C3’ and C4’

8
Y. ZHAO ET AL.
1
3
position (Dd 1.6 and 1.2 ppm of
C NMR respectively, see the
Supporting Information), which indicated that the rhamnose moiety of
the real structure of Incanoside B most possibly linked to C4’ position
other than C3’ position.
Conclusion
In summary, we have collectively synthesized ten phenylethanoid glycosides
(
PhEGs), including four disaccharide, three branched trisaccharide and
three linear trisaccharide, based on interrupted Pummerer reaction medi-
ated glycosylations in a divergent manner. The synthesis employed a core
disaccharide 11 as a key intermediate. Starting from this common inter-
mediate, PhEGs 1–4 were obtained in 5 steps in total yields of 62–68%;
branched PhEGs 5–7 were acquired in 6 steps in total yield of 30–51%;
and linear PhEGs 8–10, were produced in 7 steps in total yields of 37–51%.
Among these PhEGs, the syntheses of Darendoside B (1), Cistanoside G
(3), Decaffeoyl acteoside (4), Kankanoside F (5) are first reported. In add-
ition, during the synthesis, we also revised the structure of the glycan moi-
ety of Leonoside F isolated from Chinese foxglove, although the exact
structure requires further elucidation. We also found that the structure of
Incanoside B (10) was incorrectly assigned, elucidation of its real structure
is under way.
Experimental section
General experimental methods
NMR spectra were recorded on Bruker AM-400 spectrometer (400 MHz),
1
13
and the H and C NMR chemical shifts were referenced to the solvent or
solvent impurity peaks for CDCl at d H 7.24 and d C 77.16. Optical rota-
3
ꢂ
tions were measured at 20 C with a Rudolph Autopol IV automatic polar-
imeter using a quartz cell with 2 mL capacity and a 1 dm path length.
Concentrations (c) are given in g/100 mL. High resolution mass spectra
were recorded on a Bruker micro TOF II spectrometer using electrospray
ionization (ESI). Thin layer chromatography (TLC) was performed on sil-
ica-gel-coated TLC plates (Yantai Chemical Industry Research Institute)
and revealed with either a UV lamp (kmax ¼ 254 nm) or by spraying with
1
0% H SO (10% H SO in ethanol) and subsequent charring by heating.
2 4 2 4
Column chromatography was performed using silica gel (Qingdao Marine
Chemical Inc., China).

JOURNAL OF CARBOHYDRATE CHEMISTRY
9
Materials
Prior to running the glycosylation reactions, all reagents except Tf O and
2
ꢂ
those with low boiling point (<180 C) were dried by repeated azeotropic
removal of water using toluene and a rotary evaporator at 27 C. Solvents
ꢂ
for reactions were dried on an Innovative Technologies Pure Solv400 solv-
ent purifier. Molecular sieves (4 Å, powder <50 mm) for reactions were
flame dried immediately before use. Trifluoromethanesulfonic anhydride
(
Tf O), 3-Chloroperoxybenzoic acid (m-CPBA) and all other commercial
2
available chemicals were purchased from Adamas and used without further
purification.
S-2-Isopropylmercaptobenzyl 2-O-acetyl-3,4-di-O-benzyl-a-L-rhamnopyranosyl-
(
1!3)-2-O-benzoyl-4,6-O- benzylidene-1-thio-b-D-glucopyranoside (11)
[5a]
A solution of 14 (100 mg, 0.18 mmol)
and DTBMP (61.6 mg, 0.29 mmol)
in CH Cl (1.76 mL) in the presence of 4 Å MS (100 wt%) was stirred at
2
2
ꢂ
ꢁ
40 C for 15 min. After addition of Tf O (30 lL, 0.18 mmol), the solution
2
ꢂ
[5c]
was stirred at ꢁ40 C for 3 min, and then 13 (81.3 mg, 0.15 mmol)
in
ꢂ
CH Cl (0.98 mL) was added. The reaction mixture was stirred at ꢁ40 C for
2
2
1
h and quenched with saturated aqueous NaHCO . The organic phase was
3
washed with brine, dried (Na SO ), concentrated, and purified by silica gel
2
4
column chromatography to give compound 11 (108 mg, 80% yield) as white
2
D
0
1
solid. R ¼ 0.49 (petroleum -EtOAc 4:1). ½aꢃ ꢁ41.2 (c, 1.00 in CHCl ). H
f
3
NMR (400 MHz, CDCl ) d 7.96–7.94 (2 H, dd, J¼ 8.4, 1.2 Hz, Ar-H),
3
7
.57–7.13 (22 H, m, Ar-H), 5.54 (1 H, s, PhCHO ), 5.36 (1 H, dd, J¼ 10.0,
2
8
.8 Hz, H-2 ), 5.17 (1 H, dd, J¼ 3.2, 1.6 Hz, H-2
), 4.79 (1 H, d,
Glu
Rham
J¼ 10.8 Hz, ArCH ), 4.78 (1 H, d, J¼ 1.6 Hz, H-1Rham), 4.57 (1 H, d,
2
J¼ 10.8 Hz, ArCH ), 4.55 (1 H, d, J ¼ 10.0 Hz, H-1 ), 4.46 (1 H, d,
2
Glu
J¼ 11.0 Hz, ArCH ), 4.38 (1 H, dd, J¼ 10.4, 5.2 Hz), 4.37 (1 H, d, J¼ 11.0 Hz,
2
ArCH ), 4.22 (1 H, d, J¼ 13.2 Hz, ArCH ), 4.08–4.00 (3 H, m), 3.82 (1 H, dd,
2
2
J¼ 8.8, 3.2 Hz), 3.78 (1 H, t, J¼ 10.0Hz), 3.68 (1 H, t, J¼ 9.6 Hz), 3.52 (1 H,
td, J¼ 9.6, 4.8 Hz, H-5 ), 3.27 (1 H, hepta. J¼ 6.4 Hz, -SCH(CH ) ), 3.22
Glu
3 2
(
1 H, t, J¼ 9.6 Hz), 1.77 (3 H, s, -OAc), 1.19 (3 H, d, J ¼ 6.4 Hz, -SCH(CH ) ),
3
2
1
3
1
.16 (3 H, d, J¼ 6.4 Hz, -SCH(CH ) ), 0.89 (3 H, d, J¼ 6.4 Hz, H-6
). C
3
2
Rham
NMR (100 MHz, CDCl ) d 169.3 (C ¼ O), 165.1 (C ¼ O), 139.4, 138.8, 138.2,
3
1
1
1
7
37.0, 135.6, 133.4, 133.2, 130.5, 130.2, 130.2, 129.3, 129.1, 128.4, 128.4, 128.4,
28.4, 128.3, 128.3, 128.2, 128.2, 128.2, 128.2, 127.9, 127.8, 127.8, 127.7, 127.6,
27.2, 126.4, 126.4 (Ar), 101.8, 98.7, 83.7, 80.0, 79.2, 78.0, 77.9, 75.1, 73.0,
1.7, 71.1, 68.7, 68.4, 68.0, 39.0, 33.0, 23.2, 23.1, 20.7, 17.5. HRMS calc. for
C H NaO S [M þ Na] :943.3156, found: 943.3158.
þ
52
56
11 2

1
0
Y. ZHAO ET AL.
S-2-Isopropylsulfinylbenzyl 2-O-acetyl-3,4-di-O-benzyl-a-L-rhamnopyranosyl-
1!3)-2-O-benzoyl-4,6-O- benzylidene-1-thio-b-D-glucopyranoside (15)
A solution of 11 (500 mg, 0.54 mmol) in CH Cl (2.71 mL) was cooled to
(
2
2
ꢂ
ꢁ
20 C, followed by dropwise addition of the solution of 3-chloroperoxy-
benzoic acid (75%) (125 mg, 0.54 mmol) in CH Cl (2.71 mL). The reaction
2
2
ꢂ
mixture was stirred at ꢁ20 C for 1 h, diluted with EtOAc, washed with
0% Na S O aqueous solution. The organic phase was washed with brine,
1
2
2 3
dried (Na SO ), concentrated, and purified by silica gel column chromatog-
2
4
raphy to give compound 15 (457 mg, 90% yield) as white foam, R ¼ 0.29
f
1
(
petroleum -EtOAc 2:1). H NMR (400 MHz, CDCl ) d 8.04 (2 H, d,
3
J ¼ 7.6 Hz, Ar-H), 7.96 (2 H, d, J ¼ 7.6 Hz, Ar-H), 7.84–7.79 (2 H, m, Ar-H),
7
5
.60–7.18 (42 H, m, Ar-H), 5.55 (1 H, s, PhCHO ), 5.54 (1 H, s, PhCHO ),
2 2
.43–5.35 (2 H, m), 5.15 (1 H, dd, J ¼ 3.2, 1.6 Hz, H-2Rham), 5.12 (1 H, dd,
J ¼ 3.2, 1.6 Hz, H-2
), 4.83 (1 H, brs, H-1
Rham
), 4.79–4.75 (3 H, m), 4.64
Rham
(
1 H, d, J ¼ 10.0 Hz, H-1 ), 4.54 (1 H, d, J ¼ 11.2 Hz, ArCH ), 4.53 (1 H, d,
Glu
2
J ¼ 11.2 Hz, ArCH ), 4.49–4.46 (2 H, m), 4.44–4.38 (2 H, m), 4.37–4.30
2
(
3 H, m), 4.12–4.10 (3 H, m), 4.09–4.05 (1 H, t, J ¼ 9.2 Hz), 4.03–3.96 (3 H,
m), 3.89 (1 H, d, J ¼ 13.2 Hz, ArCH ), 3.82–3.78 (3 H, m), 3.76–3.69 (2 H,
2
m), 3.67 (1 H, t, J ¼ 9.6 Hz), 3.58–3.51 (2 H, m), 3.25–3.19 (2 H, m), 3.02
(
-
1 H, hepta. J ¼ 6.4 Hz, -SCH(CH ) ), 2.90 (1 H, hepta. J ¼ 6.4 Hz,
3
2
SCH(CH ) ), 1.77 (3 H, s, -OAc), 1.75 (3 H, s, -OAc), 1.21 (3 H, d,
3
2
J ¼ 6.8 Hz, -SCH(CH ) ), 1.12 (3 H, d, J ¼ 6.8 Hz, -SCH(CH ) ), 1.02 (3 H,
3
2
3 2
d, J ¼ 6.8 Hz, -SCH(CH ) ), 0.99 (3 H, d, J ¼ 6.8 Hz, -SCH(CH ) ), 0.89
3
2
3 2
3
1
(
(
1
1
1
1
1
1
3 H, d, J ¼ 6.4 Hz, H-6
), 0.87 (3 H, d, J ¼ 6.4 Hz, H-6
). C NMR
Rham
Rham
100 MHz, CDCl ) d 169.2, 169.2, 165.1, 164.9 (C ¼ O), 141.5, 141.4, 138.7,
3
38.6, 138.0, 138.0, 136.8, 136.8, 135.3, 134.6, 133.6, 133.6, 131.0, 131.0,
30.9, 130.7, 130.0, 130.0, 130.0, 130.0, 129.1, 129.0, 128.9, 128.8, 128.5,
28.5, 128.5, 128.5, 128.3, 128.3, 128.3, 128.3, 128.3, 128.3, 128.3, 128.3,
28.2, 128.2, 128.2, 128.2, 128.1, 128.1, 128.0, 128.0, 128.0, 127.7, 127.7,
27.7, 127.7, 127.6, 127.6, 127.5, 127.5, 126.3, 126.3, 126.3, 126.3, 126.3,
25.7, 125.7 (Ar), 101.8, 101.8, 98.7, 98.7, 83.9, 82.6, 79.8, 79.8, 79.0, 79.0,
7.8, 77.8, 77.7, 77.6, 77.2, 77.2, 75.0, 75.0, 72.7, 72.7, 71.7, 71.7, 71.2, 71.2,
7
6
8.4, 68.4, 68.0, 67.9, 53.8, 53.5, 29.8, 29.3, 20.6, 20.6, 17.4, 17.4, 17.4, 17.2,
þ
12.7, 12.7. HRMS calc. for C H NaO S
[M þ Na] :959.3111,
5
2
56
12 2
found: 959.3143.
General procedure for the preparation of 17a–d
A solution of 15 (100 mg, 0.11 mmol, 1.2 equiv), 16 (a-d) (0.09 mmol, 1.0
equiv) and DTBMP (29.8 mg, 0.14 mmol, 1.6 equiv) in CH Cl (1.78 mL) in
2
2
ꢂ
the presence of 4 Å MS (100 wt%) was stirred at 0 C for 10 min. Tf O
17.9 lL, 0.11 mmol, 1.2 equiv) was added, the solution was stirred at 0 C
2
ꢂ
(
for 30 min. The reaction mixture was quenched with Et N, then filtered
3

JOURNAL OF CARBOHYDRATE CHEMISTRY
11
and extracted with EtOAc. The organic phase was washed with brine, dried
Na SO ), concentrated, and purified by silica gel column chromatography
(
2
4
to give compound 17a-d.
3
-Benzoxyl-4-methoxylphenylethyl 2-O-acetyl-3,4-di-O-benzyl-a-L-rhamnopyra-
nosyl-(1!3)-2-O -benzoyl-4,6-O- benzylidene-b-D-glucopyranoside (17a)
2
D
0
White solid, R ¼ 0.50 (petroleum-EtOAc 3:1). ½aꢃ ꢁ11.4 (c, 3.45 in
f
1
CHCl ). H NMR (400 MHz, CDCl ) d 7.98 (2 H, d, J ¼ 8.0 Hz, Ar-H),
3
3
7
.57–7.19 (23 H, m, Ar-H), 6.67 (1 H, s, H-2), 6.62 (1 H, d, J ¼ 8.0 Hz, H-6),
6
.50 (1 H, d, J ¼ 8.0 Hz, H-5), 5.51 (1 H, s, PhCHO ), 5.31 (1 H, t,
2
J ¼ 8.0 Hz, H-2 ), 5.20 (1 H, brs, H-2
Glu
), 5.07 (2 H, s, PhCH O-), 4.81
2
Rham
(
1 H, appar. s, H-1
), 4.70 (1 H, d, J ¼ 11.8 Hz, PhCH ), 4.60 (1 H, d,
Rham
2
J ¼ 8.4 Hz, H-1 ), 4.58 (1 H, d, J ¼ 11.8 Hz, PhCH ), 4.47 (1 H, d,
Glu
2
J ¼ 10.8 Hz, PhCH ), 4.38 (1 H, d, J ¼ 10.8 Hz, PhCH ), 4.36 (1 H, dd,
2
2
J ¼ 9.6, 5.2 Hz), 4.09–3.99 (3 H, m), 3.85 (1 H, dd, J ¼ 9.2, 3.2 Hz), 3.77
(
1 H, dd, J ¼ 10.4, 10.0 Hz), 3.69 (3 H, s, -OMe), 3.66 (1 H, t, J ¼ 9.6 Hz),
3
.60 (1 H, m), 3.53 (1 H, m, H-5Glu), 3.24 (1 H, t, J ¼ 9.6 Hz), 2.71 (2 H, m,
13
ArCH CH O-), 1.80 (3 H, s, -OAc), 0.91 (3 H, d, J ¼ 6.0 Hz, H-6
).
Rham
C
2
2
NMR (100 MHz, CDCl ) d 169.4 (C ¼ O), 165.0 (C ¼ O), 148.2, 147.9,
3
1
1
1
1
7
38.8, 138.2, 137.4, 137.0, 133.3, 130.9, 130.0, 130.0, 129.4, 129.1, 128.6,
28.6, 128.4, 128.4, 128.4, 128.4, 128.3, 128.3, 128.2, 128.2, 128.2, 128.2,
27.9, 127.8, 127.8, 127.7, 127.6, 127.5, 127.5, 126.4, 126.4, 121.7 (Ar),
15.0, 111.7, 101.8, 101.4, 98.6, 80.0, 79.2, 77.9, 76.8, 75.1, 74.4, 71.7, 71.0,
0.9, 68.8, 68.5, 67.9, 66.8, 56.0, 35.6, 20.7, 17.5. HRMS calc. for
C H NaO [M þ Na] :1003.3875, found: 1003.3898.
þ
58
60
14
4
-Benzoxyl-3-methoxylphenylethyl 2-O-acetyl-3,4-di-O-benzyl-a-L-rhamnopyra-
nosyl-(1!3)-2-O -benzoyl-4,6-O- benzylidene-b-D-glucopyranoside (17b)
2
D
0
White solid, R ¼ 0.45 (petroleum-EtOAc 3:1). ½aꢃ ꢁ9.2 (c, 0.75 in CHCl ).
f
3
1
H NMR (400 MHz, CDCl ) d 7.99 (2 H, d, J ¼ 7.2 Hz, Ar-H), 7.56–7.19
3
(
5
23H, m, Ar-H), 6.66 (1 H, d, J ¼ 0.8 Hz, H-2), 6.57–6.52 (2H, m, H-5, 6),
.52 (1 H, s, PhCHO ), 5.32 (1 H, t, J ¼ 8.0 Hz, H-2 ), 5.19 (1H, dd,
2
Glu
J ¼ 3.2, 2.0 Hz, H-2
), 4.96 (2 H, s, PhCH O-), 4.81 (1 H, appar. s, H-
Rham
2
1
4
), 4.79 (1 H, d, J ¼ 11.6Hz, PhCH ), 4.65 (1 H, d, J ¼ 7.6 Hz, H-1Glu),
Rham
2
.57 (1 H, d, J ¼ 10.8 Hz, PhCH ), 4.47 (1H, d, J ¼ 10.8Hz, PhCH ), 4.37
2
2
(
1 H, d, J ¼ 10.8Hz, PhCH ), 4.36 (1 H, dd, J ¼ 10.8, 5.2 Hz), 4.09–4.00 (3H,
2
m), 3.83 (1 H, dd, J ¼ 9.2, 3.2Hz), 3.80 (3 H, s, -OMe), 3.78 (1 H, t,
J ¼ 10.4Hz), 3.67 (1 H, t, J ¼ 9.2Hz), 3.64 (1H, m), 3.53 (1H, m, H-5 ),
Glu
3
.23 (1 H, t, J ¼ 9.6 Hz), 2.74 (2 H, m, ArCH CH O-), 1.80 (3H, s, -OAc),
2
2
13
0
.90 (3H, d, J ¼ 6.4 Hz, H-6
). C NMR (100 MHz, CDCl ) d 169.3
3
Rham
(C ¼ O), 164.9 (C ¼ O), 149.4, 146.6, 138.7, 138.1, 137.4, 136.9, 133.2, 131.5,

1
2
Y. ZHAO ET AL.
1
1
1
7
29.9, 129.9, 129.3, 129.0, 128.5, 128.5, 128.4, 128.4, 128.3, 128.3, 128.2,
28.2, 128.1, 128.1, 128.1, 128.1, 127.7, 127.7, 127.7, 127.6, 127.5, 127.2,
27.2, 126.3, 126.3, 120.8, 113.8, 112.8 (Ar), 101.7, 101.3, 98.5, 79.9, 79.1,
7.8, 75.0, 74.4, 71.6, 70.9, 70.9, 68.7, 68.4, 67.9, 66.7, 55.9, 35.7, 20.6, 17.4.
13
(one C signal may overlapped with CDCl solvent peaks) HRMS calc. for
3
þ
C H NaO [Mþ Na] :1003.3875, found: 1003.3882.
58
60
14
4
2
-Benzoxylphenylethyl 2-O-acetyl-3,4-di-O-benzyl-a-L-rhamnopyranosyl-(1!3)-
-O-benzoyl-4,6-O- benzylidene-b-D-glucopyranoside (17c)
20
White solid, R ¼ 0.27 (petroleum-EtOAc 4:1). ½aꢃ ꢁ9.1 (c, 0.9 in
f
D
1
CHCl ). H NMR (400 MHz, CDCl ) d 8.00 (2 H, d, J ¼ 7.6 Hz, Ar-H),
3
3
7
.56–7.19 (23 H, m, Ar-H), 6.99 (2 H, d, J ¼ 8.4 Hz, H-2, 6), 6.65 (2 H, d,
J ¼ 8.4 Hz, H-3, 5), 5.50 (1 H, s, PhCHO ), 5.32 (1 H, dd, J ¼ 8.4, 8.0 Hz,
2
H-2 ), 5.20 (1 H, dd, J ¼ 2.8, 1.6 Hz, H-2
Glu
), 4.87–4.78 (4 H, m), 4.63
Rham
(
1 H, d, J ¼ 7.6 Hz, H-1 ), 4.58 (1 H, d, J ¼ 10.8 Hz, PhCH ), 4.47 (1 H, d,
Glu
2
J ¼ 10.8 Hz, PhCH ), 4.38 (1 H, d, J ¼ 10.8 Hz, PhCH ), 4.36 (1 H, dd,
2
2
J ¼ 9.6, 4.8 Hz), 4.09–3.98 (3 H, m), 3.84 (1 H, dd, J ¼ 9.6, 3.2 Hz), 3.77
1 H, t, J ¼ 10.4 Hz), 3.66 (1 H, t, J ¼ 9.2 Hz), 3.62 (1 H, m), 3.52 (1 H, td,
J ¼ 9.6, 4.8 Hz, H-5 ), 3.24 (1 H, t, J ¼ 9.6 Hz), 2.80–2.71 (2 H, m,
(
Glu
1
3
ArCH CH O-), 1.80 (3 H, s, -OAc), 0.90 (3 H, d, J ¼ 6.0 Hz, H-6
).
Rham
C
2
2
NMR (100 MHz, CDCl ) d 169.4 (C ¼ O), 165.0 (C ¼ O), 157.3, 138.8,
3
1
1
1
1
6
38.2, 137.2, 137.0, 133.4, 130.9, 130.1, 130.1, 130.0, 130.0, 129.5, 129.1,
28.7, 128.7, 128.5, 128.5, 128.4, 128.4, 128.4, 128.4, 128.3, 128.3, 128.2,
28.2, 128.0, 127.8, 127.8, 127.7, 127.6, 127.5, 127.5, 126.4, 126.4, 114.7,
14.7 (Ar), 101.8, 101.3, 98.6, 80.0, 79.2, 77.9, 75.1, 74.5, 71.8, 71.0, 69.9,
1
3
8.8, 68.5, 67.9, 66.8, 35.2, 20.8, 17.5. (one C signal may overlapped
with CDCl
solvent peaks) HRMS calc. for C H NaO
57 58 13
3
þ
[
M þ Na] :973.3770, found: 973.3776.
3
,4-Dibenzoxylphenylethyl 2-O-acetyl-3,4-di-O-benzyl-a-L-rhamnopyranosyl-
(
1!3)-2-O-benzoyl-4,6-O- benzylidene-b-D-glucopyranoside (17d)
20
D
White solid, R ¼ 0.50 (petroleum-EtOAc 3:1). ½aꢃ ꢁ10.9 (c, 1.24 in
f
1
CHCl ). H NMR (400 MHz, CDCl ) d 7.98 (2 H, d, J ¼ 7.6 Hz, Ar-H),
3
3
7
.54–7.18 (28 H, m, Ar-H), 6.72 (1 H, s, H-2), 6.58 (2 H, m, H-5, 6), 5.51
(
1
1 H, s, PhCHO ), 5.30 (1 H, t, J ¼ 8.4 Hz, H-2 ), 5.18 (1 H, dd, J ¼ 2.4,
2
Glu
.6 Hz, H-2
), 5.07 (2 H, s, PhCH O-), 4.95 (2 H, s, PhCH O-), 4.80
Rham 2 2
(
1 H, appar. s, H-1Rham), 4.78 (1 H, d, J ¼ 10.8 Hz, PhCH ), 4.60 (1 H, d,
2
J ¼ 7.6 Hz, H-1 ), 4.56 (1 H, d, J ¼ 10.8 Hz, PhCH ), 4.46 (1 H, d,
Glu
2
J ¼ 10.8 Hz, PhCH ), 4.37 (1 H, d, J ¼ 10.8 Hz, PhCH ), 4.36 (1 H, dd,
2
2
J ¼ 10.4, 4.8 Hz), 4.06 (1 H, t, J ¼ 9.2 Hz), 4.04–3.98 (2 H, m), 3.83 (1 H,
dd, J ¼ 9.6, 3.6 Hz), 3.78 (1 H, t, J ¼ 10.0 Hz), 3.66 (1 H, t, J ¼ 9.6 Hz),

JOURNAL OF CARBOHYDRATE CHEMISTRY
13
3
.60 (1 H, m), 3.51 (1 H, td, J ¼ 9.6, 4.8 Hz, H-5Glu), 3.23 (1 H, t,
J ¼ 9.6 Hz), 2.71 (2 H, m, ArCH CH O-), 1.79 (3 H, s, -OAc), 0.90 (3 H,
2
2
1
3
d, J ¼ 6.4 Hz, H-6
). C NMR (100 MHz, CDCl ) d 169.4 (C ¼ O),
Rham
3
1
1
1
1
1
7
65.0 (C ¼ O), 148.9, 147.6, 138.8, 138.2, 137.6, 137.6, 137.1, 133.3,
31.8, 130.0, 130.0, 129.5, 129.1, 128.5, 128.5, 128.5, 128.5, 128.5, 128.5,
28.4, 128.4, 128.4, 128.4, 128.3, 128.3, 128.2, 128.2, 127.8, 127.8, 127.8,
27.8, 127.7, 127.6, 127.5, 127.5, 127.4, 127.4, 126.4, 126.4, 122.0, 116.1,
15.1 (Ar), 101.8, 101.5, 98.7, 80.0, 79.3, 78.0, 75.1, 74.5, 71.8, 71.4, 71.4,
1
3
1.0, 68.8, 68.5, 68.0, 66.8, 35.7, 20.8, 17.5. (one C signal may over-
lapped with CDCl solvent peaks) HRMS calc. for C H NaO
14
3
64 64
þ
[
M þ Na] :1079.4188, found: 1079.4218.
General procedure for the preparation of 18a-d
7a-d (0.05 mmol, 1.0 equiv) and DTT (0.1 mmol, 2.0 equiv) was dissolved
in CH Cl (0.5 mL), followed by quick addition of CSA (0.05 mmol, 1.0
1
2
2
equiv), the reaction mixture was stirred at room temperature for 8 h,
diluted with EtOAc, washed with water and brine, dried (Na SO ), concen-
2
4
trated, and purified by silica gel column chromatography to give the depro-
tection of benzylidene product 18a-d.
3
-Benzoxyl-4-methoxylphenylethyl 2-O-acetyl-3,4-di-O-benzyl-a-L-rhamnopyra-
nosyl-(1!3)-2-O-benzoyl-b-D- glucopyranoside (18a)
White solid, R ¼ 0.24 (petroleum-EtOAc 1:1). ½aꢃ þ19.8 (c, 0.41 in
2
D
0
f
1
CHCl ). H NMR (400 MHz, CDCl ) d 8.03–8.01 (2 H, d, J ¼ 8.0 Hz, Ar-H),
3
3
7
6
.58–7.11 (18 H, m, Ar-H), 6.66 (1 H, brs, H-2), 6.63 (1 H, d, J ¼ 8.0 Hz, H-
), 6.50 (1 H, d, J ¼ 8.0 Hz, H-5), 5.14 (1 H, t, J ¼ 8.8 Hz, H-2 ), 5.06 (2 H,
Glu
s, PhCH O-), 4.95 (1 H, appar. s, H-2
), 4.84–4.82 (2 H, m), 4.54 (1 H,
Rham
2
d, J ¼ 8.0 Hz, H-1 ), 4.52 (1 H, d, J ¼ 11.2 Hz, PhCH ), 4.21 (2 H, s,
Glu
2
PhCH ), 4.04–4.00 (2 H, m), 3.98–3.90 (2 H, m), 3.84–3.77 (2 H, m), 3.71
2
(
3 H, s, -OMe), 3.68–3.56 (3 H, m), 3.41–3.34 (2 H, m), 2.70 (2 H, m,
ArCH CH O-), 2.12 (1 H, brs. -OH), 1.97 (3 H, s, -OAc), 1.30 (3 H, d,
2
2
1
3
J ¼ 6.0 Hz, H-6Rham). C NMR (100 MHz, CDCl ) d 170.0 (C ¼ O), 165.3
3
(
1
1
8
C ¼ O), 148.2, 148.0, 138.3, 137.7, 137.4, 133.4, 130.9, 129.9, 129.9, 129.8,
28.7, 128.7, 128.6, 128.6, 128.5, 128.5, 128.5, 128.5, 128.3, 128.3, 128.0,
28.0, 127.9, 127.9, 127.8, 127.5, 127.5, 121.6, 115.1, 111.8 (Ar), 101.0, 99.8,
6.6, 79.4, 77.0, 75.4, 75.3, 72.1, 71.5, 71.0, 70.9, 70.4, 69.6, 68.8, 62.6, 56.0,
þ
3
5.6, 21.0, 18.2. HRMS calc. for C H NaO [M þ Na] : 915.3562,
5
1
56
14
found: 915.3549.

1
4
Y. ZHAO ET AL.
3
,4-Dibenzoxylphenylethyl 2-O-acetyl-3,4-di-O-benzyl-a-L-rhamnopyranosyl-
(
1!3)-2-O-benzoyl-b-D- glucopyranoside (18d)
2
D
0
White solid, R ¼ 0.28 (petroleum-EtOAc 1:1). ½aꢃ þ19.7 (c, 0.3 in
f
1
CHCl ). H NMR (400 MHz, CDCl ) d 8.01 (2 H, dd, J ¼ 8.4, 1.2 Hz, Ar-
3
3
H), 7.54 (1 H, t, J ¼ 7.6 Hz, Ar-H), 7.44–7.20 (20 H, m, Ar-H), 7.11 (2 H, m,
Ar-H), 6.72 (1 H, br s, H-2), 6.61–6.56 (2 H, m, H-5,6), 5.14 (1 H, t,
J ¼ 8.8 Hz, H-2’), 5.06 (2 H, s, -ArOCH Ph), 4.96 (2 H, s, -ArOCH Ph), 4.94
2
2
0
0
(
1 H, dd, J ¼ 2.8, 2.4 Hz, H-2 ), 4.83–4.01 (2 H, m), 4.55 (1 H, d, J ¼ 8.0 Hz,
H-1’), 4.51 (1 H, d, J ¼ 10.8 Hz), 4.19 (2 H, s, ArCH ), 4.00 (2 H, m), 3.92
2
(
3
(
(
1
1
1
2 H, m), 3.82 (1 H, dd, J ¼ 9.2, 3.2 Hz), 3.78 (1 H, brs), 3.67–3.57 (3 H, m),
.39 (1 H, m), 3.36 (1 H, t, J ¼ 9.6 Hz), 2.71 (2 H, m, ArCH CH O-), 2.05
2
2
13
00
1 H, br s), 1.97 (3 H, s, -OAc), 1.30 (3 H, d, J ¼ 6.0 Hz, H-6 ). C NMR
100 MHz, CDCl ) d 170.0 (C ¼ O), 165.3 (C ¼ O), 148.8, 147.5, 138.3,
3
37.7, 137.6, 137.6, 133.4, 131.8, 129.9, 129.9, 129.7, 128.7, 128.7, 128.6,
28.6, 128.6, 128.6, 128.5, 128.5, 128.5, 128.5, 128.3, 128.3, 128.0, 128.0,
27.9, 127.8, 127.8, 127.8, 127.5, 127.5, 127.4, 127.4, 121.9, 116.0, 115.0
(
7
Ar), 101.0, 99.8, 86.8, 79.3, 77.0, 75.4, 75.3, 72.0, 71.5, 71.3, 71.3, 70.9,
0.5, 69.6, 68.8, 62.6, 35.7, 21.0, 18.2. HRMS calc. for C H NaO
14
5
7
60
þ
[
M þ Na] : 991.3881, found: 991.3903.
General procedure for the preparation of 1–4
8a–d (0.05 mmol, 1.0 equiv) was dissolved in methanol (1.0 mL), followed
1
by the addition of NaOMe (0.05 mmol, 1.0 equiv), the reaction mixture was
ꢂ
stirred at 50 C until the completion of deprotection of acyl group, the
reaction mixture was evaporated and purified by silica gel column chroma-
tography. After that, the obtained product was dissolved in methanol
(
1 mL), the solution was added to 30 wt% Pd/C (10% Palladium on acti-
vated carbon) in a Schlenk tube, the reaction system was degassed with H2,
and stirred under H atmosphere at room temperature overnight. The solid
2
materials were filtrated off, and the solution was concentrated. The residue
was chromatographed on a Sephadex LH-20 column (CH Cl /MeOH 1:1)
2
2
to give 1–4 as final products.
Darendoside B (1)
2
D
0
Colorless glass, R ¼ 0.42 (EtOAc:MeOH:H O 39:11:4). ½aꢃ ꢁ43.8 (c, 0.13
f
2
1
in CH OH). H NMR (400 MHz, methanol-d ) d 6.81 (1 H, d, J ¼ 8.4 Hz,
3
4
H-5), 6.72 (1 H, d, J ¼ 2.0 Hz, H-2), 6.67 (1 H, dd, J ¼ 8.4, 2.0 Hz, H-6), 5.15
0
0
(
1 H, d, J ¼ 2.0 Hz, H-1 ), 4.29 (1 H, d, J ¼ 8.0 Hz, H-1’), 4.07–3.97 (2 H,
m), 3.95 (1 H, m), 3.87 (1 H, dd, J ¼ 11.6, 2.0 Hz), 3.81 (3 H, s, -OMe),
.74–3.66 (3 H, m), 3.49 (1 H, t, J ¼ 8.8 Hz), 3.40 (1 H, t, J ¼ 9.6 Hz), 3.31
1 H, m), 3.31–3.26 (2 H, m), 2.80 (2 H, m, H-7), 1.25 (3 H, d, J ¼ 6.4 Hz,
3
(

JOURNAL OF CARBOHYDRATE CHEMISTRY
15
0
0
13
H-6 ). C NMR (100 MHz, methanol-d ) d 147.5, 147.3, 132.9, 121.1,
4
1
17.1, 112.9, 104.2, 102.7, 84.5, 77.8, 75.6, 74.0, 72.3, 72.2, 72.0, 70.2, 70.0,
þ
62.7, 56.5, 36.5, 17.9. HRMS calc. for C H NaO [M þ Na] : 499.1786,
2
1
32
12
found: 499.1762.
Cistanoside E (2)
2
D
0
Colorless glass, R ¼ 0.40 (EtOAc:MeOH:H O 39:11:4). ½aꢃ ꢁ48.0 (c, 0.20
f
2
1
in CH OH). H-NMR (400 MHz, methanol-d ) d 6.84 (1 H, d, J ¼ 2.0 Hz,
3
4
H-2), 6.70 (1 H, d, J ¼ 8.0 Hz, H-5), 6.67 (1 H, dd, J ¼ 8.0, 2.0 Hz, H-6), 5.16
0
0
(
(
-
1 H, d, J ¼ 1.2 Hz, H-1 ), 4.31 (1 H, d, J ¼ 7.6 Hz, H-1’), 4.04 (1 H, m), 3.99
1 H, m), 3.95 (1 H, m), 3.87 (1 H, dd, J ¼ 12.0, 2.0 Hz), 3.83 (3 H, s,
OMe), 3.76–3.66 (3 H, m), 3.50 (1 H, t, J ¼ 8.8 Hz), 3.40 (1 H, t, J ¼ 9.6 Hz),
3
.37–3.32 (2 H, m), 3.28 (1 H, m), 2.84 (2 H, m, H-7), 1.25 (3 H, d,
0
0
13
J ¼ 6.4 Hz, H-6 ). C NMR (100 MHz, methanol-d ) d 148.8, 145.8, 131.5,
4
1
22.4, 116.0, 113.7, 104.1, 102.7, 84.4, 77.8, 75.6, 73.9, 72.3, 72.0, 70.2, 70.0,
þ
6
2.6, 56.4, 36.7, 17.9. HRMS calc. for C H NaO [M þ Na] : 499.1786,
2
1
32
12
found: 499.1803.
Cistanoside G (3)
2
D
0
White solid, R ¼ 0.44 (EtOAc:MeOH:H O 39:11:4). ½aꢃ ꢁ52.5 (c, 0.08 in
f
2
1
CH OH). H-NMR (400 MHz, methanol-d ) d 7.06 (2 H, d, J ¼ 8.4 Hz, H-2,
3
4
00
6
), 6.69 (2 H, d, J ¼ 8.0 Hz, H-3, 5), 5.15 (1 H, appar. s, H-1 ), 4.29 (1H, d,
J ¼ 8.0 Hz, H-1’), 4.06–3.96 (2 H, m), 3.94 (1 H, m), 3.86 (1H, dd, J ¼ 12.0,
2
3
.0 Hz), 3.73–3.66 (3 H, m), 3.49 (1 H, t, J ¼ 8.8 Hz), 3.40 (1H, t, J ¼ 9.6 Hz),
.31 (1H, m), 3.30–3.26 (2 H, m), 2.82 (2 H, m, H-7), 1.24 (3 H, d,
0
0
13
J ¼ 6.0 Hz, H-6 ). C NMR (100MHz, methanol-d ) d 156.8, 130.9, 130.9,
4
1
7
30.8, 116.1, 116.1, 104.2, 102.8, 84.5, 77.9, 75.6, 74.0, 72.4, 72.2, 72.1, 70.2,
0.1, 62.7, 36.4, 17.9. C H NaO [Mþ Na] : 469.1680, found: 469.1662.
þ
20
30
11
Decaffeoyl acteoside (4)
Colorless glass, Rf ¼ 0.33 (EtOAc:MeOH:H O 39:11:4). H-NMR
1
2
(
400 MHz, methanol-d ) d 6.68 (1 H, d, J ¼ 2.0 Hz, H-2), 6.67 (1 H, d,
4
J ¼ 8.0 Hz, H-5), 6.55 (1 H, dd, J ¼ 8.0, 2.0 Hz, H-6), 5.16 (1 H, appar. s, H-
0
0
1
), 4.29 (1 H, d, J ¼ 8.0 Hz, H-1’), 4.03 (1 H, m), 3.99 (1 H, m), 3.94 (1 H,
m), 3.87 (1 H, dd, J ¼ 12.0, 1.6 Hz), 3.72–3.66 (3 H, m), 3.49 (1 H, t,
J ¼ 8.8 Hz), 3.42–3.37 (2 H, m), 3.32–3.26 (2 H, m), 2.77 (2 H, m, H-7), 1.24
0
0
13
(
1
7
3 H, d, J ¼ 6.4 Hz, H-6 ). C NMR (100 MHz, methanol-d ) d 146.1,
4
44.6, 131.5, 121.2, 117.1, 116.3, 104.2, 102.7, 84.4, 77.8, 75.6, 74.0, 72.3,
2.2, 72.1, 70.2, 70.0, 62.6, 36.5, 17.9. HRMS calc. for C H NaO
12
2
0
30
þ
[
M þ Na] : 485.1629, found: 485.1647.

1
6
Y. ZHAO ET AL.
General procedure for the preparation of 20a and 20d
A solution of 19 (1.0 equiv), 18a or 18d (1.0 equiv) and DTBMP (1.0
equiv) in CH Cl (C ¼ 0.05 M) in the presence of 4 Å MS (100 wt%) was
2
2
ꢂ
ꢂ
stirred at 0 C for 10 min, Tf O (1.0 equiv) was added, the solution was
stirred at 0 C for 30 min. The reaction mixture was quenched with Et N,
2
3
then filtered and extracted with EtOAc. The organic phase was washed
with brine, dried (Na SO ), concentrated, and purified by silica gel column
2
4
chromatography to give compound 20a or 20d.
2
-(3-Benzyloxy-4-methoxyphenyl)ethyl 2-O-benzoyl-3-O-(2-O-acetyl-3,4-di-O-
benzyl-a-L -rhamnopynosyl)-6-(2,3,4,6- tetra-O-benzoyl-b-D-glucopyranosyl)-
b-D-glucopyranoside (20a)
1
White solid, R ¼ 0.51 (petroleum -EtOAc 3:2). H NMR (400 MHz,
f
CDCl ) d 8.03 (2 H, d, J ¼ 7.6 Hz, Ar-H), 7.95 (2 H, d, J ¼ 7.2 Hz, Ar-H),
3
7
.90–7.87 (4 H, m, Ar-H), 7.80 (2 H, d, J ¼ 7.6 Hz, Ar-H), 7.56–7.26 (23 H,
m, Ar-H), 7.22–7.20 (5 H, m, Ar-H), 7.13–7.11 (2 H, m, Ar-H), 6.61 (1 H,
br s, H-2), 6.57 (1 H, d, J ¼ 8.0 Hz, H-6), 6.42 (1 H, d, J ¼ 8.4 Hz, H-5), 5.88
0
00
000
(
1 H, t, J ¼ 9.6 Hz, H-3 ), 5.67 (1 H, t, J ¼ 9.6 Hz, H-4 ), 5.53 (1 H, dd,
0
00
J ¼ 9.6, 8.0 Hz, H-2 ), 5.07–5.00 (3 H, m, ArOCH Ph, H-2’), 4.96 (1 H, d,
2
0
00
J ¼ 8.0 Hz, H-1 ), 4.92 (1 H, br s, ArOCH Ph), 4.82 (1 H, d, J ¼ 10.8 Hz),
2
0
00
4
.73 (1 H, d, J ¼ 1.2 Hz, H-1’’), 4.64 (1 H, dd, J ¼ 12.0, 2.8 Hz, H-6 a), 4.50
(
4
2 H, m), 4.30 (1 H, d, J ¼ 8.0 Hz, H-1’), 4.27 (1 H, appar. d, J ¼ 11.2 Hz),
.24 (1 H, d, J ¼ 12.8 Hz, PhCH ), 4.19 (1 H, d, J ¼ 11.2 Hz, PhCH ),
2
2
4
.16–4.11 (1 H, m), 3.88–3.73 (5 H, m), 3.66 (3 H, s, OMe), 3.51–3.46 (2 H,
m), 3.36–3.28 (3 H, m), 2.58–2.45 (2 H, m), 1.94 (3 H, s, OAc), 1.26 (3 H, d,
1
3
J ¼ 6.0 Hz, CH ). C NMR (100 MHz, CDCl ) d 165.1, 161.5, 161.2, 160.6,
3
3
1
1
1
1
1
8
6
60.4, 160.4, 143.3, 143.1, 133.6, 133.0, 132.8, 128.8, 128.6, 128.5, 128.5,
26.6, 125.2, 125.2, 125.2, 125.2, 125.1, 125.1, 125.1, 125.1, 125.0, 124.6,
24.2, 123.8, 123.8, 123.8, 123.8, 123.8, 123.8, 123.8, 123.8, 123.7, 123.7,
23.7, 123.7, 123.7, 123.5, 123.5, 123.5, 123.5, 123.2, 123.2, 123.2 123.2,
23.1, 123.1, 122.8, 122.8, 122.8, 122.8, 116.9, 110.2, 107.0, 97.0, 95.9, 95.1,
1.7, 74.6, 70.5, 70.4, 68.2, 67.6, 67.4, 67.3, 66.7, 66.2, 65.7, 65.6, 65.0, 64.7,
4.0, 51.2, 30.6, 16.2, 13.3.
2
-(3,4-Di-benzyloxy)ethyl 2-O-benzoyl-3-O-(2-O-acetyl-3,4-di-O-benzyl-a-L-rham-
nopynosyl)-6-(2,3,4,6- tetra-O-benzoyl-b-D-glucopyranosyl)-b-D-glucopyrano-
side (20d)
1
White solid, R ¼ 0.42 (petroleum -EtOAc 3:2). H NMR (400 MHz,
f
CDCl ) d 8.04 (2 H, d, J ¼ 8.0 Hz, Ar-H), 7.96 (2 H, d, J ¼ 8.0 Hz, Ar-H),
3
7
.91–7.88 (4 H, m, Ar-H), 7.81 (2 H, d, J ¼ 8.0 Hz), 7.54–7.46 (4 H, m, Ar-
H), 7.44–7.21 (29 H, m, Ar-H), 7.14–7.12 (2 H, m, Ar-H), 6.69 (1 H, br s,

JOURNAL OF CARBOHYDRATE CHEMISTRY
17
H-2), 6.55 (1 H, d, J ¼ 8.0 Hz, H-6), 6.52 (1 H, d, J ¼ 8.0 Hz, H-5), 5.89
1 H, t, J ¼ 9.6 Hz, H-3 ), 5.68 (1 H, t, J ¼ 9.6 Hz, H-4 ), 5.55 (1 H, dd,
0
00
000
(
0
00
J ¼ 9.6, 8.0 Hz, H-2 ), 5.06 (2 H, s, -ArOCH Ph), 5.04 (1 H, m, H-2’), 4.97
2
0
00
00
(
4
2
1 H, d, J ¼ 8.0 Hz, H-1 ), 4.92 (2 H, s, -ArOCH Ph), 4.92 (1 H, m, H-2 ),
2
0
0
.83 (1 H, d, J ¼ 10.8 Hz), 4.74 (1 H, br s, H-1 ), 4.65 (1 H, dd, J ¼ 12.0,
0
00
000
.0 Hz, H-6 a), 4.52 (1 H, m, H-6 b), 4.52 (1 H, m), 4.33 (1 H, d,
J ¼ 8.0 Hz, H-1’), 4.29 (1 H, appar. d, J ¼ 10.8 Hz), 4.24 (1 H, d, J ¼ 11.6 Hz,
PhCH -), 4.19 (1 H, d, J ¼ 11.6 Hz, PhCH -), 4.15 (1 H, m, H-5 ), 3.86
000
2
2
0
0
(
1 H, m, H-5 ), 3.81–3.74 (4 H, m), 3.53–3.47 (2 H, m), 3.37–3.29 (3 H, m),
2
.60–2.46 (2 H, m, -OCH CH Ar), 1.95 (3 H, s, -OAc), 1.27 (3 H, d,
2
2
1
3
J ¼ 6.0 Hz). C NMR (100 MHz, CDCl ) d 169.9, 166.3, 165.9, 165.3, 165.2,
3
1
1
1
1
1
1
7
6
1
65.2 (C ¼ O), 148.7, 147.3, 138.4, 137.7, 137.7, 137.7, 133.6, 133.4, 133.4,
33.3, 133.3, 132.3, 130.0, 130.0, 129.9, 129.9, 129.9, 129.9, 129.9, 129.8,
29.8, 129.8, 129.8, 129.8, 129.7, 129.3, 128.9, 128.6, 128.5, 128.5, 128.5,
28.5, 128.5, 128.5, 128.5, 128.5, 128.5, 128.5, 128.5, 128.5, 128.5, 128.5,
28.5, 128.5, 128.4, 128.3, 128.3, 128.0, 128.0, 127.8, 127.8, 127.8, 127.7,
27.5, 127.5, 127.3, 127.3, 121.9, 115.9, 115.0, 101.7, 100.6, 99.8, 86.5, 79.4,
7.0, 75.3, 75.1, 73.0, 72.4, 72.1, 72.0, 71.4, 71.3, 71.2, 70.5, 70.3, 69.8, 69.7,
þ
9.4, 68.7, 63.1, 35.4, 20.9, 18.1. HRMS calc. for C H NaO [M þ Na] :
9
1
86
23
569.5452, found: 1569.5491.
General procedure for the preparation of PhGs 5 and 6
A solution of 20a or 20d (1.0 equiv) in methanol and CH Cl was added
2
2
ꢂ
NaOMe (1.0 equiv)), the reaction mixture was stirred at 50 C until the
completion of the reaction, the reaction mixture was evaporated and puri-
fied by silica gel column chromatography. After that, the obtained product
was dissolved in methanol, the solution was added to 30 wt% Pd/C (10%
Palladium on activated carbon) in a Schlenk tube, the reaction system was
degassed with H , and stirred under H atmosphere at room temperature
2
2
overnight. The solid materials were filtrated off, and the solution was con-
centrated. The residue was chromatographed on a Sephadex LH-20 column
(
CH Cl /MeOH 1:1) to give PhGs 5 or 6.
2 2
Kankanoside F (5)
1
White solid. H NMR (400 MHz, CD OD) d 6.69 (1 H, d, J ¼ 2.0 Hz, H-2),
3
6
.67 (1 H, d, J ¼ 8.0 Hz, H-5), 6.56 (1 H, dd, J ¼ 8.0, 2.0 Hz, H-6), 5.16 (1 H,
0
00
d, J ¼ 1.2 Hz, H-1’’), 4.37 (1 H, d, J ¼ 7.6 Hz, H-1 ), 4.30 (1 H, d, J ¼ 8.0 Hz,
H-1’), 4.15 (1 H, dd, J ¼ 11.2, 1.2 Hz, H-6’), 4.00 (2 H, m), 3.93 (1 H, m),
3
3
.87 (1 H, m), 3.80 (1 H, m), 3.70 (3 H, m), 3.46 (3 H, m), 3.38 (2 H, m),
1
3
.24 (4 H, m), 2.78 (2 H, m), 1.24 (3 H, d, J ¼ 6.4 Hz). C NMR (100 MHz,
CD OD) d 146.1, 144.7, 131.5, 121.3, 117.1, 116.3, 104.9, 104.3, 102.7, 84.0,
3
78.0, 78.0, 77.0, 75.7, 75.1, 74.0, 72.4, 72.3, 72.3, 71.6, 70.0, 69.9, 69.7, 62.7,

1
8
Y. ZHAO ET AL.
3
6.6, 17.9. HRMS calc. for C H NaO
[M þ Na]þ: 647.2158,
2
6
40
17
found: 647.2163.
The NMR data of Leonoside F (6) is consistent with the literature previ-
[
5a]
ously reported by us.
2
-(3-Benzyloxy-4-methoxyphenyl)ethyl 2-O-benzoyl-3-O-(2-O-acetyl-3,4-di-O-
benzyl-a-L -rhamnopynosyl)-6-(2,3,4,6- tetra-O-benzoyl-b-D-galatopyranosyl)-
b-D- glucopyranoside (22)
A solution of 21 (50.0 mg, 0.06 mmol), 18a (56.3 mg, 0.06 mmol) and
DTBMP (12.9 mg, 0.06 mmol) in CH Cl (1.26 mL) in the presence of 4 Å
2
2
ꢂ
MS (100 wt%) was stirred at 0 C for 10 min, Tf O (10.6 lL, 0.06 mmol)
2
was added, the solution was stirred at for 30 min. The reaction mixture was
quenched with Et N, then filtered and extracted with EtOAc. The organic
3
phase was washed with brine, dried (Na SO ), concentrated, and purified
2
4
by silica gel column chromatography to give compound 22 (70.5 mg, 76%
2
D
0
yield) as white solid, R ¼ 0.47 (petroleum -EtOAc 3:2). ½aꢃ þ27.8 (c, 0.09
f
1
in CHCl ). H-NMR (400 MHz, CDCl ) d 8.07 (2 H, d, J ¼ 7.6 Hz, Ar-H),
3
3
8
.02 (2 H, d, J ¼ 7.2 Hz, Ar-H), 7.95 (2 H, d, J ¼ 7.2 Hz, Ar-H), 7.88 (2 H, d,
J ¼ 7.2 Hz, Ar-H), 7.76 (2 H, d, J ¼ 7.2 Hz, Ar-H), 7.61–7.12 (30 H, m, Ar-
H), 6.61 (1 H, appar. s, H-2), 6.56 (1 H, appar. d, J ¼ 8.0 Hz, H-6), 6.41
00
(
1 H, d, J ¼ 8.0 Hz, H-5), 5.99 (1 H, d, J ¼ 3.2 Hz, H-1 ), 5.81 (1 H, dd,
J ¼ 9.6, 8.4 Hz), 5.60 (1 H, dd, J ¼ 10.4, 3.2 Hz), 5.08–5.01 (3 H, m),
4
.96–4.93 (2 H, m), 4.83 (1 H, d, J ¼ 10.8 Hz, ArCH ), 4.74 (1 H, appar. s),
2
4
.70 (1 H, dd, J ¼ 11.2, 6.4 Hz), 4.52 (1 H, d, J ¼ 10.8 Hz, ArCH ), 4.43–4.39
2
(
4 H, m), 4.24 (1 H, d, J ¼ 11.2 Hz, ArCH ), 4.19 (1 H, d, J ¼ 11.2 Hz,
2
ArCH ), 3.86 (1 H, dd, J ¼ 9.2, 6.4 Hz), 3.81–3.73 (4 H, m), 3.66 (3 H, s,
2
-
1
OMe), 3.55–3.47 (2 H, m), 3.37–3.29 (3 H, m), 2.58–2.42 (2 H, m, H-7),
00
13
.95 (3 H, s, -OAc), 1.27 (3 H, d, J ¼ 6.4 Hz, H-6 ). C NMR (100 MHz,
CDCl ) d 169.9, 166.2, 165.7, 165.7, 165.4, 165.2 (C ¼ O), 148.0, 147.9,
3
1
1
1
1
1
8
6
38.4, 137.7, 137.5, 133.7, 133.4, 133.4, 133.4, 133.3, 131.3, 130.2, 130.2,
30.0, 130.0, 129.9, 129.9, 129.8, 129.8, 129.8, 129.7, 129.7, 129.6, 129.4,
29.2, 128.9, 128.8, 128.8, 128.6, 128.6, 128.6, 128.6, 128.6, 128.6, 128.5,
28.5, 128.5, 128.5, 128.4, 128.4, 128.3, 128.3, 128.0, 128.0, 128.0, 127.9,
27.8, 127.8, 127.5, 127.5, 127.5, 121.7, 115.0, 111.7 (Ar), 102.0, 100.6, 99.9,
6.5, 79.4, 77.0, 75.3, 75.1, 72.0, 71.8, 71.5, 71.5, 70.9, 70.4, 70.4, 70.0, 69.6,
9.5, 68.7, 68.3, 62.2, 56.0, 35.4, 20.9, 18.1. HRMS calc. for C H NaO
23
8
5
82
þ
[
M þ Na] : 1493.5145, found: 1493.5132.
0
00
-epi-Leonoside F (7)
4
A solution of 22 (41 mg, 0.03 mmol) in methanol (1.0 mL) was added
ꢂ
NaOMe (1.5 mg, 0.03 mmol), the reaction mixture was stirred at 50 C until

JOURNAL OF CARBOHYDRATE CHEMISTRY
19
the completion of the reaction, the reaction mixture was evaporated and
purified by silica gel column chromatography. After that, the obtained
product was dissolved in methanol (0.56 mL), the solution was added to
30 wt% Pd/C (10% Palladium on activated carbon) in a Schlenk tube, the
reaction system was degassed with H , and stirred under H atmosphere at
2
2
room temperature overnight. The solid materials were filtrated off, and the
solution was concentrated. The residue was chromatographed on a
Sephadex LH-20 column (CH Cl /MeOH 1:1) to give 7 (15.5 mg, 87% yield
2
2
2
D
0
for two steps) as white solid, R ¼ 0.19 (EtOAc:MeOH:H O 39:11:4). ½aꢃ
f
2
1
3 4
ꢁ
42.0 (c, 0.05 in CH OH). H-NMR (400 MHz, methanol-d ) d 6.82 (1 H,
d, J ¼ 8.0 Hz, H-5), 6.73 (1 H, d, J ¼ 2.0 Hz, H-2), 6.68 (1 H, dd, J ¼ 8.0,
00
000
2
4
(
(
(
(
.0 Hz, H-6), 5.16 (1 H, d, J ¼ 1.2 Hz, H-1 ), 4.33 (1 H, d, J ¼ 7.6 Hz, H-1 ),
.30 (1 H, d, J ¼ 8.0 Hz, H-1’), 4.15 (1 H, dd, J ¼ 11.2, 0.8 Hz), 4.05-3.99
2 H, m), 3.93 (1 H, dd, J ¼ 2.8, 1.6 Hz), 3.81 (3 H, s), 3.79 (1 H, m), 3.75
1 H, m), 3.73-3.68 (3 H, m), 3.56–3.44 (6 H, m), 3.44–3.37 (2 H, m), 3.29
00
13
1 H, m), 2.80 (2 H, m, H-7), 1.24 (3 H, d, J ¼ 6.0 Hz, H-6 ). C NMR
100 MHz, methanol-d ) d 147.5, 147.3, 133.0, 121.2, 117.1, 112.9, 106.8,
4
1
04.1, 101.6, 84.5, 82.7, 78.1, 77.9, 77.8, 75.7, 75.4, 74.3, 72.0, 71.9, 71.3,
þ
70.1, 69.9, 62.7, 62.7, 56.5, 36.5, 17.9. C H NaO [M þ Na] : 661.2314,
2
7
42
17
found: 661.2310.
S-2-Isopropylmercaptobenzyl-3,4-di-O-benzyl-a-L-rhamnopyranosyl-(1!3)-2-O-
benzoyl-4,6-O- benzylidene-1-thio-b-D-glucopyranoside (23)
To a solution of 11 (20 mg, 0.02 mmol) in THF (0.43 mL) was added
N H -H O (0.11 mL, 2.17 mmol), the reaction mixture was stirred at
2
4
2
ꢂ
6
0 C for 30 h, after the reaction mixture was cooled to r.t., it was con-
centrated and diluted with EtOAc, washed with water and brine, dried
Na SO ), concentrated, and purified by silica gel column chromatog-
(
2
4
raphy to give compound 23 (14.8 mg, 78% yield). R ¼ 0.24 (petroleum
f
2
D
0
1
-
EtOAc 4:1). ½aꢃ ꢁ50.8 (c, 1.0 in CHCl ). H NMR (400 MHz, acetone-
3
d ) d 8.02–8.00 (2 H, m, Ar-H), 7.69–7.64 (1 H, m, Ar-H), 7.56–7.20
6
(
21 H, m, Ar-H), 5.70 (1 H, s, PhCHO ), 5.29 (1 H, dd, J ¼ 10.2, 9.0 Hz,
2
0
H-2), 4.88 (1 H, d, J ¼ 10.2 Hz, H-1), 4.87 (1 H, d, J ¼ 2.4 Hz, H-1 ), 4.81
(
(
(
1 H, d, J ¼ 11.2 Hz, ArCH ), 4.62 (1 H, d, J ¼ 11.6 Hz, ArCH ), 4.52
2
2
1 H, d, J ¼ 11.2 Hz, ArCH ), 4.48 (1 H, d, J ¼ 11.6 Hz, ArCH ), 4.36
2
2
1 H, dd, J ¼ 10.4, 4.8 Hz, H-6a), 4.22 (1 H, t, J ¼ 9.0 Hz, H-3), 4.19 (1 H,
d, J ¼ 12.6 Hz, ArCH ), 4.09 (1 H, d, J ¼ 12.6 Hz, ArCH ), 4.04 (1 H, m,
2
2
0
0
0
H-5 ), 3.90 (1 H, m, H-2 ), 3.86-3.80 (3 H, m, H-4, 6 b, 2 -OH), 3.72–3.66
0
0
(
2 H, m, H-3 , 5), 3.88–3.32 (2 H, m, H-4 , SCH(CH ) ), 1.16 (3 H, d,
3 2
J ¼ 6.6 Hz, SCH(CH ) ), 1.13 (3 H, d, J ¼ 6.6 Hz, SCH(CH ) ), 0.86 (3 H,
3
2
13
3 2
0
d, J ¼ 6.0 Hz, H-6 ). C NMR (100 MHz, acetone-d ) d 165.9 (C ¼ O),
6
1
40.6, 140.2, 139.8, 138.7, 136.2, 134.3, 134.0, 131.3, 130.6, 130.5, 130.5,

2
0
Y. ZHAO ET AL.
1
1
8
3
9
29.5, 129.5, 129.5, 129.0, 129.0, 128.9, 128.9, 128.8, 128.8, 128.6, 128.4,
28.4, 128.4, 128.4, 128.1, 128.1, 128.0, 127.2, 127.2 (Ar), 102.2, 101.6,
4.3, 80.0, 80.7, 80.2, 78.0, 75.2, 74.3, 71.6, 71.5, 69.0, 68.6, 68.3, 39.3,
þ
3.3, 23.4, 23.3, 18.0. HRMS calc. for C H NaO S [M þ Na] :
5
0
54
10 2
01.3051, found: 901.3074.
2
-Isopropylmercaptobenzyl 2,3,4-tri-O-benzoyl-a-L-arabinopyranosyl-(1!2)-3,4-
di-O-benzyl-a-L- rhamnopyranosyl-(1!3)-2-O-benzoyl-4,6-O-benzylidene-1-thio-
b-D- glucopyranoside (25)
A solution of 24 (90 mg, 0.14 mmol), 23 (100 mg, 0.11 mmol) and DTBMP
(
47.7 mg, 0.23 mmol) in CH Cl (2.28mL) in the presence of 4Å MS
2 2
ꢂ
(100 wt%) was stirred at 0 C for 10min, Tf O (22.9 lL, 0.14 mmol) was added,
2
ꢂ
the solution was stirred at 0 C for 30 min. The reaction mixture was quenched
with Et N, then filtered and extracted with EtOAc. The organic phase was
3
washed with brine, dried (Na SO ), concentrated, and purified by silica gel col-
2
4
umn chromatography to give compound 25 (134 mg, 89% yield). The NMR
[5c]
data was consistent with the literature previously reported by us.
The preparation and NMR data of 26, 27a, 27d, 8 and 9 are consistent
[
5c]
with the literature previously reported by us.
2
3
-Isopropylmercaptobenzyl 2,3,4,6-tetra-O-benzoyl-b-D-glucopyranosyl-(1!2)-
,4-di-O-benzyl-a-L- rhamnopyranosyl-(1!3)-2-O-benzoyl-4,6-O-benzylidene-1-
thio-b-D- glucopyranoside (28)
A solution of 19 (108 mg, 0.14 mmol), 23 (100 mg, 0.11 mmol) and DTBMP
(
11.7 mg, 0.06 mmol) in CH Cl (2.28 mL) in the presence of 4 Å MS
2 2
ꢂ
(100 wt%) was stirred at 0 C for 10min, Tf O (22.9lL, 0.14 mmol) was added,
2
ꢂ
the solution was stirred at 0 C for 30 min. The reaction mixture was quenched
with Et N, then filtered and extracted with EtOAc. The organic phase was
3
washed with brine, dried (Na SO ), concentrated, and purified by silica gel col-
2
4
umn chromatography to give compound 28 (113 mg, 68% yield) as white solid,
2
D
0
1
R ¼ 0.45 (petroleum-EtOAc 3:1). ½aꢃ ꢁ3.9 (c, 0.66 in CHCl ). H NMR
f
3
(
400 MHz, CDCl ) d 7.97–7.95 (4 H, m, Ar-H), 7.87 (2 H, d, J¼ 7.6 Hz, Ar-H),
3
7
.82 (2 H, d, J¼ 8.0 Hz, Ar-H), 7.76 (2 H, d, J¼ 7.6 Hz, Ar-H), 7.55–7.01 (32 H,
m, Ar-H), 6.94 (2 H, m, Ar-H), 5.58 (1 H, t, J¼ 9.6 Hz), 5.47 (1 H, s, PhCHO ),
2
5
.37–5.29 (2 H, m), 5.25 (1 H, dd, J¼ 9.6, 9.2 Hz), 4.89 (1 H, s, H-1’), 4.69 (1 H,
d, J¼ 8.0 Hz), 4.43 (1 H, d, J¼ 10.4 Hz), 4.37 (2 H, s, PhCH ), 4.33 (1 H, dd,
2
J¼ 10.4, 4.4 Hz), 4.17 (1 H, d, J¼ 13.2 Hz), 4.13 (1 H, d, J¼ 11.2 Hz), 4.01 (1 H,
dd, J¼ 11.6, 3.6 Hz), 3.97–3.989 (3 H, m), 3.85–3.80 (3H, m), 3.72 (1H, t,
J¼ 10.0 Hz), 3.69 (1 H, dd, J¼ 9.2, 2.0 Hz), 3.58 (1 H, t, J¼ 9.6Hz), 3.43 (1H,
m), 3.38 (1 H, m), 3.33 (1 H, hepta. J¼ 6.8 Hz, -SCH(CH ) ), 3.04 (1 H, t,
3
2
J¼ 9.6 Hz), 1.16 (3 H, d, J¼ 6.8 Hz, -SCH(CH ) ), 1.13 (3 H, d, J¼ 6.8 Hz,
3
2

JOURNAL OF CARBOHYDRATE CHEMISTRY
21
1
3
-
1
1
1
1
1
SCH(CH ) ), 0.72 (3 H, d, J¼ 6.0 Hz, H-6’). C NMR (100 MHz, CDCl ) d
3
2
3
66.0, 165.9, 165.4, 165.3, 164.9 (C ¼ O), 139.3, 138.9, 138.6, 137.0, 135.6, 133.8,
33.5, 133.3, 133.2, 133.2, 133.2, 130.4, 130.1, 130.1, 130.1, 130.1, 130.0, 130.0,
29.9, 129.9, 129.9, 129.9, 129.8, 129.6, 129.5, 129.1, 129.0, 128.9, 128.9, 128.6,
28.6, 128.5, 128.5, 128.5, 128.5, 128.4, 128.4, 128.4, 128.4, 128.3, 128.3, 128.2,
28.2, 127.9, 127.6, 127.6, 127.6, 127.5, 127.5, 127.4, 127.2, 126.5, 126.5, 126.5
(
Ar), 101.9 (PhCHO ), 101.6, 99.8 (C-1’), 83.7, 80.5, 79.5, 79.4, 78.3, 76.1, 74.7,
2
7
3.2, 72.7, 72.1, 71.9, 71.7, 70.9, 70.0, 68.7, 68.3, 63.1, 39.0 (-SCH(CH ) ), 33.0,
3
2
2
3.2 (-SCH(CH ) ), 23.1 (-SCH(CH ) ), 17.3 (C-6’). HRMS calc. for
3 2 3 2
þ
C H NaO S [M þ Na] : 1479.4627, found: 1479.4614.
8
4
80
19 2
Compound 29
A solution of 19 (43.3 mg, 0.06 mmol), 23 (40 mg, 0.05 mmol) and DTBMP
(
19.0 mg, 0.09 mmol) in CH Cl (0.91 mL) in the presence of 4 Å MS
2 2
ꢂ
(100 wt%) was stirred at 0 C for 10min, Tf O (9.4lL, 0.06 mmol) was added,
2
ꢂ
the solution was stirred at 0 C for 30 min. The reaction mixture was quenched
with Et N, then filtered and extracted with EtOAc. The organic phase was
3
washed with brine, dried (Na SO ), concentrated, and purified by silica gel col-
2
4
umn chromatography to give compound 29 (45.8 mg, 69% yield) as white solid,
1
R ¼ 0.51 (petroleum-EtOAc 3:1). H NMR (400 MHz, CDCl ) d 8.05–8.01
f
3
(
4 H, m, Ar-H), 7.92 (2 H, d, J¼ 7.2 Hz, Ar-H), 7.82 (2 H, dd, J¼ 8.0, 0.8 Hz,
Ar-H), 7.62–7.56 (2 H, m, Ar-H), 7.50–7.11 (32H, m, Ar-H), 6.70 (2H, m, Ar-
0
0
H), 5.63 (1H, d, J¼ 5.2 Hz, H-1 ), 5.50 (1 H, dd, J¼ 3.2, 0.8 Hz), 5.47 (1 H, s,
PhCHO ), 5.41 (1 H, d, J¼ 8.0 Hz), 5.25 (1 H, dd, J¼ 10.0, 9.2 Hz, H-2), 5.01
2
(
1 H, d, J¼ 1.6 Hz, H-1’), 4.82 (1 H, d, J¼ 11.2 Hz, ArCH ), 4.69 (1 H, m), 4.46
2
(
1 H, d, J¼ 10.0 Hz, H-1), 4.47–4.43 (2 H, m), 4.34 (1 H, dd, J¼ 10.4, 4.8 Hz),
4
.17 (1 H, d, J¼ 13.2 Hz, ArCH ), 4.12 (1 H, dd, J¼ 8.8, 3.6 Hz), 4.08 (1 H, d,
2
J¼ 12.4 Hz, ArCH ), 3.96–3.92 (2 H, m), 3.90 (1 H, dd, J¼ 9.6, 6.4 Hz), 3.83
2
(
1 H, d, J¼ 12.0 Hz, ArCH ), 3.73 (1 H, dd, J¼ 10.4, 10.0 Hz), 3.66–3.61 (2 H,
2
m), 3.58 (1H, t, J¼ 9.2Hz), 3.46 (1H, td, J¼ 9.6, 4.8 Hz), 3.38 (1 H, t,
J¼ 9.6 Hz), 3.21 (1 H, hepta., J¼ 6.4 Hz, -SCH(CH ) ), 1.16 (3 H, d, J¼ 6.4 Hz,
3
2
-
SCH(CH ) ), 1.12 (3 H, d, J¼ 6.4 Hz, -SCH(CH ) ), 0.77 (3 H, d, J¼ 6.0 Hz,
3
2
3 2
13
H-6’). C NMR (100 MHz, CDCl ) d 166.2, 165.3, 165.0, 164.5 (C ¼ O), 139.2,
3
1
1
1
1
38.9, 138.8, 137.0, 135.5, 134.5, 133.7, 133.6, 133.4, 133.2, 133.1, 130.4, 130.4,
30.3, 130.3, 130.1, 130.1, 129.9, 129.9, 129.8, 129.8, 129.7, 129.6, 129.5, 129.2,
29.1, 129.1, 128.8, 128.8, 128.6, 128.6, 128.4, 128.4, 128.4, 128.4, 128.3, 128.3,
28.3, 128.2, 128.2, 128.1, 128.1, 128.1, 127.9, 127.9, 127.9, 127.5, 127.2, 127.1,
27.1, 127.1, 126.7, 126.5, 126.5 (Ar), 121.7 (PhCO ), 102.0 (PhCHO ), 99.5 (C-
1
1
3
2
0
0
’), 97.4 (C-1 ), 83.9 (C-1), 80.1, 79.6, 78.2, 77.9, 75.2, 72.9, 72.2, 71.2, 71.0,
7
0.0, 68.8, 68.6, 68.2, 67.8, 67.6, 63.8, 38.9 (-SCH(CH ) ), 33.0, 23.2
3
2
(
-SCH(CH ) ), 23.1 (-SCH(CH ) ), 17.5 (C-6’). HRMS calc. for C H NaO S
3 2 3 2 84 80 19 2
þ
[M þ Na] : 1479.4627, found: 1479.4612.

2
2
Y. ZHAO ET AL.
2
-Isopropylsulfinylbenzyl 2,3,4,6-tetra-O-benzoyl-b-D-glucopyranosyl-(1!2)-3,4-
di-O-benzyl-a-L -rhamnopyranosyl-(1!3)-2-O-benzoyl-4,6-O-benzylidene-1-thio-
b-D-glucopyranoside (30)
A solution of 28 (80 mg, 0.05 mmol) in CH Cl (0.27 mL) was cooled to
2
2
ꢂ
ꢁ
20 C, followed by the dropwise addition of the solution of 3-chloroper-
oxybenzoic acid (12.6 mg, 0.05 mmol) in CH Cl (0.27 mL). The reaction
2
2
ꢂ
mixture was stirred at ꢁ20 C for 1 h, diluted with EtOAc, washed with
10% Na S O aqueous solution. The organic phase was washed with brine,
2
2 3
dried (Na SO ), concentrated, and purified by silica gel column chromatog-
2
4
raphy to give compound 30 (75.2 mg, 93% yield) as white solid, R ¼ 0.10
f
1
(
petroleum-EtOAc 2:1). A sulfoxide mixture (R and S 1:0.8), H NMR
(
400 MHz, CDCl ) d 8.07–7.75 (21.48 H, m, Ar-H), 7.60–7.14 (60.05 H, m,
3
Ar-H), 4.94-6.92 (3.80 H, m, Ar-H), 5.62 (0.8 H, t, J ¼ 9.6 Hz), 5.59 (1 H, t,
J ¼ 9.6 Hz), 5.50 (1.8 H, s, PhCHO ), 5.38–5.26 (5.6 H, m), 4.97 (0.8 H, d,
2
J ¼ 1.6 Hz, H-1’), 4.91 (1 H, d, J ¼ 1.6 Hz, H-1’), 4.74 (1.8 H, t, J ¼ 8.0 Hz),
4
4
3
.53 (0.8 H, d, J ¼ 10.0 Hz), 4.39–4.35 (5.9 H, m), 4.30 (0.8 H, dd, J ¼ 10.4,
.8 Hz), 4.13–4.02 (5.9 H, m), 3.99 (0.8 H, m), 3.95 (0.8 H, d, J ¼ 2.8 Hz),
.93–3.77 (9.9 H, m), 3.75–3.68 (3.5 H, m), 3.63 (1 H, t, J ¼ 9.2 Hz), 3.60
(
(
-
1 H, dd, J ¼ 10.8, 9.2 Hz), 3.53–3.43 (4.1 H, m), 3.06–2.95 (2.9 H, m), 2.85
1 H, hepta. J ¼ 6.8 Hz, -SCH(CH ) ), 1.18 (2.4 H, d, J ¼ 6.8 Hz,
3
2
SCH(CH ) ), 1.08 (3 H, d, J ¼ 6.8 Hz, -SCH(CH ) ), 0.99 (2.4 H, d,
3
2
3 2
J ¼ 6.8 Hz, -SCH(CH ) ), 0.96 (3 H, d, J ¼ 6.8 Hz, -SCH(CH ) ), 0.75 (2.4 H,
3
2
3 2
1
3
d, J ¼ 6.0 Hz, H-6’), 0.71 (3 H, d, J ¼ 6.0 Hz, H-6’). C NMR (100 MHz,
CDCl ) d 166.0, 166.0, 165.8, 165.8, 165.4, 165.4, 165.3, 165.3, 165.0, 164.9
3
(
C ¼ O), 141.7, 141.5, 138.9, 138.9, 138.6, 138.6, 136.9, 136.9, 135.3, 134.6,
1
1
1
1
1
7
7
6
34.1, 133.5, 133.3, 133.3, 133.2, 133.2, 131.1, 131.0, 130.7, 130.1, 130.0,
29.9, 129.9, 129.8, 129.8, 129.7, 129.6, 129.6, 129.3, 129.2, 129.1, 129.1,
29.1, 129.1, 129.0, 128.6, 128.5, 128.5, 128.4, 128.4, 128.4, 128.3, 128.2,
28.2, 127.6, 127.6, 127.5, 127.5, 127.5, 127.5, 127.4, 126.4, 126.4, 125.9,
25.8 (Ar), 101.9, 101.9, 101.6, 101.5, 99.9, 99.8, 84.0, 82.7, 80.5, 80.5, 79.5,
9.5, 79.5, 79.4, 77.9, 77.8, 75.8, 75.8, 74.7, 74.6, 72.9, 72.8, 72.6, 72.6, 72.2,
2.2, 71.9, 71.9, 71.8, 71.7, 71.2, 71.1, 70.1, 70.1, 68.5, 68.5, 68.4, 68.4, 63.2,
3.2, 53.8, 53.5, 29.8, 29.4, 17.5, 17.3, 17.3, 17.2, 12.8, 12.8. C H NaO S
20 2
8
4
80
þ
[
M þ Na] : 1495.4576, found: 1495.4604.
3
-Benzoxyl-4-methoxylphenylethyl 2,3,4,6-tetra-O-benzoyl-b-D-glucopyranosyl-
(
1!2)-3,4-di-O-benzyl -a-L-rhamnopyranosyl-(1!3)-2-O-benzoyl-4,6-O- benzyli-
dene-1-thio-b-D-glucopyranoside (31)
A solution of 30 (70.0 mg, 0.05 mmol), 16a (10.2 mg, 0.04 mmol) and
DTBMP (16.2 mg, 0.08 mmol) in CH Cl (0.79 mL) in the presence of 4 Å
2
2
ꢂ
MS (100 wt%) was stirred at 0 C for 10 min, Tf O (8.0 lL, 0.05 mmol) was
2
ꢂ
added, the solution was stirred at 0 C for 30 min. The reaction mixture

JOURNAL OF CARBOHYDRATE CHEMISTRY
23
was quenched with Et N, then filtered and extracted with EtOAc. The
3
organic phase was washed with brine, dried (Na SO ), concentrated, and
2
4
purified by silica gel column chromatography to give compound 31
2
D
0
(
66.3 mg, 92% yield) as white solid. R ¼ 0.35 (petroleum -EtOAc 3:1). ½aꢃ
f
1
þ12.12 (c, 1.37 in CHCl ). H NMR (400 MHz, CDCl ) d 8.00–7.96 (4 H,
3
3
m, Ar-H), 7.88 (2 H, d, J ¼ 7.6 Hz, Ar-H), 7.82 (2 H, d, J ¼ 7.6 Hz, Ar-H),
.77 (2 H, d, J ¼ 7.6 Hz, Ar-H), 7.55–7.15 (33 H, m, Ar-H), 6.95 (2 H, m,
Ar-H), 6.61 (1 H, d, J ¼ 1.6 Hz, H-2), 6.56 (1 H, dd, J ¼ 8.0, 1.6 Hz, H-6),
.47 (1 H, d, J ¼ 8.0 Hz, H-5), 5.61 (1 H, t, J ¼ 9.6 Hz), 5.46 (1 H, s,
PhCHO ), 5.38 (1 H, dd, J ¼ 9.6, 4.0 Hz), 5.36 (1 H, dd, J ¼ 9.6, 5.6 Hz), 5.22
7
6
2
0
0
(
4
(
1 H, t, J ¼ 8.4 Hz), 5.04 (2 H, s, ArOCH Ph), 4.94 (1 H, appar. s, H-1 ),
2
.71 (1 H, d, J ¼ 8.0 Hz), 4.49 (1 H, d, J ¼ 8.0 Hz), 4.38 (2 H, s, ArCH ), 4.33
2
1 H, dd, J ¼ 10.4, 4.8 Hz), 4.13 (1 H, d, J ¼ 11.2 Hz, ArCH ), 4.06 (1 H, dd,
2
J ¼ 12.0, 3.6 Hz), 4.00–3.92 (3 H, m), 3.87–3.80 (3 H, m), 3.76–3.71 (2 H,
m), 3.69 (3 H, s, OMe), 3.60–3.51 (2 H, m), 3.48–3.40 (2 H, m), 3.05 (1 H, t,
0
0
J ¼ 9.6 Hz, H-4 ), 2.65 (2 H, m, ArCH CH O-), 0.74 (3 H, d, J ¼ 6.0 Hz, H-
2
2
0
0
13
6
). C NMR (100 MHz, CDCl ) d 166.0, 165.9, 165.2, 165.2, 165.0
3
(
C ¼ O), 148.2, 147.9, 138.9, 138.6, 137.4, 137.0, 133.7, 133.5, 133.3, 133.2,
1
1
1
1
1
7
6
33.1, 130.8, 130.1, 130.1, 130.0, 130.0, 129.9, 129.9, 129.9, 129.9, 129.9,
29.8, 129.7, 129.6, 129.1, 129.0, 129.0, 128.9, 128.9, 128.6, 128.6, 128.6,
28.6, 128.6, 128.5, 128.5, 128.5, 128.5, 128.4, 128.4, 128.3, 128.3, 128.2,
28.2, 128.2, 128.2, 127.9, 127.6, 127.6, 127.6, 127.5, 127.5, 127.5, 127.5,
27.4, 126.5, 126.5, 121.6, 115.0, 111.7 (Ar), 101.9, 101.7, 101.5, 99.9, 80.5,
9.6, 79.4, 76.2, 74.7, 74.6, 72.6, 72.1, 71.9, 71.7, 71.0, 71.0, 70.0, 68.8, 68.3,
1
3
6.7, 63.1, 56.0, 35.6, 17.3. (one C signal may overlapped with CDCl
3
þ
solvent peaks) HRMS calc. for C H NaO
22
found: 1539.5318.
[M þ Na] :1539.5346,
9
0
84
Proposed incanoside B (10)
A solution of 31 (40 mg, 0.03 mmol) and DTT (8.1 mg, 0.05 mmol) in
CH Cl (0.53 mL) was added CSA (6.1 mg, 0.03 mmol), the reaction mix-
2
2
ture was stirred at room temperature for 9 h, diluted with EtOAc, washed
with water and brine, dried (Na SO ), concentrated, and purified by silica
2
4
gel column chromatography to give the deprotection of benzylidene prod-
uct, which was dissolved in methanol (1.0 mL), followed by the addition of
ꢂ
NaOMe (1.4 mg, 0.03 mmol), the reaction mixture was stirred at 50 C until
the completion of deprotection of acyl group, the reaction mixture was
evaporated and purified by silica gel column chromatography. After that,
the obtained product was dissolved in methanol (0.53 mL), the solution was
added to 30 wt% Pd/C (10% Palladium on activated carbon) in a Schlenk
tube, the reaction system was degassed with H , and stirred under H
2
2

2
4
Y. ZHAO ET AL.
atmosphere at room temperature overnight. The solid materials were fil-
trated off, and the solution was concentrated. The residue was chromato-
graphed on a Sephadex LH-20 column (CH Cl /MeOH 1:1) to give 10 as
2
2
20
white solid, R ¼ 0.19 (EtOAc:MeOH:H O 39:11:4). ½aꢃ ꢁ42.0 (c, 0.05 in
f
2
D
1
CH OH). H-NMR (400 MHz, methanol-d ) d 6.82 (1 H, d, J ¼ 8.0 Hz, H-
3
4
5
(
), 6.73 (1 H, d, J ¼ 2.0 Hz, H-2), 6.68 (1 H, dd, J ¼ 8.0, 2.0 Hz, H-6), 5.57
1 H, d, J ¼ 0.8 Hz, H-1 ), 4.43 (1 H, d, J ¼ 7.6 Hz, H-1 ), 4.29 (1 H, d,
J ¼ 8.0 Hz, H-1’), 4.05-3.96 (3 H, m), 3.90–3.85 (2 H, m), 3.81 (3 H, s,
OMe), 3.78 (1 H, dd, J ¼ 10.0, 3.6 Hz), 3.74–3.67 (2 H, m), 3.65 (1 H, dd,
0
0
000
-
J ¼ 12.0, 4.4 Hz), 3.48 (1 H, t, J ¼ 8.8 Hz), 3.41–3.32 (4 H, m), 3.29–3.26
00
13
(
(
4 H, m), 2.84–2.77 (2 H, m, H-7), 1.25 (3 H, d, J ¼ 6.0 Hz, H-6 ). C NMR
100 MHz, methanol-d ) d 147.5, 147.3, 133.0, 121.2, 117.1, 112.9, 106.8,
4
1
04.1, 101.6, 84.5, 82.7, 78.1, 77.9, 77.8, 75.7, 75.4, 74.3, 72.0, 71.9, 71.3,
þ
70.1, 69.9, 62.7, 62.7, 56.5, 36.5, 17.9. C H NaO [M þ Na] : 661.2314,
2
7
42
17
found: 661.2310.
Funding
Financial support from National Natural Science Foundation of China [21672077,
1761132014, 21772050, 21702068], the State Key Laboratory of Bioorganic and Natural
Products Chemistry [SKLBNPC13425], Wuhan Creative Talent Development Fund,
Thousand Talents Program” Young Investigator Award, and Huazhong University of
2
“
Science and Technology are greatly appreciated.
References
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