Synthesis and cytotoxic activity of the N-acetylglucosamine-bearing triterpenoid saponins

Article abstract of DOI:10.1016/j.carres.2010.01.002

Fourteen ursolic acid and oleanolic acid saponins with N-acetyl-β-d-glucosamine, and (1→4)-linked and (1→6)-linked N-acetyl-β-d-glucosamine oligosaccharide residues were synthesized in a convergent manner. The structures of all compounds were confirmed by

Full text of DOI:10.1016/j.carres.2010.01.002

Carbohydrate Research 345 (2010) 607–620
Contents lists available at ScienceDirect
Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres
Synthesis and cytotoxic activity of the N-acetylglucosamine-bearing
triterpenoid saponins
Peng Wang a, Jun Wang a, TianTian Guo a, Yingxia Li b,
*
a School of Medicine and Pharmacy, Ocean University of China, Qingdao 266003, China
b School of Pharmacy, Fudan University, Shanghai 201203, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Fourteen ursolic acid and oleanolic acid saponins with N-acetyl-b-D-glucosamine, and (1?4)-linked and
Received 15 October 2009
Received in revised form 10 December 2009
Accepted 4 January 2010
(1?6)-linked N-acetyl-b-D-glucosamine oligosaccharide residues were synthesized in a convergent man-
ner. The structures of all compounds were confirmed by 1H NMR and 13C NMR spectroscopy and by mass
spectrometry, and their cytotoxic activities were assayed in three cancer cell lines. Only oleanolic acid-3-
Available online 7 January 2010
yl b-
D
-GluNAc showed significant cytotoxicity against HL-60 and BGC-823.
Ó 2010 Published by Elsevier Ltd.
Keywords:
Ursolic acid
Oleanolic acid
Saponin
N-Acetylglucosamine
Cytotoxic activity
1. Introduction
2. Results and discussion
2.1. Chemistry
Triterpenoid and steroidal saponins isolated from various natu-
ral medicinal plants have many biological and physiological activ-
ities such as anti-HIV activity, inhibition of b-glucosidase and
cytotoxicity.1–3 A common feature of saponins is their inhibitory
activity against the growth of tumour cells with the potency being
highly dependent on the structure of the 3-O-sugar residue.4–6 It is
well known that the naturally occurring N-acetylglucosamine-
bearing triterpenoid saponins are rare; however, most of these
show remarkable cytotoxicity or antiproliferative activity.7 These
findings indicate that the N-acetylglucosamine-bearing sugar
chain dramatically boosts the bioactivity of triterpenoid. Several
reviews on the synthesis of steroids/triterpene saponins have been
published.8 In a previous paper, we reported the synthesis of an
ursolic acid saponin with an N-acetylglucosamine-containing su-
gar chain, which was the active sugar moiety attached to the ole-
anolic acid saponin isolated from the Suriname rainforest plants,
Acacia tenuifolia and Albizia subdimidiata.9 In continuing work on
further probing the mode of linkage of the N-acetylglucosamine
oligosaccharide residue on the cytotoxic activity of oleanolic acid
It is considered essential to develop a concise procedure to pre-
pare saponins in high overall yield for evaluation in pharmacolog-
ical research. A convergent synthesis for the two series of target
saponins was adopted in this paper. The b-(1?4)-linked glycosyl
donors that are involved in the synthesis were prepared as shown
in Scheme 1. To increase the nucleophilic activity of the 4-OH ben-
zyl-protected disaccharide, acceptor, 19 was designed at the outset
to synthesize trisaccharide and tetrasaccharide donors. So the key
monosaccharide acceptor 1610 and donor 1711 were selected as the
basic building blocks for preparing the disaccharide unit. Starting
from known materials, glycosylation of 16 with donor 17 under
the promotion of TMSOTf (0.2 equiv) yielded b-(1?4)-linked disac-
charide 18 (81%). Deacetylation of 18 in NaOMe–MeOH at pH 12
without removal of Phth afforded the key disaccharide acceptor
19. The literature reported that if benzyl-protected glycosyl donor
was used in a reaction with the acceptor 19 for the preparation of
b-(1?4)-linked trisaccharide and tetrasaccharide donors, the con-
ditions required for the removal of the benzyl groups (Pd/C, H2,
1:1?1:2 0.1 M HCl–MeOH) and the acetyl groups12 (LiOH–
30%H2O2–THF) after coupling with ursolic acid or oleanolic acid
will destroy the carbon–carbon double bonds of the aglycon. To
address this problem the known acetyl-protected glycosyl donor
1513 was employed in the coupling reaction with disaccharide
acceptor 19 to give the b-(1?4)-linked trisaccharide 20 in 73%
yield. Subsequent removal of the anomeric O-MP protection by
and ursolic acid saponins, we have designed and synthesized b-D-
(1?4)- and (1?6)-linked mono- to tetra-(N-acetylglucosamine)
derivatives of ursolic acid and oleanolic acid (Fig. 1) and have
carried out a preliminary evaluation of their cytotoxicity against
HL-60, BGC-823 and HeP-2.
* Corresponding author. Tel./fax: +86 21 51980127.
E-mail address: liyx417@fudan.edu.cn (Y. Li).
0008-6215/$ - see front matter Ó 2010 Published by Elsevier Ltd.
doi:10.1016/j.carres.2010.01.002

608
P. Wang et al. / Carbohydrate Research 345 (2010) 607–620
Figure 1. Structures of target saponins.
oxidative cleavage14 with ammonium cerium(IV) nitrate (CAN)
yielded 21, which was then reacted with CCl3CN–DBU to produce
the trisaccharide donor 22. Herein, acetyl-protected disaccharide
donor 30 was prepared for the synthesis of the (1?4)-linked tetra-
saccharide donor. Starting from 23,15 compound 24 was obtained
by deacetylation of 23 with NaOMe–MeOH, followed by protection
of the 4,6-OHs with a benzylidene group. The free hydroxyl group
(HO-3) was then acetylated to give 25. Subsequent full debenzyli-
denation of 25 afforded 26, and selective acetylation gave 27.
Compound 27 was coupled with donor 15 under standard glycosyl-
ation conditions to afford 28 in good yield. Removal of the anomer-
ic O-MP protection and then reaction of the HO-1 group with
CCl3CN produced disaccharide donor 30. Coupling of 30 with 19
under standard conditions afforded the b-(1?4)-linked tetrasac-
charide 31 in 41% yield. Tetrasaccharide donor 33 was obtained
in the same manner as in the previous case. So b-(1?4)-linked
acetylglucosamine oligosaccharide donors 15, 22, 30 and 33 were
produced in moderate to good yields and were designed to provide
effective glycosyl donors for the preparation of target saponins in
the next part of the work.
The synthetic route to b-(1?6)-linked glycosyl donors is shown
in Scheme 2. Compound 34 was selected as the key glycosyl accep-
tor, which was coupled with donor 15, with promotion by TMSOTf,
to produce disaccharide 35. In a concise process 35 was converted
into glycosyl donor 38 and acceptor 36. Herein, the coupling of gly-
cosyl donor 15 and acceptor 36 gave trisaccharide 39, while the
coupling of donor 38 and acceptor 36 produced tetrasaccharide
42. Removal of the C-1-OMP group of 35, 39 and 42 produced b-
(1?6)-linked di-, tri- and tetrasaccharide hemiacetals 37, 40 and
43, respectively, in good yields. During the subsequent preparation
of the Schmidt donors, only trace amounts of products were de-
tected by TLC when 6 equiv of trichloroacetonitrile were added,
but trichloroacetimidates 38, 41 and 44 were obtained in accept-
able yields when the amount of trichloroacetonitrile was increased
to 15.0 equiv.
With these protected glycosyl donors 15, 22, 30, 33, 38, 41 and
44 in hand, the coupling of donors with trityl ursolate or trityl ole-
anolate was performed at ꢀ70 °C under the promotion of TMSOTf
(0.2 equiv), followed by removal of the trityl ester group by warm-
ing the reaction solutions to room temperature and adding MeOH
and TsOH (pH 2) to generate the intermediates 45–58. These prod-
ucts were then treated with hot ethylenediamine–butanol16
(90 °C) and Ac2O–pyridine, and finally with NaOMe–MeOH to pro-
duce the target saponins 1–4 and 9–14. Target compounds 5–8
were obtained by hydrogenolysis of 49–52 under Pd/C (10%) in
the presence of HOAc (Scheme 3).
2.2. Bioactivity assays
The antitumour activities of these synthetic saponins against
HL-60, BGC-823 and HeP-2 tumour cell were determined
in vitro by the standard MTT assay (HL-60) and SRB assay
(BGC-823 and HeP-2). As shown in Table 1, the cytotoxicity of
all oleanolic acid saponins were better than that of the corre-
sponding ursolic acid saponins. Only oleanolic acid saponin 1 dis-
played prominent inhibition activity against HL-60 and BGC-823
with an IC50 value at 4.70 lM against HL-60. The counterpart of
ursolic acid 2 showed weaker antitumour activity against HL-60
and no cytotoxicity against BGC-823 and Hep-2. All other sapo-
nins with di- to tetrasaccharide chains did not show distinct cyto-
toxicity. These results indicate that some N-acetylglucosamine-
containing sugar chains are important for inducing the antitu-
mour activity of triterpene saponins and branched sugar chains
with specific linkages may be essential for this pharmacological
effect.7 So there is still a lot of work to do in searching for such
active sugar residues.

P. Wang et al. / Carbohydrate Research 345 (2010) 607–620
609
Scheme 1. Preparation of b-(1?4)-linked glycosyl donors. Reagents and conditions: (a) TMSOTf (0.2 equiv), 4 Å MS, 81% for 18, 85% for 28, 73% for 20, 41% for 31; (b) NaOMe,
MeOH, rt, quant; (c) (i) NaOMe, MeOH, rt; (ii) PhCH(OCH3)2, TsOH, DMF, 60 °C, 0.1 MPa, 89.0% for two steps; (d) Ac2O, Py, rt, quant; (e) 80% HOAc, 50 °C, 92.8%; (f) Ac2O
(1.05 equiv), Py, 0 °C?rt, 76%; (g) CAN, CH3CN–H2O, 89% for 29, 88% for 21, 83% for 32; (h) DBU, CNCCl3, CH2Cl2, 0 °C?rt, 72% for 30, 82% for 22, 84% for 33.
4.2. p-Methoxyphenyl 4,6-O-benzylidene-2-deoxy-2-phthalim-
ido-b- -glucopyranoside (24)
3. Conclusions
D
In summary, 14 ursolic acid and oleanolic acid saponins bearing
Compound 23 (16.8 mmol, 9.09 g) was dissolved in 1:5 MeOH–
CH2Cl2 (100 mL) and then 1:1 NaOMe–MeOH was added to adjust
the solution to pH 9. After stirring at rt for 2 h, the solution was
neutralized with cation-exchange resin (H+) and then filtered and
concentrated to afford an amorphous solid. To a solution of the
above-mentioned compound and PhCH(OMe)2 (32.5 mmol,
4.95 g) in dry DMF (50 mL) was added TsOHꢁH2O (1.5 mmol,
0.26 g). The resulting mixture was stirred at 40 °C under reduced
pressure for 6 h, neutralized by Et3N (3 mL), diluted with EtOAc
(200 mL) and then successively washed with water (2 ꢂ 50 mL),
satd NaHCO3 (2 ꢂ 50 mL) and brine (2 ꢂ 50 mL). The organic layer
was dried over anhyd Na2SO4 and then concentrated under vac-
uum. The residue was purified by silica gel column chromatogra-
phy (4:1–3:1 petroleum ether–EtOAc) to yield 24 (8.3 g, 92%) as
N-acetyl-D-glucosamine, (1?4)-linked and (1?6)-linked N-acetyl-
D
-glucosamine oligosaccharide residues were synthesized using a
convergent strategy. Significant antitumour activity was demon-
strated for only saponin 1. Further searching for active sugar chains
that can induce antitumour activity of oleanolic acid and ursolic
acid are in progress and will be reported in due course.
4. Experimental
4.1. General procedures
Solvents were purified in the usual way. Thin-layer chromatog-
raphy (TLC) was performed on pre-coated E. Merck Silica Gel 60
F254 plates. Flash column chromatography was performed on silica
gel (200–300 mesh, Qingdao, China). Optical rotations were deter-
mined with a Perkin–Elmer Model 241 MC polarimeter. 1H NMR
and 13C NMR spectra were taken on a JEOL JNM-ECP 600 spectrom-
eter with tetramethylsilane as the internal standard and chemical
shifts are recorded in d units. Mass spectra were recorded on a Q-
TOF Global mass spectrometer.
a white solid with Rf 0.70 (15:1 CHCl3–MeOH); ½a D20
ꢃ
+11.4 (c
0.67, CHCl3); 1H NMR (CDCl3): d 7.87–7.27 (m, 4H, Phth), 7.51–
7.38 (m, 5H, Ph), 6.83–6.73 (m, 4H, Ph), 5.81 (d, 1H, J 8.4 Hz, H-
1), 5.60 (s, 1H, PhCH), 4.71 (dd, 1H, J 10.6, 8.5 Hz, H-3), 4.51 (dd,
1H, J 10.6, 8.4 Hz, H-2), 4.41 (dd, 1H, J 10.6, 4.4 Hz, H-6i), 3.90–
3.82 (m, 1H, H-6ii), 3.78–3.69 (m, 5H, H-4, H-5 and OCH3), 1.86

610
P. Wang et al. / Carbohydrate Research 345 (2010) 607–620
Scheme 2. Preparation of b-(1?6)-linked glycosyl donors. Reagents and conditions: (a) TMSOTf (0.2 equiv), 4 Å MS, 99% for 35, 92% for 39, 91% for 42; (b) (i) NaOMe, MeOH,
rt, quant; (ii) TrCl (5 equiv), DMAP, Py, 80 °C; (iii) Ac2O, Py, 92%; (iv) FeCl3ꢁ6H2O, 79%; (c) CAN, CH3CN–H2O, 96% for 37, 88% for 40, 92% for 43; (d) DBU, CNCCl3, CH2Cl2,
0 °C?rt, 74% for 38, 66% for 41, 65% for 44.
Scheme 3. Preparation of the target saponins. Reagents and conditions: (a) TMSOTf, TsOH; (b) (i) NH2CH2CH2NH2, BuOH, 90 °C; (ii) Ac2O, Py; (iii) NaOMe, MeOH; (c) (i)
NH2CH2CH2NH2, BuOH, 90 °C; (ii) Ac2O, Py; (iii) NaOMe, MeOH; (iv) Pd/C, AcOH, MeOH.

P. Wang et al. / Carbohydrate Research 345 (2010) 607–620
611
4.3.3. 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
(1?4)-3,6-di-O-acetyl-2-deoxy-2-phthalimido-b-
(1?4)-3,6-di-O-benzyl-2-deoxy-2-ph-thalimido-b-
(1?4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-b-
(32)
D
-glucopyranosyl-
Table 1
Inhibition rate at 10
tumour cell lines
lM (%) of the synthetic compounds 1–14 against different
D-glucopyranosyl-
D-glucopyranosyl-
Compound OLa
1
3
5
7
9
11
4.31
8.42 14.78
13
D-glucopyranose
HL-60
BGC-823
HeP-2
Compound UAb
HL-60
13.18 82.62 31.70 18.17
17.00 68.99 39.17 22.55
26.99 23.34 23.64 13.30
48.31 12.81
35.46 16.29
6.52
Yield 83%; Rf 0.45 (2:1 petroleum ether–EtOAc); 1H NMR
(CDCl3): d 7.94–7.54 (m, 16H, Phth), 7.22–6.68 (m, 20H, PhCH2),
5.79–5.67 (m, 2H, H-300, H-3000), 5.42 (d, 1H, J 8.5 Hz, H-100), 5.35
(d, 1H, J 8.4 Hz, H-1000), 5.13 (t, 1H, J 9.5 Hz, H-4000), 5.09 (br s, 1H,
H-1), 5.05 (d, 1H, J 8.0 Hz, H-10), 4.77 (d, 1H, J 12.8 Hz, PhCH2),
4.71 (d, 1H, J 12.8 Hz, PhCH2), 4.49–4.29 (m, 7H, H-6i000, 6 ꢂ PhCH2),
4.21 (dd, 1H, J 8.5, 10.6 Hz, H-2000), 4.16–3.88 (m, 9H, H-2, H-3, H-4,
H-20, H-30, H-40, H-200, H-6i00, H-6i000), 3.75 (ddd, 1H, J 2.2, 3.3, 10.3 Hz,
H-5000), 3.45–3.39 (m, 3H, H-6I, H-6i0, H-6i00), 3.30–3.27 (m, 2H, H-5,
37.84
2.02 10.47 21.80
2
4
6
4.11
5.99
6.84 ꢀ12.01
8
10
10.99 15.52
12
14
7.57 51.04
31.22
3.11 Ntc
7.48 Ntc
2.52 Ntc
BGC-823
HeP-2
12.49
10.77
5.43 ꢀ4.35
3.90
0.65
3.44
4.06 ꢀ6.39
a
b
c
OL = oleanolic acid.
UA = ursolic acid.
nt = not tested.
0
H-6ii), 3.19 (dd, 1H, J 2.9, 11.3 Hz, H-6ii ), 3.13 (dt, 1H, J 2.2, 9.9 Hz,
H-500), 2.99 (br s, 1H, OH), 2.90 (d, 1H, J 7.4 Hz, H-50), 2.05, 1.97,
1.89, 1.80, 1.75 (s each, 3H each, 5 ꢂ COCH3); ESIMS: calcd for
C94H88N4NaO30 1775.5, found 1775.5 [M+Na]+.
(br s, 1H, OH); ESIMS: calcd for C28H25NNaO8 526.1, found 526.0
[M+Na]+.
4.3.4. 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-D-glucopyr-
4.3. General procedure for the preparation of compounds 21,
29, 32, 37, 40 and 43
anosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
copyranose (37)
D
-glu-
Yield 88%; Rf 0.20 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+29.0 (c
0.71, CHCl3); 1H NMR (CDCl3): d 7.88–7.73 (m, 8H, Phth), 5.81
(dd, 1H, J 8.8, 10.6 Hz, H-30), 5.70 (d, 1H, J 8.4 Hz, H-10), 5.57 (dd,
1H, J 8.8, 10.6 Hz, H-3), 5.24 (d, 1H, J 8.0 Hz, H-1), 5.17 (dd, 1H, J
9.2, 10.6 Hz, H-40), 4.84 (dd, 1H, J 9.2, 10.3 Hz, H-4), 4.35–4.31
To a stirred solution of precursor compound (1 mmol) in 4:1
CH3CN–H2O (10 mL) was added ammonium cerium(IV) nitrate
(5 mmol). After stirring at rt for 1 h, the mixture was diluted with
EtOAc (100 mL) and successively washed with water (3 ꢂ 50 mL)
and brine (3 ꢂ 50 mL). The organic layer was dried over anhyd
Na2SO4 and then concentrated in vacuum to give a yellow syrup
that was purified by column chromatography to afford the pure
compound.
0
(m, 2H, H-20, H-6i0), 4.22–4.17 (m, 2H, H-2, H-6ii ), 3.90 (ddd, 1H,
J 2.2, 4.4, 10.3 Hz, H-50), 3.81 (dd, 1H, J 8.5, 12.8 Hz, H-6i), 3.71
(dd, 1H, J 1.9, 12.8 Hz, H-6ii), 3.53 (m, 1H, H-5), 2.15, 2.04, 1.93,
1.88, 1.81 (s each, 3H each, 5 ꢂ COCH3); ESIMS: calcd for
C38H38N2NaO18 833.2, found 833.2 [M+Na]+.
4.3.1. 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-D-glucopyr-
4.3.5. 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
anosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
copyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
D
-glucopyr-
anosyl-(1?4)-3,6-di-O-acetyl-2-deoxy-2-phthalimido-b-
D
-glu-
D
-glu-
copyranose (29)
Yield 89%; Rf 0.23 (2:3 petroleum ether–EtOAc); ½a D20
ꢃ
+23.5 (c
D
-glucopyranose (40)
0.50, CHCl3); 1H NMR (CDCl3): d 7.88–7.72 (m, 8H, Phth), 5.79
(dd, 1H, J 8.7, 10.0 Hz, H-3), 5.73 (dd, 1H, J 9.2, 10.6 Hz, H-30),
5.56 (d, 1H, J 8.3 Hz, H-1), 5.47 (d, 1H, J 8.7 Hz, H-10), 5.15 (dd,
1H, J 9.2, 10.1 Hz, H-40), 4.43 (dd, 1H, J 4.1, 12.4 Hz, H-6i0), 4.33
(dd, 1H, J 1.8, 11.9 Hz, H-6i), 4.26 (dd, 1H, J 8.2, 10.5 Hz, H-20),
4.11 (dd, 1H, J 8.7, 10.5 Hz, H-2), 4.08 (dd, 1H, J 2.3, 12.4 Hz, H-
Yield 88%; Rf 0.23 (1:2 petroleum ether–EtOAc); ½a D20
ꢃ
+36.8 (c
0.50, CHCl3); 1H NMR (CDCl3):d 7.92–7.73 (m, 12H, Phth), 5.78
(dd, 1H, J 9.2, 10.6 Hz, H-300), 5.66 (dd, 1H, J 9.2, 11.0 Hz, H-3),
5.56 (dd, 1H, J 9.1, 10.6 Hz, H-30), 5.52 (d, 2H, J 8.5 Hz, H-1, H-100),
5.25 (d, 1H, J 8.5 Hz, H-10), 5.18 (t, 1H, J 9.5 Hz, H-400), 4.92 (t, 1H,
J 9.1 Hz, H-4), 4.85 (dd, 1H, J 9.2, 10.3 Hz, H-40), 4.38–4.34 (m,
2H, H-200, H-6i00), 4.23–4.19 (m, 2H, H-2, H-6ii00), 4.17 (dd, 1H, J
8.4, 11.0 Hz, H-20), 3.92–3.87 (m, 2H, H-6i, H-500), 3.75–3.64 (m,
0
6ii ), 3.96 (dd, 1H, J 9.2, 9.6 Hz, H-4), 3.83 (ddd, 1H, J 2.3, 3.7,
10.1 Hz, H-50), 3.73 (ddd, 1H, J 1.8, 4.1, 10.1 Hz, H-5), 3.68 (dd,
1H, J 4.1, 11.9 Hz, H-6ii), 3.33 (br s, 1H, OH), 2.10, 2.00, 1.96, 1.91,
1.82 (s each, 3H each, 5 ꢂ COCH3); ESIMS: calcd for C38H38N2NaO18
833.2, found 833.3 [M+Na]+.
5H, H-5, H-6ii, H-6i0, H-6ii , OH), 3.47 (m, 1H, H-50), 2.16, 2.03,
0
1.91, 1.88, 1.86, 1.80, 1.80 (s, 3H each, 7 ꢂ COCH3); ESIMS: calcd
for C56H55N3NaO26 1208.3, found 1208.4 [M+Na]+.
4.3.2. 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
anosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-b-
copyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-b-
D
-glucopyr-
4.3.6. 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
anosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
copyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
-glucopyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalim-
D
-glucopyr-
D
-glu-
D
-glu-
D
-glucopyranose (21)
D
Yield 88%; Rf 0.14 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+9.1 (c
ido-b-D-glucopyranose (43)
0.1.15, CHCl3); 1H NMR (CDCl3): d 7.96–7.61 (m, 12H, Phth),
7.33–6.69 (m, 20H, PhCH2), 5.78 (dd, 1H, J 9.1, 10.6 Hz, H-300),
5.52 (d, 1H, J 8.4 Hz, H-100), 5.12 (t, 1H, J 9.2 Hz, H-400), 5.11 (d,
1H, J 9.5 Hz, H-1), 5.10 (d, 1H, J 8.0 Hz, H-10), 4.88–4.37 (m, 8H,
PhCH2), 4.32 (dd, 1H, J 8.5, 10.6 Hz, H-200), 4.26 (dd, 1H, J 8.0,
9.5 Hz, H-40), 4.21 (dd, 1H, J 3.7, 12.1 Hz, H-6i00), 4.18–4.10 (m,
3H, H-3, H-20, H-30), 4.07 (t, 1H, J 9.5 Hz, H-4), 3.95 (dd, 1H, J 8.4,
10.3 Hz, H-2), 3.91 (dd, 1H, J 1.9, 12.1 Hz, H-6ii00), 3.48–3.43 (m,
3H, H-6i, H-6i0, H-500), 3.33–3.29 (m, 2H, H-5, H-6ii), 3.22 (dd, 1H,
Yield 92%; Rf 0.14 (1:2 petroleum ether–EtOAc); ½a D20
ꢃ
+35.1 (c
0.50, CHCl3); 1H NMR (CDCl3): d 7.95–7.72 (m, 16H, Phth), 5.80
(dd, 1H, J 9.1, 10.6 Hz, H-3000), 5.65 (dd, 1H, J 9.2, 10.6 Hz, H-30),
5.61–5.58 (m, 2H, H-3, H-300), 5.50 (d, 1H, J 8.4 Hz, H-1000), 5.46 (d,
1H, J 8.4 Hz, H-100), 5.35 (d, 1H, J 8.5 Hz, H-10), 5.28 (d, 1H, J
8.4 Hz, H-1), 5.20 (dd, 1H, J 9.2, 10.3 Hz, H-4000), 4.39–4.35 (m, 2H,
H-40), 4.89 (dd, 1H, J 8.8, 10.3 Hz, H-2000, H-6i000), 4.23–4.10 (m, 4H,
H-2, H-20, H-200, H-6i000), 3.93–3.89 (m, 2H, H-6i0, H-5000), 3.79–3.66
0
(m, 5H, H-6I, H-6ii, H-50, H-6ii , H-6i00), 3.53–3.44 (m, 3H, H-5, H-
0
500, H-6ii00), 2.14, 2.04, 1.95, 1.89, 1.88, 1.86, 1.80, 1.79 (some over-
lap, 27H, 9 ꢂ COCH3); ESIMS: calcd for C74H72N4NaO34 1583.4,
found 1583.6 [M+Na]+.
J 2.9, 11.0 Hz, H-6ii ), 3.06 (d, 1H, J 3.7 Hz, OH), 2.93 (dd, 1H, J 1.4,
9.9 Hz, H-50), 1.98, 1.89, 1.84 (s each, 3H each, 3 ꢂ COCH3); ESIMS:
calcd for C76H71N3NaO22 1400.3, found 1400.4 [M+Na]+.

612
P. Wang et al. / Carbohydrate Research 345 (2010) 607–620
4.4. General procedure for preparation of the glycosyl donors
30, 22, 33, 38, 41 and 44
4.4.4. 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-D-glucopyr-
anosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
D
-glu-
copyranosyl trichloroacetimidate (38)
To a stirred solution of carbohydrate precursor compound
(1 mmol) in dry CH2Cl2 (15 mL) at 0 °C were added CCl3CN
(6 mmol–15 mmol) and DBU (0.5 mmol). The mixture was then al-
lowed to warm up to rt and stir for 2 h, after which time it was con-
centrated in vacuo. The resulting residue was purified by flash
column chromatography to afford the pure product.
Yield 74%; Rf 0.25 (2:3 petroleum ether–EtOAc); ½a D20
ꢃ
+43.2 (c
1.15, CHCl3); 1H NMR (CDCl3): d 8.36 (s, 1H, NH), 7.87–7.70 (m,
8H, Phth), 6.49 (d, 1H, J 8.8 Hz, H-1), 5.80 (dd, 1H, J 8.8, 10.6 Hz,
H-3), 5.76 (dd, 1H, J 8.3, 10.6 Hz, H-30), 5.47 (d, 1H, J 8.5 Hz, H-
10), 5.17 (dd, 1H, J 9.1, 10.2 Hz, H-40), 5.04 (dd, 1H, J 8.8, 9.9 Hz,
H-4), 4.50 (dd, 1H, J 8.8, 10.6 Hz, H-2), 4.37–4.34 (m, 2H, H-20, H-
0
6i0), 4.18 (dd, 1H, J 2.2, 12.1 Hz, H-6ii ), 3.98–3.95 (m, 2H, H-5, H-
6i), 3.85 (ddd, 1H, J 2.6, 4.8, 10.3 Hz, H-50), 3.70 (dd, 1H, J 6.2,
11.3 Hz, H-6ii), 2.14, 2.03, 1.94, 1.85, 1.82 (s each, 3H each,
5 ꢂ COCH3); ESIMS: calcd for C40H38Cl3N3NaO18 976.1, found
976.1 [M+Na]+.
4.4.1. 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-D-glucopyr-
anosyl-(1?4)-3,6-di-O-acetyl-2-deoxy-2-phthalimido-b-
D
-glu-
copyranosyl trichloroacetimidate (30)
Yield 72%; Rf 0.25 (2:3 petroleum ether–EtOAc); ½a D20
ꢃ
+31.2 (c
0.73, CHCl3); 1H NMR (CDCl3): d 8.58 (s, 1H, NH), 7.88–7.71 (m,
8H, Phth), 6.53 (d, 1H, J 9.2 Hz, H-1), 5.87 (dd, 1H, J 8.8,
10.3 Hz, H-3) 5.75 (dd, 1H, J 9.2, 10.6 Hz, H-30), 5.48 (d, 1H, J
8.5 Hz, H-10), 5.15 (dd, 1H, J 9.2, 10.3 Hz, H-40), 4.48 (dd, 1H, J
9.2, 10.6 Hz, H-2), 4.44 (dd, 1H, J 4.7, 12.4 Hz, H-6i0), 4.36 (dd,
1H, J 1.5, 12.1 Hz, H-6i), 4.28 (dd, 1H, J 8.5, 10.6 Hz, H-20), 4.14–
4.4.5. 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
anosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
copyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
D
-glucopyr-
D
-glu-
D
-glucopyranosyl trichloroacetimidate (41)
Yield 66%; Rf 0.34 (1:2 petroleum ether–EtOAc); ½a D20
ꢃ
+28.8 (c
0.45, CHCl3); 1H NMR (CDCl3): d 8.46 (s, 1H, NH), 7.93–7.70 (m,
12H, Phth), 6.46 (d, 1H, J 8.8 Hz, H-1), 5.78 (dd, 1H, J 9.2,
10.6 Hz, H-300), 5.74 (dd, 1H, J 9.2, 10.6 Hz, H-3), 5.62 (dd, 1H, J
8.8, 10.6 Hz, H-30), 5.50 (d, 1H, J 8.5 Hz, H-100), 5.32 (d, 1H, J
8.4 Hz, H-10), 5.19 (dd, 1H, J 9.2, 10.3 Hz, H-400), 4.91–4.88 (m,
2H, H-4, H-40), 4.47 (dd, 1H, J 8.8, 10.6 Hz, H-2), 4.38 (dd, 1H,
J 4.8, 12.1 Hz, H-6i00), 4.34 (dd, 1H, J 8.4, 10.6 Hz, H-200), 4.22
(dd, 1H, J 8.4, 11.0 Hz, H-20), 4.19 (dd, 1H, J 2.2, 11.8 Hz, H-
6ii00), 3.90 (ddd, 1H, J 2.2, 4.8, 10.3 Hz, H-500), 3.88 (dd, 1H, J
1.8, 11.0 Hz, H-6i0), 3.74 (dd, 1H, J 3.3, 11.0 Hz, H-6i), 3.72–3.64
0
4.06 (2H, H-4, H-6ii ), 3.89 (ddd, 1H, J 1.8, 3.7, 9.9 Hz, H-50),
3.86 (ddd, 1H, J 2.2, 4.4, 10.3 Hz, H-5), 3.75 (dd, 1H, J 3.7,
12.5 Hz, H-6ii), 2.13, 2.01, 1.94, 1.91, 1.83 (s, 15H each,
5 ꢂ COCH3); ESIMS: calcd for C40H38Cl3N3NaO18 976.1, found
976.0 [M+Na]+.
4.4.2. 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
anosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-b-
copyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-b-
D-glucopyr-
D
-glu-
(m, 3H, H-5, H-50, H-6ii ), 3.40 (dd, 1H, J 4.7, 11.0 Hz, H-6ii),
0
D
-glucopyranosyl trichloroacetimidate (22)
Yield 82%; Rf 0.27 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+5.5 (c
2.15, 2.04, 1.94, 1.92, 1.86, 1.80, 1.78 (s each, 3H each,
7 ꢂ COCH3); ESIMS: calcd for C58H55Cl3N4NaO26 1351.2, found
1351.2 [M+Na]+.
0.65, CHCl3); 1H NMR (CDCl3): d 8.38 (s, 1H, NH), 7.97–7.62 (m,
12H, Phth), 7.35–6.68 (m, 20H, PhCH2), 6.18 (d, 1H, J 8.8 Hz, H-
1), 5.78 (dd, 1H, J 9.2, 10.6 Hz, H-300), 5.53 (d, 1H, J 8.5 Hz, H-
100), 5.13 (t, 1H, J 9.1 Hz, H-400), 5.12 (d, 1H, J 8.1 Hz, H-10), 4.89–
4.40 (m, 8H, PhCH2), 4.34–4.10 (m, 8H, H-2, H-3, H-4, H-20, H-
30, H-40, H-200, H-6i00), 3.92 (dd, 1H, J 2.2, 12.1 Hz, H-6ii00), 3.54 (d,
1H, J 10.2, H-6i0), 3.24 (dd, 1H, J 2.9, 11.3 Hz, H-60), 3.46 (ddd,
1H, J 2.2, 3.7, 10.3 Hz, H-5), 3.44–3.42 (m, 2H, H-6i, H-500), 3.35
4.4.6. 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
anosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
copyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
-glucopyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalim-
D
-glucopyr-
D
-glu-
D
ido-b-D-glucopyranosyl trichloroacetimidate (44)
Yield 65%; Rf 0.22 (1:2 petroleum ether–EtOAc); ½a D20
ꢃ
+8.7 (c
0
(dd, 1H, J 3.3, 11.0 Hz, H-6ii), 3.23 (dd, 1H, J 2.9, 11.4 Hz, H-6ii ),
0.25, CHCl3); 1H NMR (CDCl3): d 8.47 (s, 1H, NH), 7.93–7.70 (m,
16H, Phth), 6.46 (d, 1H, J 8.8 Hz, H-1), 5.79 (dd, 1H, J 9.2, 10.6 Hz,
H-3000), 5.74 (dd, 1H, J 9.2, 10.6 Hz, H-3), 5.65 (dd, 1H, J 8.8,
10.6 Hz, H-30), 5.56 (dd, 1H, J 9.1, 10.6 Hz, H-300), 5.49 (d, 1H, J
8.5 Hz, H-1000), 5.30 (d, 1H, J 8.4 Hz, H-10), 5.23 (d, 1H, J 8.4 Hz, H-
100), 5.19 (dd, 1H, J 9.2, 9.9 Hz, H-4000), 4.91 (t, 2H, J 9.1 Hz, H-4, H-
40), 4.78 (dd, 1H, J 9.2, 9.8 Hz, H-400), 4.46 (dd, 1H, J 9.2, 11.0 Hz,
H-2), 4.38 (dd, 1H, J 4.8, 12.5 Hz, H-6i000), 4.35 (dd, 1H, J 9.4,
10.6 Hz, H-2000), 4.22–4.16 (m, 3H, H-20, H-200, H-6ii000), 3.93–3.89
2.91 (d, 1H, J 8.4 Hz, H-50), 1.98, 1.90, 1.84 (s each, 3H each,
3 ꢂ COCH3); ESIMS: calcd for C78H71Cl3N4NaO22 1543.4, found
1543.5 [M+Na]+.
4.4.3. 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
anosyl-(1?4)-3,6-di-O-acetyl-2-deoxy-2-phthalimido-b-
copyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-b-
-glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phthalim-
D-glucopyr-
D-glu-
D
ido-b-D-glucopyranosyl trichloroacetimidate (33)
0
(m, 2H, H-6i0, H-5000), 3.78–3.65 (m, 4H, H-6i, H-50, H-6ii , H-6i00),
Yield 84%; Rf 0.55 (1:2 petroleum ether–EtOAc); ½a D20
ꢃ
+9.0 (c
3.49 (ddd, 1H, J 3.2, 5.2, 10.3 Hz, H-500), 3.42–3.38 (m, 2H, H-6ii,
H-6ii00), 2.16, 2.04, 1.94, 1.93, 1.91, 1.86, 1.79, 1.78, 1.77 (s each,
3H each, 9 ꢂ COCH3); ESIMS: calcd for C76H72Cl3N5NaO34 1726.3,
found 1726.3 [M+Na]+.
0.25, CHCl3); 1H NMR (CDCl3): d 8.37 (s, 1H, NH), 7.93–7.49 (m,
16H, Phth), 7.22–6.68 (m, 20H, PhCH2), 6.16 (d, 1H, J 8.8 Hz, H-
1), 5.71–5.67 (m, 2H, H-300, H-3000), 5.43 (d, 1H, J 8.1 Hz, H-100),
5.36 (d, 1H, J 8.1 Hz, H-1000), 5.13 (dd, 1H, J 9.2, 10.3 Hz, H-4000),
5.07 (d, 1H, J 8.0 Hz, H-10), 4.77 (d, 1H, J 13.2 Hz, PhCH2), 4.71
4.5. General procedure for preparing compounds 18, 28, 20, 31,
35, 39 and 42
(d, 1H,
J ,
12.8 Hz, PhCH2), 4.50–4.30 (m, 8H, H-2000, H-6i000
6 ꢂ PhCH2), 4.23–4.06 (m, 7H, H-2, H-3, H-4, H-20, H-30, H-40, H-
200), 4.01–3.97 (m, 2H, H-6i00, H-6i000), 3.76 (ddd, 1H, J 2.2, 3.7,
10.3 Hz, H-5000), 3.51 (d, 1H, J 9.8 Hz, H-6i), 3.41–3.38 (m, 3H, H-
5, H-6i0, H-6ii00), 3.32 (dd, 1H, J 3.3, 11.0 Hz, H-6ii00), 3.20 (dd, 1H,
A
mixture of glycosyl acceptor (1 mmol), glycosyl donor
(1.2 mmol) and powdered 4 Å molecular sieves (300 mg) in dried
CH2Cl2 (40 mL) was stirred for 1 h at room temperature. The mix-
ture was cooled to ꢀ40 °C for 30 min, followed by the dropwise
addition of TMSOTf (0.2 mmol). After it was stirred at ꢀ40 °C for
30 min, the reaction mixture was warmed up naturally to room
temperature and quenched with Et3N. The solid was then filtered
0
J 2.5, 11.0 Hz, H-6ii ), 3.13 (ddd, 1H, J 1.8, 2.9, 9.9 Hz, H-500), 2.88
(d, 1H, J 5.9 Hz, H-50), 2.05, 1.97, 1.89, 1.81, 1.76 (s each, 3H each,
COCH3 ꢂ 5); ESIMS: calcd for C96H88Cl3N5NaO30 1918.4, found
1918.5 [M+Na]+.

P. Wang et al. / Carbohydrate Research 345 (2010) 607–620
613
off. The filtrate was concentrated under vacuum to produce a
yellow syrup that was purified by column chromatography to af-
ford the pure compound.
4.5.4. p-Methoxyphenyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalim-
ido-b- -glucopyranosyl-(1?4)-3,6-di-O-acetyl-2-deoxy-2-phth-
alimido-b- -glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-
phthalimido-b- -glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-de-
D
D
D
4.5.1. p-Methoxyphenyl 3,6-di-O-benzyl-4-O-acetyl-2-deoxy-2-
oxy-2-phthalimido-b-D-glucopyranoside (31)
phthalimido-b-
D
-glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-de-
Yield 41%; Rf 0.54 (1:2 petroleum ether–EtOAc); ½a D20
ꢃ
+17.3 (c
oxy-2-phthalimido-b-
D
-glucopyranoside (18)
0.33, CHCl3); 1H NMR (CDCl3): d 7.94–7.49 (m, 16H, Phth), 7.22–
6.68 (m, 20H, PhCH2), 6.67–6.55 (m, 4H, PhOCH3), 5.69 (dd, 2H, J
9.2, 10.5 Hz, H-300, H-3000), 5.42 (d, 1H, J 8.2 Hz, H-100), 5.38 (d, 1H,
J 8.7 Hz, H-1), 5.36 (d, 1H, J 8.3 Hz, H-1000), 5.13 (t, 1H, J 9.6 Hz, H-
4000), 5.07 (d, 1H, J 7.7 Hz, H-10), 4.78 (d, 1H, J 12.8 Hz, PhCH2),
4.70 (d, 1H, J 12.8 Hz, PhCH2), 4.49 (d, 1H, J 11.9 Hz, PhCH2), 4.46
(1H, dd, J 4.1, 12.4 Hz, H-6i000), 4.38–4.33 (m, 4H, PhCH2), 4.27 (dd,
1H, J 8.7, 10.5 Hz, H-2), 4.22 (dd, 1H, J 8.2, 10.6 Hz, H-2000), 4.16–
4.07 (m, 6H, H-3, H-4, H-20, H-30, H-40, H-200), 4.00 (dd, 1H, J 2.3,
11.9 Hz, H-6i000), 3.98 (dd, 1H, J 1.9, 12.1 Hz, H-6i00), 3.90 (dd, 1H, J
8.7, 10.1 Hz, H-400), 3.76 (ddd, 1H, J 2.8, 3.2, 10.1 Hz, H-5000), 3.63
(s, 3H, PhOCH3), 3.45–3.42 (m, 2H, H-6I, H-6i0), 3.40 (dd, 1H, J 3.2,
11.9 Hz, H-6ii00), 3.34–3.28 (m, 2H, H-5, H-6ii), 3.21 (dd, 1H, J 2.8,
Yield 81%; Rf 0.18 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+43.7 (c
1.65, CHCl3); 1H NMR (CDCl3): d 7.85–7.65 (m, 8H, Phth), 7.36–
6.83 (m, 20H, Ph), 6.70–6.58 (m, 4H, Ph), 5.44 (d, 1H, J 8.4 Hz,
H-1), 5.33 (d, 1H, J 8.4 Hz, H-10), 5.16 (t, 1H, J 9.18 Hz, H-40),
4.86 (d, 1H, J 12.4 Hz, PhCH2), 4.61 (d, 1H, J 12.1 Hz, PhCH2),
4.53–4.40 (m, 6H, H-30, 5 ꢂ PhCH2), 4.35 (dd, 1H, J 8.4, 10.3 Hz,
H-2), 4.32 (d, 1H,
J 12.1 Hz, PhCH2), 4.29 (dd, 1H, J 8.1,
10.6 Hz, H-20), 4.23 (t, 1H, J 8.5 Hz, H-3), 4.20 (t, 1H, J 8.8 Hz,
H-4), 3.65 (s, 3H, OCH3), 3.61–3.56 (m, 2H, H-50, H-6i0), 3.52–
0
3.46 (m, 2H, H-6i, H-6ii ), 3.43–3.39 (m, 2H, H-5, H-6ii), 1.92 (s,
3H, COCH3); ESIMS: calcd for C65H60N2NaO15 1131.4, found
1131.5 [M+Na]+.
0
11.0 Hz, H-6ii ), 3.12 (ddd, 1H, J 1.9, 3.2, 10.1 Hz, H-500), 2.94 (d,
1H, J 8.2 Hz, H-50), 2.05, 1.97, 1.89, 1.81, 1.76 (s each, 3H each,
5 ꢂ COCH3); 13C NMR (CDCl3): d 170.5, 170.1, 169.8, 169.7, 169.3
(5 ꢂ COCH3), 168.2–114.1 (Ph), 97.7 (C-1000), 97.4 (C-1), 96.8
(C-100), 96.5 (C-10), 76.6 (C-40), 75.7 (C-4, C-400), 74.6 (C-5), 74.2
(C-50), 72.5 (PhCH2), 72.3 (PhCH2), 72.5, 72.4 (PhCH2), 71.7 (C-500,
C-5000, PhCH2), 70.9 (C-300), 70.5 (C-3000), 68.2 (C-4000), 67.9 (C-6),
66.9 (C-60), 61.8 (C-600), 61.4 (C-6000), 56.2 (C-20), 55.7 (C-200), 55.5
(C-2, OCH3), 54.7 (C-2000), 20.3–20.7 (5 ꢂ COCH3); ESIMS: calcd for
C101H94N4NaO31 1881.6, found 1881.6 [M+Na]+.
4.5.2. p-Methoxyphenyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalim-
ido-b-D-glucopyranosyl-(1?4)-3,6-di-O-acetyl-2-deoxy-2-phtha-
limido-b-
D
-glucopyranoside (28)
Yield 85%; Rf 0.18 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+13.8 (c
0.60, CHCl3); 1H NMR (CDCl3): d 7.88–7.73 (m, 8H, Phth), 6.77–
6.67 (m, 4H, PhOCH3), 5.81 (dd, 1H, J 8.8, 10.3 Hz, H-3), 5.75 (d,
1H, J 8.4 Hz, H-1), 5.74 (dd, 1H, J 9.1, 11.0 Hz, H-30), 5.47 (d, 1H,
J 8.1 Hz, H-10), 5.16 (t, 1H, J 10.3 Hz, H-40), 4.45 (dd, 1H, J 4.1,
12.1 Hz, H-6i0), 4.41 (dd, 1H, J 8.4, 10.3 Hz, H-2), 4.31 (dd, 1H, J
1.5, 11.7 Hz, H-6i), 4.27 (dd, 1H, J 8.8, 10.6 Hz, H-20), 4.09 (dd,
4.5.5. p-Methoxyphenyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalim-
0
1H, J 2.2, 12.1 Hz, H-6ii ), 4.03 (t, 1H, J 9.1 Hz, H-4), 3.85 (ddd,
ido-b-D-glucopyranosyl-1?6)-3,4-di-O-acetyl-2-deoxy-2-phtha-
1H, J 2.2, 4.0, 9.8 Hz, H-50), 3.77 (ddd, 1H, J 1.9, 4.4, 9.9 Hz, H-
5), 3.74 (dd, 1H, J 7.3, 12.1 Hz, H-6ii), 3.69 (s, 3H, OCH3), 2.11,
2.01, 1.97, 1.93, 1.83 (s each, 3H each, 5 ꢂ COCH3); 13C NMR
(CDCl3): d 170.6, 170.1, 170.0, 169.8, 169.4 (5 ꢂ COCH3), 155.6–
114.3 (Ph), 97.4 (C-1, C-10), 75.6 (C-4), 72.4 (C-5), 71.9 (C-50),
70.6, 70.3 (C-3, C-30), 68.4 (C-40), 62.0 (C-6), 61.6 (C-60), 68.4 (C-
40), 55.6 (PhOCH3), 54.9 (C-2), 54.8 (C-20), 20.7, 20.6, 20.5, 20.3
(5 ꢂ COCH3); ESIMS: calcd for C45H44N2NaO19 939.2, found
939.2 [M+Na]+.
limido-b-
D
-glucopyranoside (35)
Yield 99%; Rf 0.18 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+37.8 (c
0.27, CHCl3); 1H NMR (CDCl3): d 7.84–7.69 (m, 8H, Phth), 6.84–
6.77 (m, 4H, PhOCH3), 5.91 (d, 1H, J 8.8 Hz, H-1), 5.80 (dd, 1H, J
9.4, 11.0 Hz, H-3), 5.64 (dd, 1H, J 9.4, 10.4 Hz, H-30), 5.53 (d, 1H, J
8.2 Hz, H-10), 5.12 (dd, 1H, J 8.8, 9.9 Hz, H-40), 4.96 (dd, 1H, J 8.8,
9.8 Hz, H-4), 4.46 (dd, 1H, J 8.3, 10.4 Hz, H-2), 4.30 (dd, 1H, J 8.8,
11.0 Hz, H-20), 4.22 (dd, 1H, J 4.4, 12.1 Hz, H-6i0), 4.10 (dd, 1H, J
0
2.2, 12.1 Hz, H-6ii ), 4.93 (dt, 1H, J 4.4, 9.3 Hz, H-5), 3.80 (d, 2H, J
4.4 Hz, H-6i, H-6ii), 3.77 (s, 3H, OCH3), 3.89 (ddd, 1H, J 2.2, 4.4,
9.9 Hz, H-50), 2.13, 2.03, 1.98, 1.85, 1.84 (s each, 3H each,
5 ꢂ COCH3); 13C NMR (CDCl3): d 170.7–169.2 (5 ꢂ COCH3), 155.5–
114.5 (Ph), 97.2 (C-10), 95.9 (C-1), 73.7 (C-5), 71.9 (C-50), 70.9 (C-
30), 70.5 (C-3), 69.5 (C-4), 68.7 (C-40), 67.6 (C-6), 61.7 (C-60), 55.6
(OCH3), 55.4 (C-2, C-20), 20.8–20.4 (5 ꢂ COCH3); ESIMS: calcd for
C45H44N2NaO19 939.2, found 939.2 [M+Na]+.
4.5.3. p-Methoxyphenyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalim-
ido-b-
halimido-b-
D
-glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-pht-
-glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-
D
2-phthalimido-b-D-glucopyranoside (20)
Yield 73%; Rf 0.23 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+13.0 (c
1.00, CHCl3); 1H NMR (CDCl3): d 7.97–7.61 (m, 12H, Phth), 7.35–
6.70 (m, 20H, Ph), 6.68–6.56 (m, 4H, PhOCH3), 5.79 (dd, 1H, J 8.8,
10.6 Hz, H-300), 5.52 (d, 1H, J 8.5 Hz, H-100), 5.40 (d, 1H, J 8.4 Hz, H-
1), 5.13 (t, 1H, J 9.5 Hz, H-400), 5.12 (d, 1H, J 8.0 Hz, H-10), 4.87 (d,
1H, J 12.5 Hz, PhCH2), 4.81 (d, 1H, J 12.8 Hz, PhCH2), 4.59 (d, 1H, J
12.1 Hz, PhCH2), 4.50–4.37 (m, 5H, PhCH2), 4.32 (dd, 1H, J 8.5,
10.6 Hz, H-200), 4.30–4.26 (m, 2H, H-2, H-40), 4.21 (dd, 1H, J 3.7,
12.1 Hz, H-6i00), 4.20–4.10 (m, 4H, H-3, H-4, H-20, H-30), 3.92 (dd,
1H, J 1.9, 12.1 Hz, H-6ii00), 3.63 (s, 3H, PhOCH3), 3.48–3.44 (m,
3H, H-6i, H-6i0, H-500), 3.36–3.31 (m, 2H, H-5, H-6ii), 3.24 (dd,
4.5.6. p-Methoxyphenyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalim-
ido-b-
alimido-b-
phthalimido-b-
D
-glucopyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phth-
D
-glucopyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-
D-glucopyranoside (39)
Yield 92%; Rf 0.28 (1:2 petroleum ether–EtOAc); ½a D20
ꢃ
+46.0 (c
0.40, CHCl3); 1H NMR (CDCl3): d 7.89–7.65 (m, 12H, Phth), 6.77–
6.76 (m, 4H, PhOCH3), 5.80 (d, 1H, J 8.5 Hz, H-1), 5.77 (dd, 1H, J
8.8, 10.6 Hz, H-300), 5.72 (dd, 1H, J 9.2, 10.6 Hz, H-3), 5.51 (dd, 1H,
J 9.2, 10.6 Hz, H-30), 5.48 (d, 1H, J 8.8 Hz, H-100), 5.32 (d, 1H, J
8.4 Hz, H-10), 5.20 (dd, 1H, J 9.2, 9.9 Hz, H-400), 4.88 (dd, 1H, J 9.2,
10.3 Hz, H-40), 4.86 (dd, 1H, J 9.2, 10.3 Hz, H-4), 4.41 (dd, 1H, J
8.4, 10.6 Hz, H-2), 4.37 (dd, 1H, J 4.4, 12.1 Hz, H-6i00), 4.35 (dd,
1H, J 8.5, 10.6 Hz, H-200), 4.19 (dd, 1H, J 1.9, 12.1 Hz, H-6ii00), 4.18
(dd, 1H, J 8.8, 11.0 Hz, H-20), 3.89 (ddd, 1H, J 2.2, 4.4, 10.3 Hz, H-
500), 3.81 (dd, 1H, J 2.2, 11.4 Hz, H-6i0), 3.75 (s, 3H, OCH3), 3.72
(dd, 1H, J 2.6, 11.0 Hz, H-6i), 3.67 (ddd, 1H, J 2.6, 6.2, 9.9 Hz, H-
0
1H, J 2.9, 11.3 Hz, H-6ii ), 2.98 (dd, 1H, J 1.4, 9.8 Hz, H-50), 1.98,
1.90, 1.84 (s each, 3H each, 3 ꢂ COCH3); 13C NMR (CDCl3): d
170.6, 170.1, 169.5 (3 ꢂ COCH3), 168.3–114.2 (Ph), 97.4 (C-1),
96.8 (C-10, C-100), 76.8 (C-30), 76.7 (C-3), 75.9 (C-40), 75.6 (C-4),
74.6 (C-5), 74.4 (PhCH2), 74.2 (C-50), 72.5, 72.4 (PhCH2), 71.4 (C-
500), 70.7 (C-300), 68.7 (C-400), 68.0 (C-6), 67.0 (C-60), 61.4 (C-600),
56.2 (C-20), 55.6, 55.5, 55.3 (C-2, C-200, OCH3), 20.6, 20.4
(3 ꢂ COCH3); ESIMS: calcd for C83H77N3NaO23 1506.5, found
1506.5 [M+Na]+.
0
5), 3.62 (dd, 1H, J 6.2, 11.3 Hz, H-6ii ), 3.50 (dd, 1H, J 6.2, 11.0 Hz,

614
P. Wang et al. / Carbohydrate Research 345 (2010) 607–620
H-6ii), 3.37 (ddd, 1H, J 2.2, 6.2, 9.9 Hz, H-50), 2.14, 2.04, 1.96, 1.93,
1.86, 1.83, 1.78 (s each, 3H each, 7 ꢂ Ac); 13C NMR (CDCl3): d
170.8–169.4 (7 ꢂ COCH3), 155.5–114.5 (Ph), 97.9 (C-100), 97.1 (C-
10), 96.5 (C-1), 73.2, 73.0 (C-5, C-50), 72.0 (C-500), 70.8, 70.6 (C-3,
C-30, C-300), 69.4 (C-4, C-40), 69.0 (C-400), 67.7 (C-60), 67.6 (C-6),
61.9 (C-600), 55.5 (OCH3), 54.2 (C-2, C-20, C-200), 20.6–20.4
(7 ꢂ COCH3); ESIMS: calcd for C63H61N3NaO27 1314.3, found
1314.3 [M+Na]+.
as a white solid with Rf 0.45 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+23.9 (c 0.75, CHCl3); 1H NMR (CDCl3): d 7.88–7.73 (m, 4H, Phth),
7.47–7.36 (m, 5H, PhCH), 6.86–6.74 (m, 4H, PhOCH3), 5.97 (d, 1H,
J 8.5 Hz, H-1), 5.95 (dd, 1H, J 9.1, 10.3 Hz, H-3), 5.57 (s, 1H, PhCH),
4.55 (dd, 1H, J 8.4, 10.3 Hz, H-2), 4.43 (dd, 1H, J 4.7, 10.6 Hz, H-6i),
3.90–3.81 (3H, m, H-4, H-5, H-6ii), 3.72 (s, 3H, OCH3), 1.92 (3H, s,
COCH3); ESIMS: calcd for C30H27KNO9 584.1, found 584.1 [M+K]+.
4.8. p-Methoxyphenyl 3-O-acetyl-2-deoxy-2-phthalimido-b-D-
4.5.7. p-Methoxyphenyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalim-
glucopyranoside (26)
ido-b-
alimido-b-
phthalimido-b-
D
-glucopyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phth-
-glucopyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-
-glucopyranosyl-(1?6)-3,4-di-O-acetyl-2-de-
D
A solution of 25 (0.229 mmol, 125 mg) in 80% AcOH (5 mL) was
stirred at 60 °C for 2 h and then concentrated in vacuum. The res-
idue was directly purified by silica gel column chromatography
(20:1 CHCl3–MeOH) to afford 26 (97 mg, 93%) as a white solid: Rf
D
oxy-2-phthalimido-b-D-glucopyranoside (42)
Yield 91%; Rf 0.19 (1:2 petroleum ether–EtOAc); ½a D20
ꢃ
+30.8 (c
0.33, CHCl3); 1H NMR (CDCl3): d 7.90–7.65 (m, 16H, Phth), 6.76–
6.72 (m, 4H, PhOCH3), 5.80 (dd, 1H, J 9.1, 10.6 Hz, H-3000), 5.75 (d,
1H, J 8.4 Hz, H-1), 5.72 (dd, 1H, J 9.2, 11.0 Hz, H-3), 5.64 (dd, 1H,
J 9.1, 10.6 Hz, H-30), 5.50 (dd, 1H, J 9.2, 10.6 Hz, H-300), 5.49 (d,
1H, J 8.5 Hz, H-1000), 5.32 (d, 1H, J 8.4 Hz, H-10), 5.29 (d, 1H, J
8.8 Hz, H-100), 5.20 (dd, 1H, J 9.5, 10.3 Hz, H-4000), 4.93 (dd, 1H, J
9.2, 9.9 Hz, H-40), 4.88 (dd, 1H, J 9.5, 10.3 Hz, H-4), 4.80 (dd, 1H, J
9.1, 10.3 Hz, H-400), 4.40–4.36 (m, 3H, H-2, H-2000, H-6i000), 4.21 (dd,
1H, J 8.4, 10.6 Hz, H-20), 4.21 (dd, 1H, J 2.2, 12.4 Hz, H-6ii000), 4.16
(dd, 1H, J 8.5, 10.6 Hz, H-200), 3.94–3.90 (m, 2H, H-6i0, H-5000),
0.23 (20:1 CHCl3–MeOH); ½a D20
ꢃ
+36.0 (c 0.40, CHCl3); 1H NMR
(CDCl3): d 7.87–7.74 (m, 4H, Phth), 6.85–6.73 (m, 4H, PhOCH3),
5.93 (d, 1H, J 8.5 Hz, H-1) 5.72 (dd, 1H, J 9.1, 10.6 Hz, H-3), 4.48
(dd, 1H, J 8.5, 10.6 Hz, H-2), 4.01 (ddd, 1H, J 3.2, 5.8, 11.8 Hz, H-
5), 3.93–3.89 (m, 2H, H-6i, H-6ii), 3.75–3.73 (m, 4H, H-4, OCH3),
2.90 (br s, 1H, OH), 2.11 (br s, 1H, OH), 1.98 (s, 3H, COCH3); ESIMS:
calcd for C23H23KNO9 496.1, found 496.1 [M+K]+.
4.9. p-Methoxyphenyl 3,6-di-O-acetyl-2-deoxy-2-phthalimido-
b-D
-glucopyranoside (27)
3.77–3.63 (m, 8H, H-5, H-6i, H-50, H-6ii , H-6i00, PhOCH3), 3.50 (dd,
0
1H, J 6.2, 11.0 Hz, H-6ii), 3.41 (dd, 1H, J 5.9, 11.3 Hz, H-6ii00), 3.28
(ddd, 1H, J 2.9, 5.5, 9.9 Hz, H-500), 2.16, 2.04, 1.97, 1.94, 1.86, 1.83,
1.78, 1.77 (some overlap, 27H, 9 ꢂ COCH3); 13C NMR (CDCl3): d
170.8–169.4 (9 ꢂ COCH3), 167.9–114.5 (Ph), 98.0 (C-1000), 97.6 (C-
10), 97.2 (C-100), 96.7 (C-1), 73.5 (C-5), 72.9 (C-50), 72.0 (C-500),
72.0 (C-5000), 70.8, 70.7, 70.6 (C-3, C-30, C-300, C-3000), 69.6 (C-40),
69.4 (C-4, C-400), 68.9 (C-4000), 68.1 (C-60), 67.4 (C-6, C-600), 62.0 (C-
6000), 55.5 (OCH3), 54.4, 54.3 (C-2, C-20, C-200, C-2000), 20.6–20.4
(9 ꢂ COCH3); ESIMS: calcd for C81H78N4NaO35 1689.4, found
1689.4 [M+Na]+.
To a solution of compound 26 (11.7 mmol, 5.34 g) in pyridine
(30 mL) and CH2Cl2 (100 mL) was added dropwise Ac2O
(12.26 mmol, 1.16 mL) in CH2Cl2 (20 mL) at 0 °C. The reaction mix-
ture was allowed to warm to rt and stir at rt for 12 h. The solution
was then diluted with EtOAc (300 mL) and successively washed
with 5% HCl (2 ꢂ 100 mL), satd NaHCO3 (2 ꢂ 100 mL) and brine
(2 ꢂ 100 mL). The organic layer was dried over anhyd Na2SO4
and then concentrated under vacuum. The residue was purified
by silica gel column chromatography (4:3 petroleum ether–EtOAc)
to afford compound 27 (4.96 g, 85%) as a white solid with Rf 0.23
(1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+16.0 (c 1.4, CHCl3); 1H NMR
4.6. p-Methoxyphenyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-
(CDCl3): d 7.86–7.73 (m, 4H, Phth), 6.87–6.72 (m, 4H, PhOCH3),
5.88 (d, 1H, J 8.4 Hz, H-1), 5.74 (dd, 1H, J 8.8, 10.6 Hz, H-3), 4.54
(dd, 1H, J 4.1, 11.8 Hz, H-6i), 4.49 (dd, 1H, J 8.5, 10.6 Hz, H-2),
4.40 (dd, 1H, J 1.9, 12.1 Hz, H-6ii), 3.85 (ddd, 1H, J 2.6, 4.8, 9.9 Hz,
H-5), 3.75 (t, 4H, J 9.5 Hz, H-4), 3.72 (s, 3H, OCH3), 3.28 (br s, 1H,
OH), 2.14, 1.95 (s each, 3H each, 2 ꢂ COCH3); ESIMS: calcd for
C25H25NNaO10 522.1, found 522.1 [M+Na]+.
b-
D
-glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phtha-
-glucopyranoside (19)
limido-b-
D
Compound 18 (1.44 mmol, 1.60 g) was dissolved in MeOH–
CH2Cl2 (1:5, 60 mL) and then NaOMe in MeOH (50%) was added
to pH 12. After stirring at rt for 2 h, the solution was neutralized
with cation-exchange resin (H+) and then filtered and concentrated
to afford 19 as an amorphous solid (1.59 g, 100%) with Rf 0.21 (10:1
CHCl3–CH3OH); 1H NMR (CDCl3): d 7.74–7.63 (m, 8H, Phth), 7.37–
6.83 (m, 20H, PhCH2), 6.72–6.58 (m, 4H, PhOCH3), 5.45 (d, 1H, J
8.8 Hz, H-1), 5.31 (d, 1H, J 8.4 Hz, H-10), 4.81 (d, 1H, J 11.8 Hz,
4.10. General procedure for protected saponins 45–58
A
mixture of trityl oleanolic ester or trityl ursolic ester
(1 mmol), glycosyl donor (1.5 mmol) and powdered 4 Å molecular
sieves (300 mg) in dried CH2Cl2 (40 mL) was stirred for 0.5 h at
room temperature. The mixture was cooled to ꢀ70 °C for 30 min,
followed by the dropwise addition of TMSOTf (0.2 mmol) under
Ar protection. After stirring at ꢀ70 °C for 45 min, the mixture
was quenched with MeOH. The reaction mixture was allowed to
warm up to room temperature, TsOH was added until the solution
was adjusted to pH 2, and stirring was continued at rt for 30 min.
The solid was then filtered off, and the filtrate was concentrated
under vacuum to afford a yellow syrup that was purified by silica
gel column chromatography to yield the pure saponin.
PhCH2), 4.79 (d, 1H,
J 12.1 Hz, PhCH2), 4.54–4.49 (m, 5H,
5 ꢂ PhCH2), 4.43 (d, 1H, J 11.7 Hz, PhCH2), 4.34 (dd, 1H, J 8.4,
10.6 Hz, H-2), 4.26 (dd, 1H, J 8.4, 11.0 Hz, H-30), 4.21–4.18 (m,
2H, H-3, H-4), 4.17 (dd, 1H, J 8.5, 10.6 Hz, H-20), 3.83 (dd, 1H, J
8.4, 9.5 Hz, H-40), 3.72 (dd, 1H, J 4.4, 9.5 Hz, H-6i), 3.65 (s, 3H,
0
OCH3), 3.58–3.53 (m, 2H, H-6i, H-6ii ), 3.45–3.40 (m, 3H, H-5, H-
6ii, H-50), 3.14 (br s, 1H, OH); ESIMS: calcd for C63H58N2NaO14
1089.4, found 1089.5 [M+Na]+.
4.7. p-Methoxyphenyl 3-O-acetyl-4,6-O-benzylidene-2-deoxy-2-
phthalimido-b-D-glucopyranoside (25)
4.10.1. 3-O-(3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
D-glu-
To a solution of compound 24 (0.236 mmol, 115 mg) in pyridine
(5 mL) was added Ac2O (2 mL). The reaction mixture was stirred at
rt for 3 h, then co-evaporated with toluene under reduced pressure
to afford a syrup that was purified by silica gel column chromatog-
raphy (2:1 hexane–EtOAc) to yield compound 25 (125 mg, 100%)
copranosyl)oleanolic acid (45)
Yield 78%; Rf 0.59 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+51.4 (c
0.65, CHCl3); 1H NMR (DMSO-d6): d 12.02 (br s, 1H, COOH),
7.89–7.87 (m, 4H, Phth), 5.69 (dd, 1H, J 9.1, 11.0 Hz, H-30),
5.31 (d, 1H, J 8.2 Hz, H-10), 5.14 (t, 1H, J 3.2 Hz, H-12), 4.96 (t,

P. Wang et al. / Carbohydrate Research 345 (2010) 607–620
615
1H, J 9.1 Hz, H-40), 4.28 (dd, 1H, J 5.0, 11.9 Hz, H-6i0), 4.08 (dd,
4.10.5. 3-O-(3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
copyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-b-
-glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phthalim-
D-glu-
0
1H, J 8.3, 10.6 Hz, H-20), 4.04–4.01 (m, 2H, H-50, H-6ii ), 3.04
(dd, 1H, J 4.6, 11.9 Hz, H-3), 2.72 (dd, 1H, J 3.7, 12.8 Hz, H-18),
2.05–0.59 (m, 22H), 2.03, 2.00, 1.80 (s each, 3H each,
3 ꢂ COCH3), 1.05, 0.87, 0.86, 0.79, 0.66, 0.46, 0.34 (s each, 3H
each, 7 ꢂ Me); ESIMS: calcd for C50H66NO12 872.4585, found
872.4588 [MꢀH]ꢀ.
D
ido-b-D-glucopyranosyl)oleanolic acid (49)
Yield 89%; Rf 0.46 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+22.7 (c
1.20, CHCl3); 1H NMR (CDCl3): d 7.95–7.49 (m, 12H, Phth), 7.34–
6.70 (m, 20H, PhCH2), 5.78 (dd, 1H, J 9.1, 10.3 Hz, H-3000), 5.51 (d,
1H, J 8.5 Hz, H-1000), 5.18 (t, 1H, J 3.3 Hz, H-12), 5.13 (d, 1H, J
8.8 Hz, H-100), 5.12 (t, 1H, J 10.1 Hz, H-4000), 4.88 (d, 1H, J 9.6 Hz,
H-10), 4.87 (d, 1H, J 12.9 Hz, PhCH2), 4.79 (d, 1H, J 12.9 Hz, PhCH2),
4.57 (d, 1H, J 12.1 Hz, PhCH2), 4.47–4.42 (m, 3H, PhCH2), 4.36–4.30
(m, 3H, 2 ꢂ PhCH2, H-2000), 4.27 (dd, 1H, J 8.5, 9.8 Hz, H-400), 4.22–
4.07 (m, 5H, H-20, H-30, H-200, H-300, H-6i000), 3.97–3.91 (m, 2H, H-
40, H-6ii000), 3.47–3.44 (m, 2H, H-6ii00, H-5000), 3.39 (d, 1H, J 9.1 Hz,
H-6i0), 3.27–3.24 (m, 3H, H-50, H-6i0, H-6ii00), 3.02 (d, 1H, J 9.1, H-
500), 2.77–2.73 (m, 2H, H-3, H-18), 1.98, 1.91, 1.84 (s each, 3H each,
3 ꢂ COCH3), 1.76–0.41 (m, 22H), 0.98, 0.87, 0.85, 0.71, 0.59, 0.38,
0.24 (s each, 3H each, 7 ꢂ Me); 13C NMR (CDCl3): d 170.7, 170.1,
169.5 (COCH3 ꢂ 3), 168.3–167.6 (NCOPh), 138.7–122.5 (Ph),
134.5, 123.7, 100.0 (C-10), 97.0 (C-100), 96.8 (C-1000), 89.7, 76.3 (C-
40), 76.0 (C-400), 74.4 (C-500), 74.3 (C-50), 74.2 (PhCH2 ꢂ 2), 72.5
(PhCH2), 72.4 (PhCH2), 71.4 (C-5000), 70.7 (C-3000), 68.8 (C-4000), 68.3
(C-60), 67.1 (C-600), 61.5 (C-6000), 56.6 (C-200), 56.0 (C-20), 55.3, 55.0
(C-2000), 47.4, 46.5, 45.9, 41.5, 40.9, 39.1, 38.2, 38.1, 36.6, 33.8,
33.0, 32.4, 30.6, 29.4, 27.6, 27.3, 25.8, 25.4, 23.5, 23.3, 22.9, 20.6–
20.4 (3 ꢂ COCH3), 17.9, 17.0, 16.2, 15.1; ESIMS: calcd for
C106H116N3O24 1814.7949, found 1814.7915 [MꢀH]ꢀ.
4.10.2. 3-O-(3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
D
-glu-
copranosyl)ursolic acid (46)
Yield 77%; Rf 0.59 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+16.4 (c
0.30, CHCl3); 1H NMR (CDCl3): d 7.88–7.72 (m, 4H, Phth), 5.83
(dd, 1H, J 9.2, 11.0 Hz, H-30), 5.37 (d, 1H, J 8.4 Hz, H-10), 5.21
(t, 1H, J 3.7 Hz, H-12), 5.13 (dd, 1H, J 9.1, 9.8 Hz, H-40), 4.36
(dd, 1H, J 8.5, 10.6 Hz, H-20), 4.31 (dd, 1H, J 5.5, 12.1 Hz, H-6i0),
0
4.15 (dd, 1H, J 2.6, 12.1 Hz, H-6ii ), 3.88 (ddd, 1H, J 2.2, 5.5,
9.9 Hz, H-50), 3.04 (dd, 1H, J 4.4, 11.8 Hz, H-3), 2.15 (d, 1H, J
11.3 Hz, H-18), 2.06–0.56 (m, 22H), 2.10, 2.04, 1.87 (s each, 3H
each, 3 ꢂ COCH3), 1.01 (s, 3H), 0.93 (d, 3H, J 6.5 Hz), 0.85 (d,
3H, J 6.6 Hz), 0.84 (s, 3H), 0.70 (s, 3H), 0.55 (s, 3H), 0.41 (s,
3H); ESIMS: calcd for C50H66NO12 872.4585, found 872.4557
[MꢀH]ꢀ.
4.10.3. 3-O-(3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-D-gluco-
pyranosyl-(1?4)-3,6-di-O-acetyl-2-deoxy-2-phthalimido-b-D-
glucopyranosyl)oleanolic acid (47)
Yield 69%; Rf 0.28 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+28.8 (c
0.40, CHCl3); 1H NMR (CDCl3): d 7.87–7.71 (m, 8H, Phth), 5.77
(dd, 1H, J 8.8, 10.6 Hz, H-30), 5.74 (dd, 1H, J 9.2, 10.6 Hz, H-300),
5.45 (d, 1H, J 8.0 Hz, H-100), 5.27 (d, 1H, J 8.5 Hz, H-10), 5.22 (t,
1H, J 3.7 Hz, H-12), 5.15 (t, 1H, J 9.8 Hz, H-400), 4.43 (dd, 1H, J
4.4, 12.4 Hz, H-6i00), 4.27–4.24 (m, 2H, H-6i0, H-200), 4.19 (dd,
1H, J 8.5, 10.6 Hz, H-20), 4.08 (dd, 1H, J 2.2, 12.5 Hz, H-6ii00),
3.90 (t, 1H, J 9.5 Hz, H-40), 3.83 (ddd, 1H, J 2.2, 4.0, 10.3 Hz, H-
4.10.6. 3-O-(3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
pyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-b-
glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-
D-gluco-
D
-
b-D-glucopyranosyl)ursolic acid (50)
Yield 86%; Rf 0.44 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+5.5 (c
0.65, CHCl3); 1H NMR (CDCl3): d 7.96–7.49 (m, 12H, Phth), 7.34–
6.69 (m, 20H, PhCH2), 5.79 (dd, 1H, J 9.2, 10.5 Hz, H-3000), 5.51 (d,
1H, J 8.3 Hz, H-1000), 5.14–5.11 (m, 3H, H-12, H-100, H-4000), 4.88 (d,
1H, J 8.7 Hz, H-10), 4.86 (d, 1H, J 13.3 Hz, PhCH2), 4.79 (d, 1H, J
12.8 Hz, PhCH2), 4.58 (d, 1H, J 11.9 Hz, PhCH2), 4.47–4.42 (m, 3H,
PhCH2), 4.36–4.30 (m, 3H, 2 ꢂ PhCH2, H-2000), 4.27 (t, 1H, J 9.6 Hz,
H-400), 4.23–4.05 (m, 5H, H-20, H-30, H-200, H-300, H-6i000), 3.97–3.91
(m, 2H, H-40, H-6ii000), 3.47–3.43 (m, 2H, H-6ii00, H-5000), 3.39 (d, 1H,
J 8.7 Hz, H-6i0), 3.27–3.23 (m, 3H, H-50, H-6i0, H-6ii00), 3.02 (d, 1H, J
9.6 Hz, H-500), 2.76 (dd, 1H, J 4.1, 11.5 Hz, H-3), 2.10 (d, 1H, J
11.0 Hz, H-18), 1.98, 1.91, 1.84 (s each, 3H each, 3 ꢂ COCH3),
1.94–0.42 (m, 22H), 0.90 (d, 3H, J 6.4 Hz), 0.79 (d, 3H, J 5.9 Hz),
0.93, 0.73, 0.61, 0.39, 0.25 (s each, 3H each, 5 ꢂ Me); 13C NMR
(CDCl3): d 183.0, 170.7, 170.1, 169.5 (3 ꢂ COCH3), 168.3–167.6
(NCOPh), 138.7–122.9 (Ph), 137.8, 125.7, 100.0 (C-10), 97.0 (C-100),
96.8 (C-1000), 89.6, 76.3 (C-40), 76.0 (C-400), 74.4 (C-500), 74.3 (C-50),
74.2 (2 ꢂ PhCH2), 72.4 (2 ꢂ PhCH2), 71.4 (C-5000), 70.7 (C-3000), 68.8
(C-4000), 68.3 (C-60), 67.1 (C-600), 61.4 (C-6000), 56.6 (C-200), 56.0 (C-
20), 55.3, 55.0 (C-2000), 52.5, 47.9, 47.3, 41.8, 39.3, 39.0, 38.7, 38.3,
38.2, 36.6, 36.5, 32.7, 30.6, 27.9, 27.3, 25.5, 24.0, 23.4, 23.2, 21.1,
20.6–20.4 (3 ꢂ COCH3), 17.9, 16.9, 16.2, 15.2; ESIMS: calcd for
C106H116N3O24 1814.7949, found 1814.7929 [MꢀH]ꢀ.
0
500), 3.71–3.66 (m, 2H, H-50, H-6ii ), 2.94 (dd, 1H, J 4.4, 11.8 Hz,
H-3), 2.76 (dd, 1H, J 4.0, 13.5 Hz, H-18), 2.13–0.51 (m, 22H),
2.11, 2.00, 1.96, 1.91, 1.83 (s each, 3H each, 5 ꢂ COCH3), 1.04,
0.89, 0.88, 0.76, 0.63, 0.49, 0.35 (s each, 3H each, 7 ꢂ Me);
ESIMS: calcd for C68H83N2O20 1247.5539, found 1247.5588
[MꢀH]ꢀ.
4.10.4. 3-O-(3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-D-glu-
copyranosyl-(1?4)-3,6-di-O -acetyl-2-deoxy-2-phthalimido-b-D-
glucopyranosyl)ursolic acid (48)
Yield 72%; Rf 0.28 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+12.2 (c
0.60, CHCl3); 1H NMR (CDCl3): d 7.87–7.71 (m, 8H, Phth), 5.78
(dd, 1H, J 9.2, 10.6 Hz, H-30), 5.73 (dd, 1H, J 9.2, 10.3 Hz, H-300),
5.45 (d, 1H, J 8.0 Hz, H-100), 5.27 (d, 1H, J 8.5 Hz, H-10), 5.17 (t,
1H, J 3.7 Hz, H-12), 5.15 (dd, 1H, J 9.5, 9.8 Hz, H-400), 4.42 (dd,
1H, J 4.4, 12.5 Hz, H-6i00), 4.27 (d, 1H, J 10.6 Hz, H-6i0), 4.26
(dd, 1H, J 8.5, 10.6 Hz, H-200), 4.19 (dd, 1H, J 8.5, 10.3 Hz, H-20),
4.08 (dd, 1H, J 2.2, 12.4 Hz, H-6ii00), 3.90 (t, 1H, J 9.5 Hz, H-40),
3.84 (ddd, 1H, J 2.2, 4.0, 9.9 Hz, H-500), 3.72–3.66 (m, 2H, H-50,
0
H-6ii ), 2.94 (dd, 1H, J 4.4, 11.7 Hz, H-3), 2.13 (d, 1H, J 11.0 Hz,
H-18), 2.04–0.49 (m, 22H), 2.11, 2.00, 1.96, 1.91, 1.83 (s each,
3H each, 5 ꢂ COCH3), 0.92 (d, 3H,
6.2 Hz), 0.98, 0.78, 0.65, 0.49, 0.36 (s each, 3H each, 5 ꢂ Me);
13C NMR (CDCl3):
J 6.2 Hz), 0.82 (d, 3H, J
4.10.7. 3-O-(3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
copyranosyl-(1?4)-3,6-di-O-acetyl-2-deoxy-2-phthalimido-b-
glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-
b- -glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phtha-
limido-b-
D-glu-
D
-
d
182.7, 170.6–169.4 (5 ꢂ COCH3), 137.8,
134.4–123.4 (Ph), 125.7, 99.7 (C-10), 97.3 (C-100), 90.6, 75.9 (C-
40), 72.1 (C-50), 71.9 (C-500), 70.7 (C-30), 70.6 (C-300), 68.4 (C-400),
62.3 (C-60), 61.6 (C-600), 55.3 (C-20), 55.0, 54.8 (C-200), 52.5, 47.8,
47.3, 41.8, 39.3, 39.0, 38.8, 38.3, 36.6, 32.7, 30.5, 27.9, 27.4,
25.3, 24.0, 23.5, 23.2, 21.1, 20.7–20.3 (5 ꢂ COCH3), 17.9, 17.0,
16.3, 15.3; ESIMS: calcd for C68H83N2O20 1247.5539, found
1247.5538 [MꢀH]ꢀ.
D
D
-glucopyranosyl)oleanolic acid (51)
Yield 82%; Rf 0.65 (1:2 petroleum ether–EtOAc); ½a D20
ꢃ
+14.5 (c
1.10, CHCl3); 1H NMR (CDCl3): d 7.92–7.47 (m, 16H, Phth), 7.22–
6.67 (m, 20H, PhCH2), 5.69–5.67 (m, 2H, H-3000, H-30000), 5.41 (d,
1H, J 8.4 Hz, H-1000), 5.36 (d, 1H, J 8.4 Hz, H-10000), 5.18 (t, 1H, J
3.3 Hz, H-12), 5.13 (t, 1H, J 9.9 Hz, H-40000), 5.08 (d, 1H, J 8.4 Hz,

616
P. Wang et al. / Carbohydrate Research 345 (2010) 607–620
H-100), 4.87 (d, 1H, J 8.1 Hz, H-10), 4.75 (d, 1H, J 13.1 Hz, PhCH2), 4.70
(d, 1H, J 12.8 Hz, PhCH2), 4.49–4.48 (m, 7H, 6 ꢂ PhCH2, H-6i0000), 4.22
(dd, 1H, J 8.5, 10.6 Hz, H-20000), 4.16–3.86 (m, 10H, H-20, H-30, H-40,
H-200, H-300, H-400, H-2000, H-4000, H-6000, H-60000), 3.76 (ddd, 1H, J 2.6,
3.3, 10.3 Hz, H-50000), 3.43–3.34 (m, 3H, H-6i0, H-6i00, H-6ii000), 3.24–
69.9 (C-40), 68.9 (C-400), 68.0 (C-60), 62.1 (C-600), 55.0, 54.8 (C-20),
54.4 (C-200), 47.4, 46.5, 45.9, 41.5, 40.9, 39.2, 38.3, 38.1, 36.7, 33.8,
33.1, 32.4, 30.6, 29.7, 27.6, 27.3, 25.8, 25.2, 23.6, 23.5, 22.9, 20.8–
20.4(5 ꢂ COCH3), 17.9, 17.1, 16.2, 15.2.
0
3.20 (m, 3H, H-50, H-6ii , H-6ii00), 3.11 (dt, 1H, J 3.3, 9.5 Hz, H-5000),
4.10.10. 3-O-(3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-D-glu-
2.98 (d, 1H, J 7.3 Hz, H-500), 2.76–2.71 (m, 2H, H-3, H-18), 2.05,
1.97, 1.89, 1.81, 1.77 (3H each, s each, 5 ꢂ COCH3), 1.76–0.40 (m,
22H), 0.98, 0.87, 0.85, 0.71, 0.59, 0.38, 0.22 (s each, 3H each,
7 ꢂ Me); 13C NMR (CDCl3): d 182.8, 170.5, 170.1, 169.9, 169.7,
169.3 (5 ꢂ COCH3), 168.2–167.5 (NCOPh), 138.7–123.5 (Ph),
134.5, 123.6, 99.8 (C-10), 97.7 (C-10000), 96.9 (C-100), 96.6 (C-1000),
89.6, 76.1 (C-400), 75.7 (C-40, C-4000), 74.2 (2 ꢂ PhCH2), 74.1 (C-50,C-
500), 72.4 (PhCH2), 72.2 (PhCH2), 71.7 (C-5000, C-50000), 70.9 (C-30000),
70.5 (C-3000), 68.8 (C-40000), 68.2 (C-60), 66.9 (C-600), 61.8 (C-6000),
61.4 (C-60000), 56.5 (C-200), 56.0 (C-20), 55.7 (C-2000), 55.0, 54.7 (C-20000),
47.4, 43.4, 45.8, 41.4, 40.8, 39.1, 38.1, 36.5, 33.7, 33.0, 32.4, 30.6,
29.3, 27.5, 27.2, 25.7, 25.4, 23.5, 23.3, 22.8, 20.6–20.3 (5 ꢂ COCH3),
17.8, 16.9, 16.1, 15.1.
copyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-D-
glucopyranosyl)ursolic acid (54)
Yield 64%; Rf 0.28 (1:1 petroleum ether–EtOAc); ½a D20
ꢃ
+50.8 (c
0.28, CHCl3); 1H NMR (CDCl3): d 7.90–7.72 (m, 8H, Phth), 5.73
(dd, 1H, J 8.8, 10.4 Hz, H-30), 5.72 (dd, 1H, J 8.8, 10.4 Hz, H-300),
5.59 (d, 1H, J 8.8 Hz, H-100), 5.31 (d, 1H, J 8.2 Hz, H-10), 5.22 (t,
1H, J 3.3 Hz, H-12), 5.16 (t, 1H, J 9.9 Hz, H-400), 4.88 (t, 1H, J
9.3 Hz, H-40), 4.32–4.29 (m, 2H, H-200, H-6i00), 4.26 (dd, 1H, J 8.8,
11.0 Hz, H-20), 4.20 (dd, 1H, J 1.7, 12.1 Hz, H-6ii00), 3.84 (ddd, 1H, J
2.2, 4.9, 10.4 Hz, H-500), 3.78–3.75 (m, 3H, H-50, H-6i0, H-6ii ), 3.16
0
(dd, 1H, J 4.4, 11.5 Hz, H-3), 2.16 (d, 1H, J 11.6 Hz, H-18), 2.05–
0.61 (m, 22H), 2.15, 2.02, 1.96, 1.84, 1.82 (s each, 3H each,
5 ꢂ COCH3), 0.93 (d, 3H, J 6.6 Hz), 0.84 (d, 3H, J 6.1 Hz), 1.03,
0.78, 0.70, 0.44, 0.40 (s each, 3H each, 5 ꢂ Me); 13C NMR (CDCl3):
d 170.7–169.4 (5 ꢂ COCH3), 137.9, 134.3–123.6 (Ph), 125.7, 99.8
(C-10), 97.4 (C-100), 90.1, 73.4 (C-50), 72.0 (C-500), 70.8 (C-300), 70.5
(C-30), 69.8 (C-40), 68.9 (C-400), 67.7 (C-60), 62.0 (C-600), 54.9, 54.7
(C-20), 54.4 (C-200), 52.5, 47.9, 47.3, 41.8, 39.3, 39.0, 38.7, 38.3,
38.2, 36.7, 36.6, 32.7, 30.6, 27.9, 27.3, 25.3, 24.0, 23.4, 23.3, 21.1,
20.8–20.4 (5 ꢂ COCH3), 17.9, 17.0, 16.9, 16.2, 15.4; ESIMS: calcd
for C68H83N2O20 1247.5539, found 1247.5544 [MꢀH]ꢀ.
4.10.8. 3-O-(3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
copyranosyl-(1?4)-3,6-di-O-acetyl-2-deoxy-2-phthalimido-b-
glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-
b- -glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-phtha-
limido-b- -glucopyranosyl)ursolic acid (52)
D-glu-
D-
D
D
Yield 84%; Rf 0.47 (1:2 petroleum ether–EtOAc); 1H NMR
(CDCl3): d 7.92–7.47 (m, 16H, Phth), 7.22–6.68 (m, 20H, PhCH2),
5.71–5.67 (m, 2H, H-3000, H-30000) 5.41 (d, 1H, J 8.2 Hz, H-1000), 5.36
(d, 1H, J 8.7 Hz, H-10000), 5.15–5.12 (m, 2H, H-12, H-40000), 5.08 (d,
1H, J 8.2 Hz, H-100), 4.86 (d, 1H, J 7.8 Hz, H-10), 4.75 (d, 1H, J
12.8 Hz, PhCH2), 4.70 (d, 1H, J 12.8 Hz, PhCH2), 4.49–4.28 (m, 7H,
6 ꢂ PhCH2, H-6i0000), 4.22 (dd, 1H, J 8.3, 10.6 Hz, H-20000), 4.17–3.86
(m, 10H, H-20, H-30, H-40, H-200, H-300, H-400, H-2000, H-4000, H-6000, H-
4.10.11. 3-O-(3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
copyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
glucopyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
D-glu-
D-
D
-glucopyranosyl)oleanolic acid (55)
Yield 69%; Rf 0.39 (1:2 petroleum ether–EtOAc); ½a D20
ꢃ
+29.9 (c
6
0000), 3.76 (dt, 1H, J 2.8, 10.8 Hz, H-50000), 3.43–3.33 (m, 3H, H-6i0,
0.70, CHCl3); 1H NMR (CDCl3): d 7.93–7.71 (m, 12H, Phth), 5.59
(dd, 1H, J 9.2, 10.6 Hz, H-3000), 5.66 (dd, 1H, J 9.2, 10.5 Hz, H-30),
5.59 (dd, 1H, J 9.2, 10.6 Hz, H-300), 5.50 (d, 1H, J 8.8 Hz, H-1000),
5.42 (d, 1H, J 8.3 Hz, H-100), 5.27 (t, 1H, J 3.2 Hz, H-12), 5.23 (d,
1H, J 8.7 Hz, H-10), 5.20 (t, 1H, J 9.7 Hz, H-4000), 4.92 (t, 1H, J
9.7 Hz, H-400), 4.74 (t, 1H, J 9.2 Hz, H-40), 4.38 (dd, 1H, J 4.6,
12.4 Hz, H-6i000), 4.35 (dd, 1H, J 8.3, 10.6 Hz, H-2000), 4.23–4.16 (m,
3H, H-20, H-200, H-6ii000), 3.91 (ddd, 1H, J 2.3, 5.0, 10.6 Hz, H-5000),
3.87 (d, 1H, J 8.7 Hz, H-600), 3.73–3.68 (m, 2H, H-500, H-6ii00), 3.63
H-6i00, H-6ii000), 3.24–3.20 (m, 3H, H-50, H-6ii , H-6ii00), 3.11 (d, 1H, J
9.6 Hz, H-5000), 2.98 (d, 1H, J 7.7 Hz, H-500), 2.75 (dd, 1H, J 4.1,
11.5 Hz, H-3), 2.09 (d, 1H, J 11.5 Hz, H-18), 2.05, 1.97, 1.89, 1.81,
1.77 (s each, 3H each, 5 ꢂ COCH3), 1.79–0.38 (m, 22H), 0.90 (d,
3H J 5.9 Hz), 0.79 (d, 3H, J 6.4 Hz), 0.92, 0.72, 0.61, 0.38, 0.24 (s
each, 3H each, 5 ꢂ Me); 13C NMR (CDCl3): d 182.8, 170.6–169.4
(5 ꢂ COCH3), 168.3–167.5 (NCOPh), 138.7–122.8 (Ph), 137.8,
125.7, 100.0 (C-10), 97.7 (C-10000), 97.0 (C-100), 96.6 (C-1000), 89.5,
76.2 (C-400), 75.7 (C-40, C-4000), 74.2 (2 ꢂ PhCH2), 74.1 (C-50,C-500),
72.4 (PhCH2), 72.3 (PhCH2), 71.8 (C-50000), 71.8 (C-5000), 70.9 (C-30000),
70.5 (C-3000), 68.8 (C-40000), 68.2 (C-60), 66.9 (C-600), 61.8 (C-6000), 61.4
(C-60000), 56.5 (C-200), 56.0 (C-20), 55.7 (C-2000), 55.0, 54.7 (C-20000), 52.4,
47.8, 47.3, 41.8, 39.3, 39.0, 38.7, 38.3, 38.2, 36.6, 36.5, 32.7, 30.5,
27.9, 27.3, 25.5, 24.0, 23.4, 23.2, 21.2, 20.7–20.4 (5 ꢂ COCH3),
17.8, 16.9, 16.2, 15.2.
0
(dd, 1H, J 2.2, 12.4 Hz, H-6i0), 3.55–3.49 (m, 2H, H-50, H-6ii ), 3.10
0
(dd, 1H, J 4.6, 11.9 Hz, H-3), 2.80 (dd, 1H, J 4.1, 13.7 Hz, H-18),
2.16, 2.05, 1.99, 1.94, 1.86, 1.83, 1.78 (3H each, s each, 7 ꢂ COCH3),
2.17–0.59 (m, 22H), 1.07, 0.92, 0.89, 0.76, 0.68, 0.43, 0.38 (s each,
3H each, 7 ꢂ Me); 13C NMR (CDCl3): d 170.8–169.5 (7 ꢂ COCH3),
168.2–167.3 (NCOPh), 143.5, 134.6–122.6 (Ph), 123.8, 99.6 (C-10),
98.0 (C-1000), 97.2 (C-100), 89.8, 73.1 (C-50), 73.0 (C-500), 72.1 (C-5000),
70.8 (C-300, C-3000), 70.5 (C-30), 69.9 (C-40), 69.6 (C-400), 68.9 (C-4000),
68.0 (C-600), 67.8 (C-60), 62.0 (C-6000), 54.9 (C-20), 54.8 (C-200), 54.4
(C-5, C-2000), 47.4, 46.5, 45.9, 41.5, 41.0, 39.2, 38.3, 38.2, 36.7, 33.8,
33.1, 32.4, 30.6, 29.7, 27.6, 27.3, 25.8, 25.2, 23.6, 23.5, 22.7, 20.9–
20.4 (7 ꢂ COCH3), 18.0, 17.1, 16.2, 15.2; ESIMS: calcd for
C86H100N3O28 1622.6493, found 1622.6415 [MꢀH]ꢀ.
4.10.9. 3-O-(3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-D-glu-
copyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-D-
glucopyranosyl)oleanolic acid (53)
Yield 62%; Rf 0.28 (1:1 petroleum ether–EtOAc); 1H NMR
(CDCl3): d 7.90–7.72 (m, 8H, Phth), 5.72 (dd, 1H, J 8.8, 10.4 Hz, H-
30), 5.71 (dd, 1H, J 8.8, 10.4 Hz, H-300), 5.56 (d, 1H, J 8.7 Hz, H-100),
5.31 (d, 1H, J 8.2 Hz, H-10), 5.27 (t, 1H, J 3.3 Hz, H-12), 5.16 (t, 1H,
J 9.6 Hz, H-400), 4.90 (t, 1H, J 9.6 Hz, H-40), 4.33–4.29 (m, 2H, H-200,
H-6i00), 4.25 (dd, 1H, J 8.2, 10.6 Hz, H-20), 4.20 (dd, 1H, J 2.3,
12.4 Hz, H-6ii00), 3.85 (ddd, 1H, J 2.3, 5.0, 10.1 Hz, H-500), 3.82–3.72
4.10.12. 3-O-(3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
copyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
glucopyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
D-glu-
D-
D
-glucopyranosyl)ursolic acid (56)
(m, 3H, H-50, H-6i0, H-6ii ), 3.08 (dd, 1H, J 4.6, 11.9 Hz, H-3), 2.80
Yield 61%; Rf 0.39 (1:2 petroleum ether–EtOAc); ½a D20
ꢃ
+45.3 (c
0
(dd, 1H, J 3.7, 13.7 Hz, H-18), 2.13–0.58 (m, 22H), 2.15, 2.03, 1.96,
1.85, 1.82(s each, 3H each, 5 ꢂ COCH3), 1.07, 0.92, 0.89, 0.75,
0.67, 0.44, 0.36 (s each, 3H each, 7 ꢂ Me); 13C NMR (CDCl3): d
170.7–169.5 (3 ꢂ COCH3), 134.3–122.5 (Ph), 123.7, 99.7 (C-10),
97.5 (C-100), 90.3, 73.1 (C-50), 72.1 (C-500), 71.0 (C-300), 70.6 (C-30),
0.41, CHCl3); 1H NMR (CDCl3): d 7.94–7.71 (m, 12H, Phth), 5.79
(dd, 1H, J 9.1, 10.5 Hz, H-3000), 5.67 (dd, 1H, J 9.1, 10.5 Hz, H-30),
5.60 (dd, 1H, J 9.2, 10.6 Hz, H-300), 5.50 (d, 1H, J 8.7 Hz, H-1000),
5.45 (d, 1H, J 8.2 Hz, H-100), 5.23 (d, 1H, J 8.3 Hz, H-10), 5.22 (t,
1H, J 3.3 Hz, H-12), 5.20 (t, 1H, J 9.6 Hz, H-4000), 4.92 (t, 1H, J

P. Wang et al. / Carbohydrate Research 345 (2010) 607–620
617
9.6 Hz, H-400), 4.74 (t, 1H, J 9.7 Hz, H-40), 4.39 (dd, 1H, J 4.6, 12.4 Hz,
H-6i000), 4.35 (dd, 1H, J 8.3, 10.6 Hz, H-2000), 4.22–4.19 (m, 2H, H-20,
H-6ii000), 4.17 (dd, 1H, J 8.7, 11.0 Hz, H-200), 3.91 (ddd, 1H, J 2.3,
5.0, 10.5 Hz, H-5000), 3.87 (d, 1H, J 9.2 Hz, H-6i00), 3.72–3.68 (m, 2H,
0.39 (s each, 3H each, 5 ꢂ Me); 13C NMR (CDCl3): d 182.9, 170.8–
169.4 (9 ꢂ COCH3), 168.2–167.3 (NCOPh), 138.0, 134.4–113.9
(Ph), 125.8, 99.7 (C-10), 98.1 (C-10000), 97.7 (C-1000), 97.0 (C-100),
89.9, 73.3 (C-5000), 73.0 (C-50), 72.8 (C-500), 72.1 (C-50000), 70.8 (C-
300), 70.7 (C-30,C-30000), 70.5 (C-3000), 69.8 (C-4000), 69.7 (C-400), 69.6
(C-40), 69.0 (C-40000), 68.2 (C-60), 67.6 (C-600), 67.3 (C-6000), 62.0 (C-
0
H-500, H-6ii00), 3.62–3.56 (m, 2H, H-6i0, H-6ii ), 3.50 (ddd, 1H, J 3.2,
5.9, 10.1 Hz, H-50), 3.17 (dd, 1H, J 4.1, 11.9 Hz, H-3), 2.15 (d, 1H, J
11.9 Hz, H-18), 2.16, 2.05, 1.99, 1.93, 1.86, 1.83, 1.77 (3H each, s
each, 7 ꢂ COCH3), 2.04–0.61 (m, 22H), 0.92 (d, 3H, J 5.9 Hz), 0.83
(d, 3H, J 6.4 Hz), 1.02, 0.77, 0.70, 0.43, 0.40 (s each, 3H each,
5 ꢂ Me); 13C NMR (CDCl3): d 182.9, 170.8–169.4 (7 ꢂ COCH3),
168.2–167.3 (NCOPh), 134.5–123.4 (Ph), 137.9, 125.7, 99.7 (C-10),
97.9 (C-1000), 97.0 (C-100), 89.9, 73.3 (C-50), 73.1 (C-500), 72.0 (C-5000),
70.8 (C-300), 70.7 (C-3000), 70. (C-30), 69.9 (C-40), 69.6 (C-400), 68.9(C-
4000), 67.9 (C-600), 67.5 (C-60), 61.9 (C-6000), 54.9 (C-20), 54.8 (C-200),
54.4 (C-5, C-2000), 52.5, 47.9, 47.3, 41.8, 39.4, 39.0, 38.8, 38.3, 38.2,
36.7, 36.6, 32.8, 30.6, 28.0, 27.4, 25.3, 24.1, 23.4, 23.3, 21.2, 20.8–
20.4 (7 ꢂ COCH3), 18.0, 17.1, 17.0, 16.2, 15.4; ESIMS: calcd for
C86H100N3O28 1622.6493, found 1622.6470 [MꢀH]ꢀ.
6
0000), 55.0, 54.8 (C-20), 54.4 (C-200, C-2000, C-20000), 52.6, 47.9, 47.3,
41.9, 39.4, 39.1, 38.8, 38.3, 38.2, 36.7, 36.6, 32.8, 30.6, 28.0, 27.4,
25.3, 24.1, 23.4, 23.3, 21.2, 20.8–20.4 (9 ꢂ COCH3), 18.0, 17.1,
17.0, 16.2, 15.4; ESIMS: calcd for C104H117N4O36 1997.7448, found
1997.7440 [MꢀH]ꢀ.
4.11. General procedure for target saponins 1–14
Compounds 45–58 (0.1 mmol) were each mixed in BuOH
(10 mL) and NH2CH2CH2NH2 (5 mL) was added. After stirring over-
night at 80–90 °C, the mixture was concentrated to afford a yellow
syrup, which was co-evaporated with toluene twice and then dis-
solved in 1:1 pyridine–Ac2O (5 mL). The resulting mixture was stir-
red at rt overnight and then concentrated to yield a yellow solid,
which was dissolved in 5:1 MeOH–CH2Cl2 (30 mL) and then
NaOMe (20 mg, 50%) in MeOH was added to adjust to pH 10. After
stirring at rt for 1 h, the solution was neutralized with cation-ex-
change resin (H+), and then filtered and concentrated to give a syr-
up. The resulting residues of 45–48 and 53–58 were purified by
column chromatography to afford the pure target saponins. The
resulting residue of 49–52 was dissolved in MeOH (10 mL) and
4.10.13. 3-O-(3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
pyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
pyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
D-gluco-
D
-gluco-
-gluco-
-gluco-
D
pyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
D
pyranosyl)oleanolic acid (57)
Yield 54%; Rf 0.29 (1:2 petroleum ether–EtOAc); 1H NMR
(CDCl3): d 7.92–7.71 (m, 16H, Phth), 5.79 (dd, 1H, J 9.2, 10.6 Hz,
H-30000), 5.67–5.64 (m, 2H, H-30, H-3000), 5.56 (dd, 1H, J 9.1, 10.6 Hz,
H-300), 5.49 (d, 1H, J 8.8 Hz, H-10000), 5.37 (d, 1H, J 8.5 Hz, H-100),
5.32 (d, 1H, J 8.8 Hz, H-1000), 5.23–5.18 (m, 3H, H-12, H-10, H-4000),
4.93 (t, 1H, J 9.9 Hz, H-40), 4.83 (t, 1H, J 9.9 Hz, H-400), 4.74 (t, 1H,
J 9.5 Hz, H-4000), 4.39–4.36 (m, 2H, H-20000, H-6i0000), 4.22–4.12 (m,
4H, H-20, H-200, H-2000,H-6ii0000), 3.98–3.90 (m, 2H, H-50000, H-6i0),
then HOAc (200 lL) and Pd/C (100 mg) was added. [Caution! Ex-
treme fire hazard.] The mixture was vigorously stirred at room
temperature under a hydrogen atmosphere (balloon) until the deb-
enzylation was complete as determined by TLC. The catalyst was
removed by filtration through Celite, and the filter was washed
with EtOAc and MeOH. The filtrate was concentrated and purified
by column chromatography to give the target saponin.
0
3.78–3.67 (m, 3H, H-50, H-6ii , H-6i000), 3.61–3.45 (m, 5H, H-500, H-
6i00, H-6ii00, H-5000, H-6ii000), 3.09 (dd, 1H, J 4.0, 11.3 Hz, H-3), 2.81
(dd, 1H, J 3.7, 13.3 Hz, H-3), 2.16, 2.04, 1.99, 1.94, 1.86, 1.82,
1.78, 1.77 (some overlap, 27H, 9 ꢂ COCH3), 2.02–0.58 (m, 22H),
1.08, 0.92, 0.89, 0.75, 0.69, 0.43, 0.38 (s each, 3H each, 7 ꢂ Me);
13C NMR (CDCl3): d 182.5, 170.8–169.4 (9 ꢂ COCH3), 168.2–167.4
(NCOPh), 143.7, 134.5–113.9 (Ph), 123.8, 99.6 (C-10), 98.1 (C-10000),
97.7 (C-1000), 97.2 (C-100), 89.9, 73.3 (C-5000), 73.0 (C-50), 72.8 (C-500),
72.1 (C-50000), 70.8 (C-300, C-30000), 70.7 (C-30), 70.6 (C-3000), 69.6 (C-
4000), 69.7 (C-40, C-400), 69.0 (C-40000), 68.2 (C-60), 67.6 (C-600), 67.3
(C-6000), 62.0 (C-60000), 55.0, 54.9 (C-20), 54.4 (C-200, C-2000, C-20000),
47.5, 46.5, 46.0, 41.7, 41.1, 39.2, 38.3, 38.2, 36.7, 33.9, 33.1, 32.5,
30.7, 29.7, 27.7, 27.3, 25.8, 25.2, 23.6, 23.5, 22.7, 20.8–20.4
(9 ꢂ COCH3), 18.0, 17.1, 16.3, 15.2; ESIMS: calcd for
C104H117N4O36 1997.7448, found 1997.7445 [MꢀH]ꢀ.
4.11.1. 3-O-(2-Acetamido-2-deoxy-b-D-glucopranosyl)oleanolic
acid (1)
Yield 69%; Rf 0.13 (6:1 CHCl3–CH3OH); ½a D20
ꢃ
+18.8 (c 1.73,
CH3OH); 1H NMR (DMSO-d6): d 12.05 (br s, 1H, COOH), 7.70 (d,
1H, J 9.2 Hz, NH0), 5.15 (t, 1H, J 2.9 Hz H-12), 4.94 (d, 1H, J 4.7 Hz,
OH), 4.83 (d, 1H, J 5.1 Hz, OH), 4.41 (t, 1H, J 5.5 Hz, OH), 4.25 (d,
1H, J 8.4 Hz, H-10), 3.66 (dd, 1H, J 5.5, 10.6 Hz, H-6i ), 3.43 (dd,
0
0
1H, J 3.7, 10.3 Hz, H-6ii ), 3.38 (t, 1H, J 9.5 Hz, H-20), 3.27 (dd, 1H,
J 8.1, 10.3 Hz, H-30), 3.04–3.01 (m, 2H, H-40, H-50), 2.97 (dd, 1H, J
4.4, 11.7 Hz, H-3), 2.74 (dd, 1H, J 4.0, 14.3 Hz, H-18), 1.91–0.68
(m, 22H), 1.76 (s, 3H, COCH3), 1.09, 0.89, 0.89, 0.85, 0.71, 0.65,
0.42 (s each, 3H each, 7 ꢂ Me); 13C NMR (DMSO-d6): d 178.3,
169.2 (COCH3), 144.4, 122.0.4, 104.1 (C-10), 88.6, 77.3 (C-50), 74.6
(C-30), 71.3 (C-40), 61.7 (C-60), 56.4 (C-20), 55.4, 47.6, 46.3, 46.0,
41.8, 41.4, 39.4, 38.8, 38.6, 36.9, 33.9, 33.4, 33.0, 32.7, 31.0, 28.1,
27.8, 26.1, 25.9, 23.9, 23.7 (COCH3), 23.5, 23.0, 18.3, 17.5, 16.9,
15.6; ESIMS: calcd for C38H60NO8 658.4319, found 658.4337
[MꢀH]ꢀ.
4.10.14. 3-O-(3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-b-
copyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
glucopyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-b-
-glucopyranosyl-(1?6)-3,4-di-O-acetyl-2-deoxy-2-phthalimido-
D-glu-
D-
D
b-D-glucopyranosyl)ursolic acid (58)
Yield 51%; Rf 0.29 (1:2 petroleum ether–EtOAc); ½a D20
ꢃ
+16.7 (c
0.85, CHCl3); 1H NMR (CDCl3): d 7.92–7.71 (m, 16H, Phth), 5.79
(dd, 1H, J 9.2, 10.3 Hz, H-30000), 5.68–5.64 (m, 2H, H-30, H-3000), 5.56
(dd, 1H, J 9.2, 10.3 Hz, H-300), 5.49 (d, 1H, J 8.4 Hz, H-10000), 5.41 (d,
1H, J 8.4 Hz, H-100), 5.33 (d, 1H, J 8.4 Hz, H-1000), 5.23–5.19 (m, 3H,
H-12, H-10, H-4000), 4.93 (t, 1H, J 9.5 Hz, H-40), 4.83 (t, 1H, J 9.8 Hz,
H-400), 4.74 (t, 1H, J 9.5 Hz, H-4000), 4.39–4.36 (m, 2H, H-20000, H-6i0000),
4.23–4.16 (m, 3H, H-20, H-2000,H-6ii0000), 4.14 (dd, 1H, J 8.8, 10.6 Hz,
H-200), 3.98–3.90 (m, 2H, H-50000, H-6i0), 3.78–3.67 (m, 3H, H-50, H-
4.11.2. 3-O-(2-Acetamido-2-deoxy-b-D-glucopranosyl)ursolic
acid (2)
Yield 69%; Rf 0.13 (6:1 CHCl3–MeOH); ½a D20
ꢀ11.0 (c 0.17,
ꢃ
CH3OH); 1H NMR (DMSO-d6): d 11.89 (br s, 1H, COOH), 7.71 (d,
1H, J 9.1 Hz, NH0), 5.13 (t, 1H, J 2.9 Hz H-12), 4.94 (br s, 1H, OH),
4.84 (d, 1H, J 5.2 Hz, OH), 4.39 (t, 1H, J 5.5 Hz, OH), 4.25 (d, 1H, J
8.5 Hz, H-10), 3.65 (dd, 1H, J 4.4, 8.1 Hz, H-6i0), 3.43 (dd, 1H, J 5.9,
0
9.9 Hz, H-6ii ), 3.39 (t, 1H, J 9.1 Hz, H-20), 3.30 (m, 1H, H-30),
6ii , H-6i000), 3.61–3.45 (m, 5H, H-500, H-6i00, H-6ii00, H-5000, H-6ii000),
3.05–3.02 (m, 2H, H-40, H-50), 2.98 (dd, 1H, J 4.4, 11.7 Hz, H-3),
2.11 (d, 1H, J 11.4 Hz, H-18), 1.93–0.68 (m, 22H), 1.76 (s, 3H,
COCH3), 0.91 (d, 3H, J 6.6 Hz), 0.81 (d, 3H, J 6.6 Hz), 1.04, 0.89,
0.87, 0.74, 0.65, (s each, 3H each, 5 ꢂ Me); 13C NMR (DMSO-d6): d
0
3.15 (dd, 1H, J 4.0, 11.7 Hz, H-3), 2.16, 2.04, 1.99, 1.94, 1.86, 1.83,
1.78, 1.77 (some overlap, 27H, 9 ꢂ COCH3), 2.16–0.60 (m, 23H),
0.93 (d, 3H, J 6.5 Hz), 0.84 (d, 3H, J 6.2 Hz), 1.03, 0.77, 0.71, 0.43,

618
P. Wang et al. / Carbohydrate Research 345 (2010) 607–620
178.3, 168.7 (COCH3), 138.2, 124.5, 103.5 (C-10), 88.0, 76.7 (C-50),
74.0 (C-30), 70.7 (C-40), 61.2 (C-60), 55.8 (C-20), 54.9, 52.4, 47.0,
46.8, 41.6, 40.4, 38.5, 38.4, 38.3, 38.1, 36.3, 36.2, 32.6, 30.2, 27.6,
27.5, 25.3, 23.8, 23.2, 23.1 (COCH3), 22.8, 21.1, 17.7, 17.0, 16.9,
16.3, 15.2; ESIMS: calcd for C38H60NO8 658.4319, found 658.4302
[MꢀH]ꢀ.
(C-400), 78.2 (C-5000), 76.5 (C-500), 76.2 (C-50), 75.8 (C-30000), 74.2 (C-
30, C-300), 72.0 (C-4000), 62.6 (C-6000), 61.7 (C-60), 61.6 (C-600), 57.3 (C-
2000), 57.0 (C-20), 56.9, 56.6 (C-200), 47.8, 45.4, 42.9, 42.8, 40.6, 39.9,
39.6, 37.9, 35.0, 34.0, 33.6, 31.6, 28.9, 28.6, 26.8, 26.4, 24.5, 24.2,
24.0, 23.1, 23.0, 22.9 (3 ꢂ COCH3), 19.3, 17.9, 17.0, 15.9; ESIMS:
calcd for C54H86N3O18 1064.5906, found 1064.5942 [MꢀH]ꢀ.
4.11.3. 3-O-(2-Acetamido-2-deoxy-b-
D-glucopranosyl-(1?4)-2-
4.11.6. 3-O-(2-Acetamido-2-deoxy-b-D-glucopranosyl-(1?4)-2-
acetamido-2-deoxy-b- -glucopyranosyl)oleanolic acid (3)
D
acetamido-2-deoxy-b- -glucopranosyl-(1?4)-2-acetamido-2-
D
Yield 61%; Rf 0.50 (4:1 CHCl3–MeOH); 1H NMR (DMSO-d6): d
12.02 (br s, 1H, COOH), 7.80 (d, 1H, J 8.4 Hz, NH), 7.77 (d, 1H, J
9.5 Hz, NH), 5.15 (br s, 1H, H-12), 5.10 (br s, 1H, OH), 5.00 (br s,
1H, OH), 4.72 (dt, 1H, J 5.1 Hz, OH), 4.68 (br s, 1H, OH), 4.48 (t,
1H, J 5.9 Hz, OH), 4.33 (d, 1H, J 8.4 Hz, H-100), 4.26 (d, 1H, J 7.7 Hz,
H-10), 3.73 (d, 1H, J 12.5 Hz, H-6i00), 3.58 (d, 1H, J 7.3 Hz, H-6i0),
deoxy-b-D-glucopranosyl)ursolic acid (6)
Yield 71%; Rf 0.26 (1:1 CHCl3–MeOH); ½a D20
ꢀ2.3 (c 0.10,
ꢃ
CH3OH); 1H NMR (CD3OD): d 5.20 (br s, 1H, H-12), 4.48 (dd, 2H, J
8.4, 8.4 Hz, H-100, H-1000), 4.40 (d, 1H, J 8.5 Hz, H-10), 3.89 (dd, 1H, J
1.9, 11.8 Hz, H-6i000), 3.81 (d, 1H, J 10.6 Hz, H-6i0), 3.79–3.75 (m,
2H, H-200, H-6i000), 3.73 (dd, 1H, J 8.8, 10.3 Hz, H-20), 3.69 (dd, 1H, J
3.49–3.42 (m, 4H, H-20, H-30, H-6ii , H-200), 3.35 (1H, H-6ii00), 3.27
8.8, 10.3 Hz, H-2000), 3.64–3.56 (m, 5H, H-30 H-6ii , H-300, H-6ii00, H-
0
0
(t, 1H, J 9.1 Hz, H-300), 3.22 (t, 1H, J 9.1 Hz, H-40), 3.17 (dt, 1H, J
2.2, 8.4 Hz, H-500), 3.12 (dt, 1H, J 2.9, 6.3 Hz, H-50), 3.03 (t, 1H, J
9.2 Hz, H-400), 2.99 (dd, 1H, J 4.0, 11.3 Hz, H-3), 2.74 (dd, 1H, J 3.7,
13.6 Hz, H-18), 1.94–0.68 (m, 22H), 1.82 (s, 3H, COCH3), 1.75 (s,
3H, COCH3), 1.09, 0.89, 0.89, 0.87, 0.85, 0.71, 0.65 (s each, 3H each,
7 ꢂ Me); 13C NMR (DMSO-d6): d 169.1, 168.5 (2 ꢂ COCH3), 143.9,
121.4, 103.4 (C-10), 102.2 (C-100), 88.2, 81.7 (C-40), 76.9 (C-500),
74.6 (C-50), 74.1 (C-300), 72.4 (C-30), 70.7 (C-400), 61.0 (C-600), 60.0
(C-60), 55.4 (C-200), 55.0 (C-20), 54.8, 47.0, 45.7, 45.4, 41.3, 40.8,
38.9, 38.4, 38.0, 36.3, 33.3, 32.8, 32.4, 32.1, 30.4, 27.5, 27.2, 25.5,
25.3, 23.4, 23.0 (2 ꢂ COCH3), 22.9, 22.6, 17.8, 16.9, 16.3, 15.1;
ESIMS: calcd for C46H73N2O13 861.5113, found 861.5086 [MꢀH]ꢀ.
6ii000), 3.52 (t, 1H, J 9.2 Hz, H-40), 3.50 (t, 1H, J 8.1 Hz, H-400), 3.44
(dd, 1H, J 8.8, 10.3 Hz, H-3000), 3.40 (ddd, 1H, J 1.5, 4.8, 8.8 Hz, H-
50), 3.36–3.33 (m, 1H, H-5000), 3.30–3.27 (m, 2H, H-500, H-4000), 3.09
(dd, 1H, J 4.1, 11.4 Hz, H-3), 2.19 (d, 1H, J 11.3 Hz, H-18), 2.04–
0.75 (m, 22H), 2.00, 1.99, 1.93 (s each, 3H each, 3 ꢂ COCH3), 1.10,
0.95, 0.95, 0.84, 0.75 (s each, 3H each, 5 ꢂ Me), 0.94 (d, 3H, J
6.2 Hz), 0.87 (d, 3H, J 6.2 Hz); 13C NMR(CD3OD): d 173.8, 173.7,
173.3 (3 ꢂ COCH3), 139.8, 126.7, 104.9 (C-10), 103.2 (C-100), 103.1
(C-1000), 91.1, 81.4 (C-40), 81.2 (C-400), 78.2 (C-5000), 76.5 (C-500), 76.2
(C-50), 75.8 (C-3000), 74.2 (C-30, C-300), 72.0 (C-4000), 62.6 (C-6000), 61.7
(C-60), 61.6 (C-600), 57.4 (C-2000), 57.0 (C-20), 56.9, 56.6 (C-200), 54.4,
43.3, 40.8, 40.5, 40.4, 39.9, 39.8, 38.2, 37.8, 34.3, 31.9, 29.3, 28.6,
26.8, 25.4, 24.4, 24.1, 23.1, 23.0(3 ꢂ COCH3), 21.6, 19.3, 17.9,
17.7, 17.1, 16.0; ESIMS: calcd for C54H86N3O18 1064.5906, found
1064.5907 [MꢀH]ꢀ.
4.11.4. 3-O-(2-Acetamido-2-deoxy-b-D-glucopranosyl-(1?4)-2-
acetamido-2-deoxy-b-D-glucopyranosyl)ursolic acid (4)
Yield 59%; Rf 0.50 (4:1 CHCl3–MeOH); ½a D20
ꢀ1.9 (c 0.09,
ꢃ
CH3OH); 1H NMR (CD3OD): d 5.21 (t, 1H, J 3.3 Hz, H-12), 4.48 (d,
1H, J 8.4 Hz, H-100), 4.41 (d, 1H, J 8.4 Hz, H-10), 3.89 (dd, 1H, J 2.2,
12.1 Hz, H-6i00), 3.78 (dd, 1H, J 1.9, 12.1 Hz, H-6i0), 3.75–3.69 (m,
4.11.7. 3-O-(2-Acetamido-2-deoxy-b-
acetamido-2-deoxy-b- -glucopranosyl-(1?4)-2-acetamido-2-
deoxy-b- -glucopranosyl-(1?4)-2-acetamido-2-deoxy-b- -glu-
copranosyl)oleanolic acid (7)
D-glucopranosyl-(1?4)-2-
D
D
D
0
2H, H-20, H-200), 3.64–3.61 (m, 2H, H-6ii , H-6ii00), 3.59 (dd, 1H, J
8.4, 10.3 Hz, H-30), 3.51 (t, 1H, J 8.4 Hz, H-40), 3.43 (dd, 1H, J 8.8,
10.3 Hz, H-300), 3.36–3.28 (m, 3H, H-50, H-400, H-500), 3.09 (dd, 1H, J
4.4, 12.1 Hz, H-3), 2.19 (d, 1H, J 11.3 Hz, H-18), 2.05–0.74 (m,
22H), 2.00 (s, 3H, COCH3), 1.93 (s, 3H, COCH3), 1.10, 0.96, 0.95,
0.83, 0.75 (s each, 3H each, 5 ꢂ Me), 0.94 (d, 3H, J 6.2 Hz), 0.87
Yield 73%; Rf 0.18 (1:1 CHCl3–MeOH); 1H NMR (DMSO-d6 and
D2O): d 5.09 (br s, 1H, H-12), 4.38 (d, 2H, J 8.1 Hz, H-100, H-1000),
4.35 (d, 1H, J 8.4 Hz, H-10000), 4.28 (br s, 1H, H-10), 3.73–3.14 (m,
23H), 3.04–3.03 (m, 2H, H-40000, H-3), 1.85–0.68 (m, 22H), 1.83,
1.82, 1.75, 1.72 (s each, 3H each, 4 ꢂ COCH3), 1.06, 0.94, 0.88,
0.87, 0.85, 0.73, 0.64 (s each, 3H each, 7 ꢂ Me); 13C NMR (DMSO-
d6 and D2O): d 169.5–169.2 (4 ꢂ COCH3), 145.0, 120.8, 103.3 (C-
10), 102.1, 101.9, 101.8 (C-100, C-1000, C-10000), 88.3, 81.7, 81.5, 81.4
(d, 3H, J 6.2 Hz); 13C NMR (CD3 OD):
(2 ꢂ COCH3), 139.7,
173.8, 173.3
d
126.8, 104.9 (C-10), 103.3 (C-100), 91.2, 81.5 (C-40), 78.2 (C-500),
76.2 (C-50), 75.9 (C-300), 74.2 (C-30), 72.0 (C-400), 62.5 (C-600), 61.8
(C-60), 57.3 (C-200), 57.0 (C-20), 56.9, 54.4, 43.2, 40.8, 40.4, 39.9,
39.8, 38.1, 37.8, 34.3, 31.8, 29.2, 28.6, 26.8, 25.3, 24.4, 24.1, 23.1
(2 ꢂ COCH3), 21.6, 19.3, 17.9, 17.7, 17.1, 16.0; ESIMS: calcd for
C46H73N2O13 861.5113, found 861.5116 [MꢀH]ꢀ.
(C-40, C-400, C-4000), 77.0, 74.8, 74.7, 73.9, 72.4 (C-30, C-300, C-3000, C-30000
C-50, C-500, C-5000, C-50000), 70.6 (C-40000), 61.0, 60.1 (C-60, C-600, C-6000, C-
0000), 55.4, 55.1, 54.7, 54.6 (C-30, C-300, C-3000, C-30000, C-5), 47.3, 46.5,
,
6
45.7, 41.5, 41.3, 39.0, 38.4, 38.1, 36.4, 33.9, 33.2 (C-7, C-29), 32.6,
30.6, 27.6, 27.5, 25.6, 25.3, 23.7, 23.2–22.9 (C-11, C-16, 4 ꢂ COCH3),
17.9, 17.4, 16.4, 15.2; ESIMS: calcd for C62H99N4O23 1267.6700,
found 1267.6747 [MꢀH]ꢀ.
4.11.5. 3-O-(2-Acetamido-2-deoxy-b-
D-glucopranosyl-(1?4)-2-
acetamido-2-deoxy-b- -glucopranosyl-(1?4)-2-acetamido-2-
D
deoxy-b-D-glucopranosyl)oleanolic acid (5)
Yield 74%; Rf 0.26 (1:1 CHCl3–MeOH); ½a D20
ꢃ
ꢀ8.0 (c 0.15,
4.11.8. 3-O-(2-Acetamido-2-deoxy-b-
acetamido-2-deoxy-b- -glucopranosyl-(1?4)-2-acetamido-2-
deoxy-b- -glucopranosyl-(1?4)-2-acetamido-2-deoxy-b- -glu-
copranosyl)ursolic acid (8)
D-glucopranosyl-(1?4)-2-
CH3OH); 1H NMR (CD3OD): d 5.22 (t, 1H, J 3.3 Hz, H-12), 4.50 (d,
2H, J 8.4 Hz, H-100, H-1000), 4.41 (d, 1H, J 8.5 Hz, H-10), 3.90 (dd, 1H,
J 1.9, 11.8 Hz, H-6i000), 3.81 (dd, 1H, J 1.9, 12.1 Hz, H-6i0), 3.78–3.75
(m, 2H, H-200, H-6i000), 3.73 (dd, 1H, J 8.8, 10.6 Hz, H-20), 3.70 (dd,
D
D
D
Yield 71%; Rf 0.26 (1:1 CHCl3–MeOH); 1H NMR (DMSO-d6 and
D2O): d 5.11 (br s, 1H, H-12), 4.41 (d, 2H, J 8.4 Hz, H-100, H-1000),
4.38 (d, 1H, J 8.4 Hz, H-10000), 4.32 (d, 1H, J 7.3 Hz, H-10), 3.73–3.14
(m, 23H), 3.09 (t, 1H, J 9.2 Hz, H-40000), 3.02 (br s, 1H, H-3), 2.14
(d, 1H, J 10.3 Hz, H-18), 2.01–0.69 (m, 22H), 1.88, 1.87, 1.81, 1.74
(s each, 3H each, 4 ꢂ COCH3), 1.03, 0.89, 0.88 0.76, 0.66 (s each,
3H each, 5 ꢂ Me), 0.95 (d, 3H, J 4.7 Hz), 0.82 (d, 3H, J 4.7 Hz); 13C
NMR (DMSO-d6 and D2O): d 177.0, 170.9–170.2 (4 ꢂ COCH3),
139.2, 124.6, 103.6 (C-10), 102.4, 102.1, 102.0 (C-100, C-1000, C-10000),
89.1, 81.8, 81.6, 81.5 (C-40, C-400, C-4000), 77.2, 75.2, 75.0, 72.8
1H, J 8.4, 10.3 Hz, H-2000), 3.64–3.57 (m, 5H, H-30 H-6ii , H-300, H-
0
6ii00, H-6ii000), 3.52 (t, 1H, J 8.8 Hz, H-40), 3.50 (t, 1H, J 8.1 Hz, H-400),
3.45 (dd, 1H, J 8.5, 10.3 Hz, H-3000), 3.40 (ddd, 1H, J 2.2, 5.5,
9.5 Hz, H-50), 3.36–3.33 (m, 1H, H-5000), 3.29–3.27 (m, 2H, H-500, H-
4000), 3.08 (dd, 1H, J 4.4, 11.7 Hz, H-3), 2.84 (dd, 1H, J 4.0, 13.9 Hz,
H-18), 2.05–0.76 (m, 22H), 2.00, 1.99, 1.94 (s each, 3H each,
3 ꢂ COCH3), 1.14, 0.95, 0.93, 0.92, 0.89, 0.80, 0.74 (s each, 3H each,
7 ꢂ Me); 13C NMR (CD3OD): d 173.8, 173.7, 173.3 (3 ꢂ COCH3),
145.4, 123.4, 104.9 (C-10), 103.0 (C-1000), 91.1, 81.5 (C-40), 81.2

P. Wang et al. / Carbohydrate Research 345 (2010) 607–620
619
(C-30, C-300, C-3000, C-30000, C-50, C-500, C-5000, C-50000), 70.9 (C-40000), 61.4,
60.4 (C-60, C-600, C-6000, C-60000), 55.8, 55.5, 55.1, 55.0 (C-30, C-300, C-
3000, C-30000, C-5), 53.2, 47.7 (C-9, C-17), 42.2, 38.8, 37.1, 36.8,
323.3, 31.0, 28.2, 28.0, 25.8, 24.9, 24.6, 23.7, 23.4–23.2
(4 ꢂ COCH3), 21.7, 18.3, 17.7, 16.9, 15.7; ESIMS: calcd for
C62H99N4O23 1267.6700, found 1267.6726 [MꢀH]ꢀ.
(C-2000), 57.3 (C-200), 57.1, 47.7, 47.4, 42.9, 42.8, 40.6, 39.9, 39.8,
38.0, 34.9, 34.1, 33.9, 33.6, 31.6, 28.9, 28.6, 26.4, 24.6, 24.1, 24.0,
23.3 (3 ꢂ COCH3), 19.3, 17.8, 17.1, 15.9; ESIMS: calcd for
C54H86N3O18 1064.5906, found 1064.5903 [MꢀH]ꢀ.
4.11.12. 3-O-(2-Acetamido-2-deoxy-b-
2-acetamido-2-deoxy-b- -glucopranosyl-(1?6)-2-acetamido-
2-deoxy-b- -glucopranosyl)ursolic acid (12)
D-glucopranosyl-(1?6)-
D
4.11.9. 3-O-(2-Acetamido-2-deoxy-b-
D-glucopranosyl-(1?6)-2-
D
acetamido-2-deoxy-b-
D
-glucopyranosyl)oleanolic acid (9)
Yield 56%; Rf 0.31 (1:1 CHCl3–MeOH); 1H NMR (CD3OD): d 5.21
(t, 1H, J 3.3 Hz, H-12), 4.46 (d, 1H, J 8.4 Hz, H-100), 4.45 (d, 1H, J
8.4 Hz, H-1000), 4.44 (d, 1H, J 8.4 Hz, H-10), 4.10 (dd, 1H, J 1.9,
11.8 Hz, H-6i00), 4.06 (dd, 1H, J 1.9, 11.0 Hz, H-6i0), 3.88 (dd, 1H, J
Yield 64%; Rf 0.21 (2:1 CHCl3–MeOH); ½a D20
ꢀ12.8 (c 0.11,
ꢃ
CH3OH); 1H NMR (CD3OD): d 5.23 (t, 1H, J 3.3 Hz, H-12), 4.49 (d,
1H, J 8.4 Hz, H-100), 4.41 (d, 1H, J 8.0 Hz, H-10), 4.12 (dd, 1H, J 1.8,
11.0 Hz, H-6i0), 3.88 (dd, 1H, J 2.2, 12.1 Hz, H-6i00), 3.71–3.62 (m,
0
2.2, 12.1 Hz, H-6i000), 3.74–3.66 (m, 5H, H-20, H-6ii , H-200, H-6ii00, H-
0
4H, H-20, H-6ii , H-200, H-6ii00), 3.45 (dd, 1H, J 8.8, 10.3 Hz, H-300),
6ii000), 3.62–3.57 (m, 2H, H-50, H-2000), 3.51 (dt, 1H, J 1.4, 8.8 Hz, H-
500), 3.47 (dd, 1H, J 8.8, 10.3 Hz, H-30), 3.45–3.41 (m, 2H, H-300, H-
3000), 3.35 (t, 1H, J 9.5 Hz, H-4000), 3.29–3.27 (m, 1H, H-5000), 3.22 (t,
1H, J 9.5 Hz, H-40), 3.19 (t, 1H, J 9.5 Hz, H-400), 3.07 (dd, 1H, J 4.4,
11.7 Hz, H-3), 2.19 (d, 1H, J 11.7 Hz, H-18), 2.09–0.73 (m, 22H),
2.00, 1.98, 1.96 (s each, 3H each, 3 ꢂ COCH3), 1.10, 0.96, 0.94,
0.84, 0.75 (s each, 3H each, 5 ꢂ Me), 0.94 (d, 3H, J 6.6 Hz), 0.88
3.43 (dd, 1H, J 8.8, 10.3 Hz, H-30), 3.39 (ddd, 1H, J 1.8, 5.5, 9.9 Hz,
H-50), 3.34–3.26 (m, 3H, H-40, H-400, H-500), 3.08 (dd, 1H, J 4.8,
11.2 Hz, H-3), 2.85 (dd, 1H, J 3.3, 13.6 Hz, H-18), 2.05–0.76 (m,
22H), 2.00 (s, 3H, COCH3), 1.94 (s, 3H, COCH3), 1.14, 0.95, 0.93,
0.92, 0.90, 0.81, 0.75 (s each, 3H each, 7 ꢂ Me); 13C NMR (CD3OD):
d 173.9, 173.4 (2 ꢂ COCH3), 145.4, 123.5, 104.8 (C-10), 102.8 (C-100),
91.1, 78.0 (C-500), 76.5 (C-50), 76.3 (C-300), 75.8 (C-30), 72.2 (C-40),
72.1 (C-400), 70.0 (C-60), 62.8 (C-600), 57.8 (C-20), 57.4 (C-200), 56.9,
49.9, 47.8, 47.4, 42.9, 42.8, 40.6, 39.9, 39.8, 37.9, 35.0, 34.0, 33.9,
33.6, 31.6, 28.9, 28.6, 26.7, 26.4, 24.6, 24.1, 24.0, 23.2 (3 ꢂ COCH3),
19.4, 17.9, 17.1, 15.9; ESIMS: calcd for C46H73N2O13 861.5113,
found 861.5104 [MꢀH]ꢀ.
(d, 3H,
J d 173.8, 173.6, 173.5
6.6 Hz); 13C NMR (CD3OD):
(3 ꢂ COCH3), 139.8, 126.9, 104.4 (C-10), 103.9 (C-100), 103.0 (C-1000),
91.1, 78.0 (C-5000), 76.9 (C-500), 76.4 (C-300), 76.1 (C-30, C-3000), 76.0
(C-50), 72.8 (C-40), 72.7 (C-400), 72.0 (C-4000), 71.3 (C-600), 71.1 (C-60),
62.8 (C-6000), 57.8 (C-20), 57.5 (C-2000), 57.4 (C-200), 57.1, 54.4, 43.2,
40.8, 40.5, 40.4, 40.0, 39.8, 38.1, 37.9, 34.3, 31.8, 29.2, 28.7, 26.4,
25.3, 24.4, 24.1, 23.3, 23.1 (3 ꢂ COCH3), 21.6, 19.3, 17.9, 17.7,
17.1, 16.0; ESIMS: calcd for C54H86N3O18 1064.5906, found
1064.5880 [MꢀH]ꢀ.
4.11.10. 3-O-(2-Acetamido-2-deoxy-b-D-glucopranosyl-(1?6)-
2-acetamido-2-deoxy-b-D-glucopyranosyl)ursolic acid (10)
Yield 60%; Rf 0.21 (2:1 CHCl3–MeOH); ½a D20
ꢀ4.3 (c 0.14,
ꢃ
CH3OH); 1H NMR (CD3OD): d 5.21 (t, 1H, J 3.3 Hz, H-12), 4.48 (d,
1H, J 8.4 Hz, H-100), 4.41 (d, 1H, J 8.5 Hz, H-10), 4.13 (dd, 1H, J 1.9,
11.0 Hz, H-6i0), 3.88 (dd, 1H, J 2.2, 11.9 Hz, H-6i00), 3.70–3.62 (m,
4.11.13. 3-O-(2-Acetamido-2-deoxy-b-
2-acetamido-2-deoxy-b- -glucopranosyl-(1?6)-2-acetamido-
2-deoxy-b- -glucopranosyl-(1?6)-2-acetamido-2-deoxy-b-
glucopranosyl)oleanolic acid (13)
D-glucopranosyl-(1?6)-
D
D
D-
0
4H, H-20, H-6ii , H-200, H-6ii00), 3.45 (dd, 1H, J 8.5, 10.3 Hz, H-300),
3.44 (dd, 1H, J 8.8, 10.3 Hz, H-30), 3.39 (ddd, 1H, J 1.8, 5.5, 9.8 Hz,
H-50), 3.32 (t, 1H, J 9.5 Hz, H-400), 3.29–3.26 (m, 2H, H-40, H-500),
3.08 (dd, 1H, J 4.4, 11.7 Hz, H-3), 2.19 (d, 1H, J 11.0 Hz, H-18),
2.05–0.76 (m, 22H), 2.00 (s, 3H, COCH3), 1.94 (s, 3H, COCH3),
1.10, 0.95, 0.94, 0.83, 0.75 (s each, 3H each, 5 ꢂ Me), 0.94 (d, 3H,
J 6.6 Hz), 0.87(d, 3H, J 6.6 Hz); 13C NMR (CD3OD): d 173.9, 173.5
(2 ꢂ COCH3), 139.7, 126.8, 104.9 (C-10), 102.8 (C-100), 91.1, 78.0
(C-500), 76.4 (C-50), 76.3 (C-300), 75.8 (C-30), 72.2 (C-40), 72.1 (C-400),
70.0 (C-60), 62.8 (C-600), 57.7 (C-20), 57.4 (C-200), 56.9, 54.4, 43.3,
40.8, 40.5, 40.4, 39.9, 38.2, 37.9, 34.3, 31.8, 29.2, 28.6, 26.7, 25.4,
24.4, 24.1, 23.2 (2 ꢂ COCH3), 21.6, 19.3, 17.9, 17.7, 17.2, 16.1;
ESIMS: calcd for C46H73N2O13 861.5113, found 861.5184 [MꢀH]ꢀ.
Yield 47%; Rf 0.21 (1:1 CHCl3–MeOH); 1H NMR (CD3OD): d 5.23
(t, 1H, J 3.7 Hz, H-12), 4.55 (d, 1H, J 8.4 Hz), 4.51 (d, 1H, J 8.4 Hz),
4.40 (d, 1H, J 8.0 Hz), 4.39 (d, 1H, J 8.4 Hz, 4.02–3.10 (m, 24H),
3.07 (dd, 1H, J 4.4, 11.8 Hz, H-3), 2.85 (dd, 1H, J 4.0, 13.6 Hz, H-
18), 2.10–0.71 (m, 22H), 2.01, 2.00, 1.99, 1.98 (s each, 3H each,
4 ꢂ COCH3), 1.15, 0.93, 0.89, 0.89, 0.81, 0.81, 0.75 (s each, 3H each,
7 ꢂ Me), 13C NMR (CD3OD): d 174.8, 173.8, 173.2 (4 ꢂ COCH3),
145.3, 123.7, 104.9, 104.5, 104.1, 103.0 (C-10, C-100, C-1000, C-10000),
91.1, 78.0, 77.3, 76.7, 76.6, 76.5, 76.1, 75.4, 75.1 (C-30, C-300, C-3000,
C-30000, C-50, C-500, C-5000, C-50000), 73.6, 73.5, 72.9, 72.7, 72.6, 72.1,
71.8 (C-40, C-400, C-4000, C-40000, C-60, C-600, C-6000), 62.8 (C-60000), 57.8,
57.4, 57.3, 57.2 (C-5, C-20, C-200, C-2000, C-20000), 47.7, 47.4, 42.9,
42.8, 40.6, 40.0, 39.8, 38.0, 34.9, 34.1, 33.9, 33.6, 31.6, 28.9, 28.6,
26.4, 24.6, 24.1, 24.0, 23.2–23.1 (4 ꢂ COCH3), 19.4, 17.8, 17.1,
15.9; ESIMS: calcd for C62H99N4O23 1267.6700, found 1267.6736
[MꢀH]ꢀ.
4.11.11. 3-O-(2-Acetamido-2-deoxy-b-
D-glucopranosyl-(1?6)-
2-acetamido-2-deoxy-b- -glucopranosyl-(1?6)-2-acetamido-
D
2-deoxy-b-D-glucopranosyl)oleanolic acid (11)
Yield 60%; Rf 0.31 (1:1 CHCl3–MeOH); ½a D20
ꢃ
2.9 (c 0.47, CH3OH);
1H NMR (CD3OD): d 5.23 (t, 1H, J 3.3 Hz, H-12), 4.46 (d, 1H, J 8.1 Hz,
H-100), 4.45 (d, 1H, J 8.0 Hz, H-1000), 4.44 (d, 1H, J 8.0 Hz, H-10), 4.10
(dd, 1H, J 1.9, 11.8 Hz, H-6i00), 4.05 (dd, 1H, J 1.9, 11.8 Hz, H-6i0), 3.89
4.11.14. 3-O-(2-Acetamido-2-deoxy-b-
2-acetamido-2-deoxy-b- -glucopranosyl-(1?6)-2-acetamido-
2-deoxy-b- -glucopranosyl-(1?6)-2-acetamido-2-deoxy-b-
glucopranosyl)ursolic acid (14)
D-glucopranosyl-(1?6)-
D
D
D-
(dd, 1H, J 1.9, 11.7 Hz, H-6i000), 3.75–3.66 (m, 5H, H-20, H-6ii , H-200,
0
H-6ii00, H-6ii000), 3.62–3.58 (m, 2H, H-50, H-2000), 3.53 (dt, 1H, J 1.9,
8.6 Hz, H-500), 3.47 (dd, 1H, J 8.8, 10.3 Hz, H-30), 3.45–3.41 (m, 2H,
H-300, H-3000), 3.36 (t, 1H, J 8.8 Hz, H-4000), 3.29–3.27 (m, 1H, H-5000),
3.22 (t, 1H, J 9.5 Hz, H-40), 3.19 (t, 1H, J 9.5 Hz, H-400), 3.07 (dd,
1H, J 4.0, 11.3 Hz, H-3), 2.84 (dd, 1H, J 4.0, 13.9 Hz, H-18), 2.00–
0.73 (m, 22H), 2.00, 1.98, 1.96 (s each, 3H each, 3 ꢂ COCH3), 1.14,
0.95, 0.93, 0.90, 0.81, 0.81, 0.75 (s each, 3H each, 7 ꢂ Me); 13C
NMR (CD3OD): d 173.8, 173.6 (3 ꢂ COCH3), 145.3, 123.6, 104.5
(C-10), 103.9 (C-100), 103.0 (C-1000), 91.1, 78.0 (C-5000), 76.9 (C-500),
76.5 (C-300), 76.1 (C-30, C-3000), 75.9 (C-50), 72.8 (C-40), 72.7 (C-400),
71.9 (C-4000), 71.3 (C-600), 71.1 (C-60), 62.8 (C-6000), 57.7 (C-20), 57.5
Yield 46%; Rf 0.21 (1:1 CHCl3–MeOH); 1H NMR (CD3OD): d 5.21
(t, 1H, J 3.7 Hz, H-12), 4.54 (d, 1H, J 8.4 Hz), 4.50 (d, 1H, J 8.5 Hz),
4.41 (d, 1H, J 8.8 Hz), 4.39 (d, 1H, J 8.4 Hz), (H-10, H-100, H-1000, H-
1
0000), 4.02–3.11 (m, 24H), 3.08 (dd, 1H, J 4.4, 11.7 Hz, H-3), 2.20
(d, 1H, J 11.0 Hz, H-18), 2.08–0.73 (m, 22H), 2.01, 2.00, 1.98 (s,
12H each, 4 ꢂ COCH3), 1.10, 0.95, 0.94, 0.84, 0.75 (s each, 3H each,
5 ꢂ Me), 0.94 (d, 3H, J 6.6 Hz), 0.88 (d, 3H, J 6.6 Hz); 13C NMR
(CD3OD): d 174.1, 173.7, 173.3 (4 ꢂ COCH3), 139.9, 126.7, 104.8,
104.3, 104.1, 103.0 (C-10, C-100, C-1000, C-10000), 91.1, 78.0, 77.2, 76.7,
76.6, 76.4, 76.1, 75.6, 75.2 (C-30, C-300, C-3000, C-30000, C-50, C-500, C-
5000, C-50000), 73.5, 73.3, 72.8, 72.7, 72.5, 72.0, 71.8 (C-40, C-400, C-4000,

620
P. Wang et al. / Carbohydrate Research 345 (2010) 607–620
C-40000, C-60, C-600, C-6000), 62.8 (C-60000), 57.8, 57.7, 57.4, 57.3 (C-5, C-
20, C-200, C-2000, C-20000), 54.5, 43.2, 40.8, 40.5, 40.4, 40.1, 39.8, 38.2,
37.9, 34.4, 31.9, 29.3, 28.7, 26.2, 25.4, 24.4, 24.1, 23.2–23.1
(4 ꢂ COCH3), 21.6, 19.3, 17.9, 17.8, 17.2, 16.1; ESIMS: calcd for
C62H99N4O23 1267.6700, found 1267.6700 [MꢀH]ꢀ.
2. (a) Liu, J. J. Ethnopharmacol. 1995, 49, 57–68; (b) Kashiwada, Y.; Wang, H. K.;
Nagao, T.; Kitanaka, S.; Yasuda, I.; Fujioka, T.; Yamagishi, T.; Cosentino, L. M.;
Kozuka, M.; Okabe, H.; Ikeshiro, Y.; Hu, C. Q.; Yeh, E.; Lee, K. H. J. Nat. Prod. 1998,
61, 1090–1095.
3. Yogeeswari, P.; Sriram, D. Curr. Med. Chem. 2005, 12, 657–666.
4. Nakamura, T.; Komori, C.; Lee, Y.-y.; Hashimoto, F.; Yahara, S.; Nohara, T.;
Ejima, A. Biol. Pharm. Bull. 1996, 19, 564–566.
5. Jung, H. J.; Lee, C. O.; Lee, K. T.; Choi, J.; Parkm, H. J. Biol. Pharm. Bull. 2004, 27,
744–747.
6. Park, H. J.; Kwon, S. H.; Lee, J. H.; Lee, K. H.; Miyamoto, K.; Lee, K. T. Planta Med.
2001, 67, 118–121.
Acknowledgements
7. (a) Yan, M. C.; Liu, Y.; Chen, H.; Ke, Y.; Xu, Q. C.; Cheng, M. S. Bioorg. Med. Chem.
Lett. 2006, 16, 4200–4204; (b) Abdel-Kader, M.; Hoch, J.; Berger, J. M.; Evans, R.;
Miller, J. S.; Wisse, J. H.; Mamber, S. W.; Dalton, J. M.; Kingston, D. G. I. J. Nat.
Prod. 2001, 64, 536–539; (c) Sun, J. S.; Han, X. W.; Yu, B. Carbohydr. Res. 2003,
338, 827–833.
8. (a) Plé, K.; Chwalek, M.; Laurence, V. N. Tetrahedron 2005, 61, 4347–4362; (b)
Yu, B.; Zhang, Y. C.; Tang, P. P. Eur. J. Org. Chem. 2007, 5145–5161; (c) Yu, B.;
Sun, J. S. Chem. Asian J. 2009, 4, 642–654; (d) Kong, F. Z. Front. Chem. China 2009,
4, 10–31.
9. Wang, P.; Li, C. X.; Wang, G. F.; Li, Y. X. Chin. J. Chem. 2006, 24, 1421–1426.
10. Dan, A.; Ito, Y.; Qgawa, T. J. Org. Chem. 1995, 60, 4680–4681.
11. Yamazaki, F.; Kitajima, T.; Nukada, T.; Ito, Y.; Ogawa, T. Carbohydr. Res. 1990,
201, 15–30.
12. (a) Defaye, J.; Gadelle, A.; Pedersen, C.; Demande, Fr. 2640628, 1990; Chem.
Abstr., 1991, 114, 247674x.; (b) Nakahara, Y.; Shibayama, S.; Nakahara, Y.;
Ogawa, T. Carbohydr. Res. 1996, 280, 67–84.
13. (a) Macmillan, D.; Daines, A. M.; Bayrhuber, M.; Flitsch, S. L. Org. Lett. 2002, 4,
1467; (b) Grundler, G.; Schmidt, R. R. Carbohydr. Res. 1985, 135, 203; (c)
Kretzschmar, G.; Stahl, W. Tetrahedron 1998, 54, 6341–6358.
14. Li, A. X.; Zeng, Y.; Kong, F. Z. Carbohydr. Res. 2004, 339, 673–681.
15. Ding, X.; Wang, W.; Kong, F. Carbohydr. Res. 1997, 303, 445–448.
16. Konstantin, V.; Antonov, L. V.; Backinowsky, G.; Brade, L.; Holst, O.; Zamojski,
A. Carbohydr. Res. 1998, 314, 85–93.
This work was supported by the National Natural Science Foun-
dation of China (No. 30701046). We would like to thank Dr. Jing-
rong Cui in State Key Laboratory of Natural and Biomimetic
Drugs for evaluating the antitumour activity of these synthetic
saponins.
Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.carres.2010.01.002.
References
1. (a) Kashiwada, Y.; Hashimoto, F.; Cosentino, L. M.; Chen, C. H.; Garrett, P. E.;
Lee, K. H. J. Med. Chem. 1999, 39, 1016–1017; (b) Kashiwada, Y.; Nagao, T.;
Hashimoto, A.; Ikeshiro, Y.; Okabe, H.; Cosentino, L. M.; Lee, K. H. J. Nat. Prod.
2000, 63, 1619–1622; (c) Min, B. S.; Jung, H. J.; Lee, J. S.; Kim, Y. H.; Bok, S. H.;
Ma, C. M.; Nakamura, N.; Hattori, M.; Bae, K. Planta Med. 1999, 65, 374–375.