Seven new triterpene glycosides from the pericarps of Stryphnodendron fissuratum

Article abstract of DOI:10.1016/j.phytol.2011.04.010

Seven new triterpene glycosides on the basis of the lupane skeleton (1-7) were isolated from the pericarps of Stryphnodendron fissuratum (Leguminosae). The structures of 1-7 were determined on the basis of extensive spectroscopic analysis, including two-dimensional NMR data, and the results of hydrolytic cleavage.

Full text of DOI:10.1016/j.phytol.2011.04.010

Phytochemistry Letters 4 (2011) 259–266
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Phytochemistry Letters
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Seven new triterpene glycosides from the pericarps of Stryphnodendron fissuratum
a
b
a,
Akihito Yokosuka a, , Sachiko Kawakami , Mitsue Haraguchi , Yoshihiro Mimaki
*
*
a Laboratory of Medicinal Pharmacognosy, School of Pharmacy, Tokyo University of Pharmacy and Life Sciences, 1432-1, Horinouchi, Hachioji, Tokyo 192-0392, Japan
b Centro de Sanidade Animal, Instituto Biolo´gico, Av. Conselheiro Rodrigues Alves, 1252, CEP 04014-002, Sa˜o Paulo, SP, Brazil
A R T I C L E I N F O
A B S T R A C T
Article history:
Seven new triterpene glycosides on the basis of the lupane skeleton (1–7) were isolated from the
pericarps of Stryphnodendron fissuratum (Leguminosae). The structures of 1–7 were determined on the
basis of extensive spectroscopic analysis, including two-dimensional NMR data, and the results of
hydrolytic cleavage.
Received 5 January 2011
Received in revised form 15 April 2011
Accepted 21 April 2011
Available online 7 June 2011
ß 2011 Phytochemical Society of Europe. Published by Elsevier B.V. All rights reserved.
Keywords:
Triterpene glycosides
Lupane
Stryphnodendron fissuratum
Leguminosae
1. Introduction
total of 47 signals and DEPT data. The IR spectrum of 1 showed a
broad absorption band for hydroxy groups at 3395 cmꢀ1, as well as
Stryphnodendron fissuratum Mart. (Leguminosae) is mainly
found in the tropical regions of the continent of South America
(Hashimoto and Nishimoto, 1996). The fruits of this plant are
poisonous and cause bovine death (Ferreira et al., 2009; Mendonc¸a
et al., 2010). Previously, we reported on the isolation and structural
characterization of six new triterpene glycosides on the basis of the
oleanane skeleton, named stryphnosides A–F, from the pericarps of
S. fissuratum (Yokosuka et al., 2008a). Further phytochemical
analysis of the plant suggested that it also contained triterpene
glycosides with a lupane skeleton, but they remain to be isolated
and identified (Haraguchi et al., 2006). Our detailed examination of
the EtOH extract of S. fissuratum pericarps resulted in the isolation
of seven new lupane-type triterpene glycosides (1–7). This paper
deals with the structural determination of the new glycosides on
the basis of spectroscopic analysis, including various two-
dimensional (2D) NMR spectroscopic techniques, and the results
of hydrolytic cleavage.
strong absorption due to a carbonyl group at 1725 cmꢀ1. The 1H
NMR spectrum of 1 showed signals for six triterpenoid methyl
groups at
exomethylene group at
characteristic of the lup-20(29)-en structure, as well as signals for
three anomeric protons at 5.99 (br s), 4.59 (d, J = 7.6 Hz), and 4.40
(d, J = 7.5 Hz). The three-proton doublet signal at 1.27 (J = 6.3 Hz)
d
1.70, 1.08, 1.01, 0.94, 0.92, and 0.87 (each s), and an
d
4.75 and 4.62 (each br s), which are
d
d
indicated the presence of one deoxyhexopyranosyl unit in 1. Acid
hydrolysis of 1 with 1.0 M HCl in dioxane–H2O (1:1) resulted in the
production of an aglycone (1a), identified as 2
20(29)-en-28-oic acid (2 -hydroxybetulinic acid) (Kumar et al.,
1985), as well as -rhamnose, -xylose, and -glucose as the
carbohydrate components. In the 13C NMR spectrum of 1, the C-3
and C-28 carbons of the aglycone moiety were observed at 96.4
a,3b-dihydroxylup-
a
L
D
D
d
and 175.6, respectively, which suggested that 1 was a 3,28-
bisdesmoside. The 1H–1H COSY experiment with 1 allowed the
sequential assignments of the signals from H-1 to H2-6, H2-5, and
Me-6 of the monosaccharides. Their signal multiplet patterns and
coupling constants (Table 1) indicated the presence of a
xylopyranosyl (4C1) unit (Xyl), a -glucopyranosyl (4C1) unit
(Glc), and an
-rhamnopyranosyl (1C4) unit (Rha). The proton
b-D-
2. Results and discussion
b
-D
a
-L
Compound 1 was obtained as an amorphous powder. The
HRESI-TOFMS of 1 showed an accurate [M+Na]+ ion peak at m/z
935.4889 in accordance with the empirical molecular formula of
resonances correlated with those of the one-bond coupled carbons
using the HMQC spectrum. Comparison of the carbon chemical
shifts thus assigned with those of the reference methyl glycosides
suggested that the Xyl and Rha groups were presented as the
terminal units, whereas the Glc group was substituted at C-2
(Agrawal et al., 1985; Agrawal, 1992). The anomeric conformations
of the Glc and Xyl groups were ascertained by the relatively large J
values of their anomeric protons (7.5–7.6 Hz). For the Rha moiety,
C
47H76O17, which was supported by the 13C NMR spectrum with a
* Corresponding authors. Tel.: +81 42 676 4573; fax: +81 42 676 4579.
E-mail addresses: yokosuka@toyaku.ac.jp (A. Yokosuka), mimakiy@toyaku.ac.jp
(Y. Mimaki).
1874-3900/$ – see front matter ß 2011 Phytochemical Society of Europe. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.phytol.2011.04.010

Table 1
1H and 13C NMR chemical shift assignments for the sugar moieties of compounds 1–7 in CD3OD.a
Position
Glc
1
Position
Glc
2
Position
Glc
3
Position
Glc
4
1
2
3
4
5
6
4.40 d (7.5)
104.8
82.2
78.5
71.1
78.0
62.3
1
2
3
4
5
6
4.41 d (7.6)
104.7
82.4
78.5
71.0
78.0
62.3
1
2
3
4
5
6
4.45 d (7.7)
3.62 dd (8.9, 7.7)
3.75 t (8.9)
3.61 t (8.9)
3.50 m
104.7
81.3
76.7
80,0
76.4
61.4
1
2
3
4
5
6
4.45 d (7.7)
3.62 dd (8.9, 7.7)
3.74 t (8.9)
3.61 t (8.9)
3.48 m
104.7
81.3
76.7
80.0
76.4
61.4
3.52 dd (8.8, 7.5)
3.57 t (8.8)
3,51 dd (9.1,7.6)
3,57 t (9.1)
3.36 t (8.8)
3.37 t (9.1)
3.35 m
3.34 m
a
3.84 dd (12.0, 1.8)
3.65 dd (12.0, 3.5)
a
3.85 dd (11.8, 1.7)
3.65 dd (11.8, 3.5)
(2H)
3.85 m
(2H)
3.85 m
b
b
Xyl
1
2
3
4
4.59 d (7.6)
105.9
76.1
78.0
71.2
Xyl
1
2
3
4
4.63 d (7.5)
105.8
75.8
76.1
78.0
Xyl
1
2
3
4
4.69 d (7.5)
105.4
75.8
76.1
78.0
Xyl
1
2
3
4
4.69 d (7.5)
105.4
75.8
76.1
78.0
3.21 dd (9.0, 7.6)
3.30 t (9.0)
3.27 dd (9.0, 7.5)
3.46 t (9.0)
3.25 dd (8.7, 7.5)
3.46 t (8.7)
3.25 dd (8.7, 7.5)
3.46 t (8.7)
3.43 ddd
3.62 ddd
3.60 ddd
3.62 ddd
(10.6, 9.0, 5.0)
3.78 dd (11.3, 5.0)
3.12 dd (11.3, 10.6)
(10.5, 9.0, 5.3)
3.96 dd (11.6, 5.3)
3.24 dd (11.6, 10.5)
(10.6, 8.7, 5.2)
3.96 dd (11.5, 5.2)
323 dd (11.5, 10.6)
(10.7, 8.7, 5.2)
3.96 dd (11.5, 5.2)
323 dd (11.5, 10.7)
5
a
67.1
5
a
64.7
5
a
64.7
5
a
64.7
b
b
b
b
Rha
1
2
3
4
5
6
5.99 br s
95.1
71.4
72.5
73.4
72.8
18.2
Ara
Rha
1
2
3
4
5
4,27 d (7.0)
103.8
72.0
74.1
69.7
67.3
Ara
1
2
3
4
5
4.27 d (7.0)
103.8
72.0
74.2
69.7
67.3
Ara
1
2
3
4
5
4.27 d (7.0)
103.8
72.0
74.2
69.7
67.3
3,79 br d (3.5)
3.65 dd (9.6, 3.5)
3.45 t (9.6)
3.56 dd (8.8, 7.0)
3.51 dd (8.8, 3.2)
3.79 m
3.56 dd (9.1, 7.0)
3.51 dd (9.1, 3.6)
3.80 m
3.56 dd (9.0, 7.0)
3.50 dd (9.0, 3.6)
3.80 m
3.67 dq (9.6, 6.3)
1.27 d (6.3)
a
3.90 dd (12.5, 2.7)
3.58 dd (12.5, 2.8)
a
3.90 dd (12.2, 2.7)
3.24 dd (12.2, 2.9)
a
3.89 dd (11.6, 2.9)
3.58 dd (11.6, 4.1)
b
b
b
1
2
3
4
5.99 br s
95.0
71.4
72.5
73.4
Xyl0
1
2
3
4
4.34 d (7.7)
105.3
74.9
77.9
71.0
Xyl0
1
2
3
4
4.34 d (7.7)
105.3
74.9
77.9
71.0
3.79 br d (3.3)
3.66 dd (9.5, 3.3)
3.45 t (9.5)
3.19 dd (8.9, 7.7)
3.30 t (8.9)
3.19 dd (8.9, 7.7)
3.30 t (8.9)
3.48 ddd
3.49 ddd
(10.6, 8.9, 6.1)
3.90 dd (11.2, 6.1)
3.24 dd (11.2, 10.6)
(9.5, 8.9, 5.0)
3.89 dd (11.6, 5.0)
3.24 dd (11.6, 9.5)
5
6
3.66 dq (9.5, 6.1)
1.27 d (6.1)
72.8
18.2
5
a
67.1
5
a
67.1
b
b
Rha
1
2
3
4
5
6
5.99 br s
95.1
71.4
72.5
73.3
72.8
18.2
Rha
1
2
3
4
5
6
4.64 br s
102.3
72.4
72.7
73.9
70.0
18.1
3.79 br d (3.1)
3.65 dd (9.5, 3.1)
3.45 t (9.5)
3.79 br d (3.1)
3.62 dd (9.3, 3.1)
3.39 t (9.3)
3.57 m
3.67 dq (9.5, 6.1)
1.27 d (6.1)
1.27 d (6.3)
Position
Glc
5
Position
6
Position
7
1
2
3
4
5
6
4.45 d (7.8)
104.7
81.3
76.7
80.0
76.4
61.4
Glc
1
2
3
4
5
6
4.43 d (7.7)
104.7
81.2
76.8
80.2
76.4
61.3
Glc
1
2
3
4
5
6
4.41 d (7.7)
105.1
82.4
76 6
80.7
75.9
61.8
3.62 dd (8.8, 7.8)
3.75 t (8.8)
3.60 t (8.8)
3.50 m
3.60 dd (9.1, 7.7)
3.72 t (9.1)
3.59 t (9.1)
3.47
3.49 dd (9.2, 7.7)
3.67 t (9.2)
3.54 t (9.2)
3.54 m
(2H)
3.85 m
(2H)
3.85 m
(2H)
3.83 m
Xyl
1
2
1
4
4.69 d (7.7)
105.4
75.8
76.1
78.0
Xyl
1
2
3
4
4.67 d (7.7)
105.7
76.5
79 9
71.8
Xyl
1
2
3
4
4.57 d (7.7)
106.1
76.9
79 9
71.8
3.25 dd (9.0, 7.7)
3 46 t (9 0)
3.48 dd (8.8, 7.7)
3 80 t (8.8)
3.20 dd (9.5, 7.7)
134 t (9.5)
3 62 ddd
3.78 ddd
3.49 ddd
(10.5, 9.0, 5.3)
3.96 dd (11.6, 5.3)
3.23 dd (11.6, 10.5)
(9.3, 8.8, 3.7)
4.00 dd (11.2, 3.7)
3.20 dd (11.2, 9.3)
(9.5, 9.5, 4.2)
4.02 dd (11.5, 4.2)
3.31 dd (11.5, 9.5)
5
a
64.7
5
a
64.3
5
a
64.4
b
b
b

Ara
1
2
3
4
5
4.27 d (7.0)
103.8
72.0
74.1
69.7
67.3
Glc0
1
2
3
4
5
6
4.90 d (7.3)
102.6
80.4
79.1
70.7
78.1
62.1
Glc0
1
2
3
4
5
6
4.89 d (7.3)
3.40 dd (9.4, 7.3)
3.47 t (9.4)
102.7
80.0
79.1
70.7
7S.1
62.1
3.56 dd (9.1, 7.0)
3.51 dd (9.1, 3.7)
3.79 m
3.41 dd (9.5, 7.3)
3.43 t (9.5)
3.46 t (9.5)
3.49 t (9.4)
a
3.90 dd (12.7, 3.0)
3.58 dd (12.7, 3.5)
3.19 m
3.22 m
b
a
3.82 br d (12.5)
3.72 br d (12.5)
a
3.82 br d (12.1)
3.73 br d (12.1)
b
b
Xyl0
1
2
3
4
5
4.34 (1(7.7)
105.3
74 .9
77.9
71.0
67.1
Rha
Ara
Xyl0
Rha0
1
2
3
4
5
6
5.11 br s
102.7
72.2
72.3
74.0
69.7
18.1
Rha
Ara
1
2
3
4
5
6
5.13 br s
102.6
72.2
72,.1
73.9
69.7
18.0
3.19 dd (9.0, 7.7)
3.30 t (9.0)
3.95 br d (3.6)
3.71 dd (9.2, 3.6)
3.39 t (9.2)
3.96 br d (4.0)
3.72 dd (9.1, 4.0)
3.34 t (9.1)
3.49 ddd (10.5, 9.0, 4.7)
3.90 dd (11.4, 4.7)
3.23 dd (11.4, 10.5)
a
4.11 dq (9.2, 7.4)
1 29 d (7.4)
4.12 dq (9.1, 6.2)
1.27 d (6.2)
b
1
2
3
4
5
4.63 d (2.9)
99.4
70.7
73.0
65.9
62 1
l
2
3
4
5
4.61 d (3.7)
99.4
70.7
73.0
66.0
62.1
3.76 dd (3.7, 2,9)
3.69 t (3.7)
3.74 dd (4.2, 3.7)
3.68 t (4.2)
3.91 ddd (8.9, 3.7, 2.6)
4.09 dd (11.5, 8.9)
3.50 dd (11.5, 2.6)
3.92 ddd (8.8, 4.2, 3.5)
4.07 dd (11.6, 8.8)
3.51 dd (11.6, 3.5)
a
a
b
b
1
2
3
4
5
4.33 d (7.7)
105.4
74.9
77.9
71.0
67.1
Xyl0
1
2
3
5
4.33 d (7.7)
105.3
74.9
77 9
71.0
67.1
3.19 dd (9.1,7.7)
3.31 t (9.1)
3.19 dd (9.2, 7.7)
3.37 t (9.2)
3 49 ddd (10.3, 9.1, 4.1)
3.92 dd (11.0, 4.1)
3.24 dd (11.0, 10.3)
3.50 ddd (10.8, 9.2, 4.8)
3.93 dd (11.5, 4.8)
3.24 dd (11.5, 10.8)
a
a
b
b
1
2
3
4
5
6
4.62 br s
102.3
72.4
72.6
73.9
70.0
18.1
Rha0
1
2
3
4
5
6
4.62 br s
105.3
72.3
72 6
74.0
70.0
18.1
3.79 br d (3.8)
3.62 dd (9.4, 3.8)
3.39 t (9.4)
3.80 br d (4.1)
3 63 dd (9.2, 4.1)
3.34 t (9.2)
3.57 dq (9.4, 7,4)
l.29 d (7.4)
3.56 dq (9.2, 6.2)
1.27 d (6.2)
a
Values in parentheses are coupling constants in Hz.

262
A. Yokosuka et al. / Phytochemistry Letters 4 (2011) 259–266
1
the large JC-1,H-1 value (173.0 Hz) indicated that the anomeric
proton was equatorial thus possessing an -pyranoid anomeric
form (Jia et al., 1998). In the HMBC spectrum of 1, long-range
correlations were observed between H-1 of Rha at 5.99 and C-28
of aglycone at 175.6, H-1 of Xyl at 4.59 and C-2 of Glc at 82.2,
and between H-1 of Glc at 4.40 and C-3 of aglycone at 96.4. Thus,
1 was determined to be 2 -hydroxy-3 -[(O- -xylopyranosyl-
(1 ! 2)- -glucopyranosyl)oxy]lup-20(29)-en-28-oic acid
rhamnopyranosyl ester (Fig. 1).
(
dC 30.4), C-17 (dC 48.5), and C-22 (dC 35.1). A long-range
correlation was also observed between H-1 of Rha at 4.64 and
C-28 of aglycone at 67.4. Accordingly, the structure of the
aglycone moiety of 4 was determined to be lup-20(29)-en-2 ,3
28-triol (Schmidt et al., 1995), and 4 to be 2 -hydroxy-28-[(
rhamnopyranosyl)oxy]lup-20(29)-en-3 -yl O- -arabinopyra-
nosyl-(1 ! 4)-O- -xylopyranosyl-(1 ! 2)-O-[ -xylopyrano-
syl-(1 ! 4)]- -glucopyranoside.
The 1H NMR spectrum of compound 5 (C51H84O20) exhibited
signals for four anomeric protons at 4.69 (d, J = 7.7 Hz), 4.45 (d,
J = 7.8 Hz), 4.34 (dd, J = 7.7 Hz), and 4.27 (d, J = 7.0 Hz), together
with signals for six triterpenoid methyl groups at 1.68, 1.09, 1.07,
1.00, 0.92, and 0.87 (each s), and an exomethylene group at 4.68
and 4.57 (each br s). Acid hydrolysis 5 gave -rhamnose,
arabinose, -xylose, and
-glucose. When the 1H and 13C NMR
a
d
d
d
a b,
a-L-
d
d
d
a
d
d
b
a-L
b-D
a
b
b
-D
b
-
D
b
-
D
a
-
L
-
b-D
Compound 2 was shown to have the molecular formula
52H84O21 on the basis of HRESI-TOFMS (m/z 1045.5582
d
C
[M+H]+). The deduced molecular formula was higher than that of
d
1 by C5H8O4, corresponding to one pentose unit. The 1H NMR
d
spectrum of 2 exhibited signals for four anomeric protons at
(br s), 4.63 (d, J = 7.5 Hz), 4.41 (d, J = 7.6 Hz), and 4.27 (d, J = 7.0 Hz),
as well as signals for six triterpenoid methyl groups at 1.70, 1.08,
1.01, 0.94, 0.92, and 0.86 (each s), and an exomethylene group at
4.75 and 4.62 (each br s). Acid hydrolysis of 2 with 1 M HCl gave 1a,
-rhamnose, -arabinose, -xylose, and -glucose. On comparison of
the 13C NMR spectrum of 2 with that of 1, a set of five additional
signals corresponding to a terminal -arabinopyranosyl unit (Ara)
were observed at 103.8, 72.0, 74.1, 69.7, and 67.3, and the signals
due to C-4 of the Xyl moiety and its neighboring carbons varied,
while all other signals remained almost unaffected. In the HMBC
spectrum, long-range correlations were observed between H-1 of
Rha and C-28 of the aglycone, H-1 of Ara and C-4 of Xyl, H-1 of Xyl
and C-2 of Glc, and between H-1 of Glc and C-3 of the aglycone.
d
5.99
L
L-
D
D
d
signals of 5 were compared with those of 4, the two compounds
were in complete agreement as to the signals arising from the
tetraglycoside group attached to C-3 of the aglycone. However, the
d
L
L
D
D
signals assignable to the a-L-rhamnopyranosyl residue bonded to
C-28 of the aglycone could not be observed in the 1H and 13C NMR
spectra of 5, and the C-28 carbon signal of 5 was shifted upfield by
7.0 ppm in comparison with that of 4. The above chemical and
spectral data implied that 5 was the C-28 derhamnosyl derivative
of 4 and allowed for the structural determination of 5 to be
a-L
d
made as 2
pyranosyl-(1 ! 4)-O-
pyranosyl-(1 ! 4)]-
a
,28-dihydroxylup-20(29)-en-3
-xylopyranosyl-(1 ! 2)-O-[
-glucopyranoside.
b
-yl O-
a
-
L
-arabino-
b
-
D
b-D-xylo-
b
-D
Thus, 2 was formulated as 3
O-
-xylopyranosyl-(1 ! 2)-
xylup-20(29) -en-28-oic acid
b
b
a
-[(O- -arabinopyranosyl-(1 ! 4)-
-glucopyranosyl)oxy]-2
-rhamnopyranosyl ester.
a
-
L
Compound 6 had the molecular formula C69H114O33 on the
basis of HRESI-TOFMS (m/z: 1493.7139 [M+Na]+). The 1H NMR
spectrum of 6 contained signals for six quaternary methyl groups
b-D
-
D
a
-hydro-
-L
Compound 3 was analyzed for C57H92O25 by HRESI-TOFMS (m/z
1177.5925 [M+H]+), higher than that of 2 by C5H8O4. On the basis of
the spectral properties of 3 and the results of acid hydrolysis, giving
at
group at
5.11 (br s), 4.90 (d, J = 7.3 Hz), 4.67 (d, J = 7.7 Hz), 4.63 (d,
J = 2.9 Hz), 4.62 (br s), 4.43 (d, J = 7.7 Hz), and 4.33 (d, J = 7.7 Hz).
Acid hydrolysis of 6 yielded -rhamnose, -arabinose, -xylose, and
-glucose. In comparison of 13C NMR spectrum of 6 with that of 4,
the signals due to the aglycone moiety and an -rhamnopyr-
anosyl group linked to C-28 of the aglycone were observed at
almost the same positions for each of the compounds. However,
differences were recognized in the glycoside moiety attached to C-
3 of the aglycone. Detailed analysis of the 1D TOCSY and 2D NMR
spectra resulted in the assignments of all the proton resonances
due to the seven glycosyl units, including identification of their
multiplet patterns and coupling constants, and the corresponding
one-bond coupled carbons (Table 1). The carbon chemical shifts
d
1.69, 1.09, 1.07, 1.00, 0.93, and 0.86 (each s), an exomethylene
d
4.71 and 4.58 (each br s), and seven anomeric protons at
d
1a, L-rhamnose, L-arabinose, D-xylose, and D-glucose, 3 was shown
to be a triterpene glycoside closely related to 2; however the 1H
NMR spectrum of 3 contained resonances for five anomeric protons
L
L
D
D
at
d
5.99 (br s), 4.69 (d, J = 7.5 Hz), 4.45 (d, J = 7.7 Hz), 4.34 (d,
a-L
J = 7.7 Hz), and 4.27 (d, J = 7.0 Hz). On comparison of the 13C NMR
spectrum of 3 with that of 2, a set of five additional signals
corresponding to a terminal b-D d 105.3,
-xylopyranosyl unit (Xyl0) [
74.9, 77.9, 71.0, and 67.1] were observed, and C-4 of Glc was
significantly shifted downfield. In the HMBC spectrum of 3, long-
range correlations were detected between H-1 of Rha and C-28 of
the aglycone, H-1 of Ara and C-4 of Xyl, H-1 of Xyl and C-2 of Glc, H-
1 of Xyl0 and C-4 of Glc, and between H-1 of Glc and C-3 of the
aglycone. Thus, 3 was characterized as 3
b
-[(O-
-xylopyranosyl-(1 ! 2)-O-[
-glucopyranosyl)oxy]-2 -hydroxylup-20(29)-en-
-rhamnopyranosyl ester.
a
-
L
-arabinopyr-
thus assigned indicated that
6
contained
-glucopyranosyl moiety (Glc), a C-3 and C-4
-xylopyranosyl moiety (Xyl), a C-2 substituted
-rhamnopyrano-
-arabinopyranosyl moiety
-xylopyranosyl moiety (Xyl0). The
a C-2 and C-4
anosyl-(1 ! 4)-O-
b
-
D
b
-D
-xylopyrano-
disubstituted
disubstituted
b-D
syl-(1 ! 4)]-
b
-D
a
b
-D
b-
28-oic acid
a-
L
D
-glucopyranosyl moiety (Glc0), two terminal
syl moieties (Rha, Rha0), a terminal
(Ara), and a terminal
a-L
Compound 4 was deduced as C57H94O24 on the basis of HRESI-
TOFMS (m/z 1163.6212 [M+H]+). The 1H NMR spectrum of 4
showed signals for five anomeric protons at
4.64 (br s), 4.45 (d, J = 7.7 Hz), 4.34 (d, J = 7.7 Hz), and 4.27 (d,
J = 7.0 Hz), along with signals for six triterpenoid methyl groups at
a-L
b
-D
b-
d
4.69 (d, J = 7.5 Hz),
orientations of the anomeric centers of the Glc, Glc0, Xyl, Xyl0
3
moieties were supported by the relatively large JH-1,H-2 values of
1
their anomeric protons (7.3–7.7 Hz) and JH-1,C-1 values (Glc:
d
1.69, 1.08, 1.07, 1.01, 0.92, and 0.87 (each s), and an
exomethylene group at 4.71 and 4.59 (each br s). Acid hydrolysis
4 gave -rhamnose, -arabinose, -xylose, and -glucose, while the
aglycone was decomposed under acidic conditions. The 1H and 13
158.4 Hz; Xyl: 156.6 Hz; Glc0: 157.8 Hz; Xyl0: 154.9 Hz). For the
1
d
Rha and Rha0 moieties, the large JH-1,C-1 values (Rha: 171.8 Hz;
L
L
D
D
Rha0: 168.0 Hz) indicated that each anomeic proton possessed an
C
a-pyranoid anomeric form. The proton chemical shifts and spin-
NMR spectral properties of 4 ware essentially analogues to those of
3 except for the signals arising from the ring D and E portions of the
aglycone. However, the ester carbonyl group attached to C-28 of
the aglycone could not be observed in the IR and 13C NMR spectra
coupling constants of the Ara moiety of 6 were different from those
of 2–5. The coupling constants assigned by the 1D TOCSY spectra,
the large 1JH-1,C-1 value (172.8 Hz), and three-bond coupled strong
HMBC correlations from the anomeric proton to the C-3 and C-5
carbons, indicated that the conformation of the Ara group is
of 4. The signals for an oxymethylene group [
dH 3.41 and 3.22 (ABq,
J = 9.4 Hz)/
d
C 68.0] newly appeared in the 1H and 13C NMR spectra
present as 1C4 with an
a-orientation of the anomeric center. This
of 4. In the HMBC spectrum, the oxymethylene protons, which
were assigned to H2-28, showed long-range correlations with C-16
phenomenon has been observed in the case of stryphnosides C–F
isolated from the title plant (Yokosuka et al., 2008a). In the HMBC

A. Yokosuka et al. / Phytochemistry Letters 4 (2011) 259–266
263
29
20
H
H
C
O
HO
O
2
3
28
HO
H
O
O
R2O
HO
O
H
O
Me
O
R1O
HO
HO
OH
HO
OH
R1 R2
1
2
3
H
H
H
Ara
Ara
Xyl
H
28
H
CH2OR
HO
HO
H
O
O
OH
HO
HO
O
O
HO
HO
H
O
O
O
HO
O
HO
OH
OH
R
Rha
H
4
5
H
H
CH2
O
2
R
HO
H
O
O
HO
O
O
HO
HO
H
OH
O
O
Me
O
O
HO
HO
O
HO
HO
OH
OH
HO
O
HO
O
HO
O
OH
Me
O
HO
HO
OH
R
OH
H
6
7
HO
HO
O
O
Me
HO
O
HO
Rha:
HO
Ara:
Xyl:
OH
OH
HO
OH
Fig. 1. Structures of 1–7.
spectrum of 6, long-range correlations were observed between H-1
of Rha at H 4.90 and
H 5.11 and C-2 of Glc0 at C 80.4, H-1 of Glc0 at
H 4.67 and C-2 of Glc at C 81.2,
H 4.63 and C-4 of Xyl at H 4.33
C 71.8, H-1 of Xyl0 at
and C-4 of Glc at dC 80.2, H-1 of Glc at dH 4.43 and C-3 of the
aglycone at H 4.62 and C-28 of
C 96.6, and between H-1 of Rha0 at
the aglycone at dC 67.3. Accordingly, the structure of 6 was
elucidated as -hydroxy-28-[( -rhamnopyranosyl)oxy]lup-
d
d
d
d
d
d
C-3 of Xyl at
H-1 of Ara at
d
d
C 79.9, H-1 of Xyl at
d
d
d
2a
a-L

264
A. Yokosuka et al. / Phytochemistry Letters 4 (2011) 259–266
20(29)-en-3
b
-yl O-
a
-
b
-
L
-arabinopyranosyl-(1 ! 4)-O-[
-glucopyranosyl-(1 ! 3)]-O-
-xylopyranosyl-(1 ! 4)]- -glucopyra-
a
-
L
-rham-
concentrated under reduced pressure, and the viscous concentrate
(70 g) was passed through a Diaion HP-20 column and successively
eluted with 20% MeOH, 40% MeOH, 80% MeOH, MeOH, and EtOAc
(each 5 L). Column chromatography (CC) of the 80% MeOH eluate
portion on silica gel and elution with a stepwise gradient mixture
of CHCl3–MeOH–H2O (30:10:1; 20:10:1; 10:10:1), and finally with
MeOH alone, gave seven fractions (A–H). Fraction C was subjected
to CC on ODS silica gel eluted with MeCN–H2O (1:2) and MeOH–
H2O (2:1) to give 1 (9.1 mg). Fraction E was chromatographed on
ODS silica gel eluted with MeCN–H2O (1:2) and MeOH–H2O (2:1)
and silica gel with CHCl3–MeOH–H2O (20:10:1) to give 2 (10.0 mg)
and 5 (10.3 mg). Fraction F was subjected to CC on ODS silica gel
eluted with MeCN–H2O (1:2) and MeOH–H2O (3:2; 2:1) and silica
gel with CHCl3–MeOH–H2O (20:10:1) to give 7 (7.0 mg). Fraction G
was chromatographed on ODS silica gel eluted with MeOH–H2O
(2:1) and MeCN–H2O (1:2) to give 3 (53.2 mg) and 4 (10.7 mg).
Fraction H was subjected to CC on ODS silica gel eluted with
MeOH–H2O (4:1) and MeCN–H2O (1:2), and preparative HPLC
using MeCN–H2O (1:2) to give 6 (9.3 mg).
nopyranosyl-(1 ! 2)-O-
-
D
b-D-xylo-
pyranosyl-(1 ! 2)-O-[
b
D
b-D
noside.
Compound 7 exhibited a molecular formula of C69H114O32 on
the basis of HRESI-TOFMS (m/z 1477.7146 [M+Na]+). Comparison
of the 1H and 13C NMR spectra of 7 with those of 6 showed
considerable structural similarities. However, the molecular
formula of 7 was lower by one oxygen atom than that of 6,
implying the lack of one hydroxy group. When the 13C NMR
spectrum of 7 was compared with that of 6, the signal due to the C-
2 hydroxymethine carbon, which was observed at
displaced by a methylene carbon signal at 27.3 in 7. In addition,
the carbon signals due to C-1 and C-3 were shifted upfield by 7.7
and 5.5 ppm, respectively. All other NMR signals of 7, which were
assigned by the 1D-TOCSY, 1H–1H COSY, HMQC, and HSQC-TOCSY
spectra, were almost superimposable with those of 6. Acid
d 68.2 in 6, was
d
hydrolysis of 7 gave L-rhamnose, L-arabinose, D-xylose, and D-
glucose, while the aglycon was decomposed under acidic condi-
tions. Analysis of the HMBC spectrum of 7 indicated that the
hexaglycoside attached to C-3 of the aglycone is the same as that of
3.4. Compound 1
6, and that an
C-28 of the aglycone. Thus, the structure of 7 was formulated as 28-
[( -rhamnopyranosyl)oxy]lup-20(29)-en-3 -yl O- -arabino-
pyranosyl-(1 ! 4)-O-[ -rhamnopyranosyl-(1 ! 2)-O-
copyranosyl-(1 ! 3)]-O- -xylopyranosyl-(1 ! 2)-O-[
pyranosyl-(1 ! 4)]- -glucopyranoside.
a-L-rhamnopyranosyl group forms a linkage with the
Amorphous powder; ½a D25
ꢁ
ꢀ84.58 (c 0.10, MeOH); IR
nmax (film)
a
-
L
b
a-
L
cmꢀ1: 3395 (OH), 2931 (CH), 1725 (C55O); 1H NMR (500 MHz,
a
-L
b
-D-glu-
CD3OD): d 4.75 and 4.62 (each 1H, br s, H2-29), 3.69 (1H, ddd,
b
-
D
b-
D-xylo-
J = 11.8, 9.3, 4.4 Hz, H-2), 2.94 (1H, d, J = 9.3 Hz, H-3), 1.70 (3H, s,
Me-30), 1.08 (3H, s, Me-23), 1.01 (3H, s, Me-27), 0.94 (3H, s, Me-
26), 0.92 (3H, s, Me-25), 0.87 (3H, s, Me-24); For 1H NMR data of the
sugar moiety, see Table 1; for 13C NMR (125 MHz, CD3OD)
spectroscopic data, see Tables 1 and 2; HRESI-TOFMS m/z:
935.4889 [M+Na]+ (calculated for C47H76O17Na, 935.4980).
b
-D
Compounds 1–7 are new lupane-type triterpene glycosides
with up to seven monosaccharides. This is the first report of the
isolation of lupane-type triterpene glycosides from the genus
Stryphnodendron. Compound 1 contains an O-b-D-xylopyranosyl-
(1 ! 2)-
b-D
-glucopyranosyl group at the C-3 hydroxy group of the
aglycone. Triterpene 3-O-diglycoside is first isolated from S.
fissuratum. Compounds 4–6 have the common aglycone of lup-
3.5. Acid hydrolysis of 1
20(29)-ene-2
a
,3
b
,28-triol, among which 4 and 6 are bisdesmo-
A solution of 1 (8.4 mg) in 1 M HCl (dioxane–H2O, 1:1, 2 mL)
was heated at 95 8C for 1 h under an Ar atmosphere. After cooling,
the reaction mixture was neutralized by passage through an
Amberlite IRA-96SB (Organo, Tokyo, Japan) column (10 mm
i.d. ꢂ 100 mm) and chromatographed on Diaion HP-20 (10 mm
i.d. ꢂ 100 mm), eluted with H2O–MeOH (3:2) followed by EtOH–
Me2CO (1:1), to yield an aglycone fraction and a sugar fraction
(2.5 mg). The aglycone fraction was chromatographed on silica gel
(12 mm i.d. ꢂ 120 mm) eluted with hexane–Me2CO (1:1) to give
sides with the sugar unit at the C-3 and C-28 hydroxy groups
whereas 5 is a monodesmoside with the sugar unit at the C-3
hydroxy group. To the best of our knowledge, these types of
triterpene glycosides have not been isolated from natural sources.
The structure of the aglycone moiety of 7 is lup-20(29)-ene-3b,28-
diol (betulin). Betulin glycosids are mainly synthesized (Gauthier
et al., 2006) and have been isolated only from Oplopanax elatus
Nakai (Araliaceae) (Wang and Xu, 1993).
2a,3b-dihydroxylup-20(29)-en-28-oic acid (1a, 2.1 mg). The
3. Experimental
sugar fraction was dissolved in H2O (1 mL) and passed through
a Sep-Pak C18 cartridge (Waters, Milford, MA, USA), which was
then analyzed by HPLC under the following conditions: column,
3.1. General
Capcell Pak NH2 SG80 (4.6 mm i.d. ꢂ 250 mm, 5
solvent, MeCN–H2O (17:3); flow rate, 1.0 mL/min; detection, RI
and OR. Identification of -glucose, -xylose, and -rhamnose
present in the sugar fraction was carried out by comparison of
their retention times and optical rotations with those of authentic
mm, Shiseido);
The instruments and experimental conditions were the same as
described in the previous papers (Yokosuka and Mimaki, 2008b;
Yokosuka et al., 2009).
D
D
L
3.2. Plant material
samples; tR (min) 13.6 (D-glucose, positive optical rotation), 8.7 (D-
xylose, positive optical rotation), 6.9 (
optical rotation).
L-rhamnose, negative
The pericarps of S. fissuratum Mart. were collected in the fields
´
of Agua Boa ward, Mato Grosso State, Brazil, in May and June 2003.
The plant was identified by Dr. Heleno Dias Ferreira (Department
3.6. Compound 1a
ˆ
´
of Morphology, Instituto de Ciencias Biologicas, Universidade
Federal de Goias, Goias State, Brazil). A voucher specimen has been
deposited in the Instituto Biologico with the number 26796.
Amorphous powder; ½a D25
ꢁ
+1.18 (c 0.10, MeOH); IR nmax (film)
´
´
cmꢀ1: 3365 (OH), 2944 (CH), 1696 (C55O); 1H NMR (500 MHz,
´
CD3OD):
d 4.70 and 4.59 (each 1H, br s, H2-29), 3.60 (1H, ddd,
3.3. Extraction and isolation
J = 11.3, 9.6, 4.6 Hz, H-2), 2.88 (1H, d, J = 9.6 Hz, H-3), 1.69 (3H, s,
Me-30), 1.00 (3H, s, Me-27), 0.98 (3H, s, Me-23), 0.96 (3H, s, Me-
26), 0.91 (3H, s, Me-25), 0.77 (3H, s, Me-24); for 13C NMR
(125 MHz, CD3OD) spectroscopic data, see Table 2; HRESI-TOFMS
m/z: 473.3643 [M+H]+ (calculated for C30H49O4, 473.3631).
The pericarps of S. fissuratum (2.0 kg) were macerated and
extracted with EtOH, and the EtOH extract (353 g) was partitioned
between n-BuOH and H2O. The n-BuOH soluble portion was

A. Yokosuka et al. / Phytochemistry Letters 4 (2011) 259–266
265
Table 2
13C NMR chemical shift assignments for the aglycone moieties of compounds 1–7 in CD3OD.
Position
1
la
48.7
2
3
4
5
6
7
1
2
47.7
68.2
96.4
41.8
56.9
19.3
35.4
42.0
51.9
39.0
22.2
26.8
40.0
43.7
30.8
33.1
58.2
50.5
48.7
47.7
68.2
96.4
41.8
56.9
19.3
35.4
42.0
51.9
39.0
22.2
26.8
40.0
43.7
30.8
33.1
58.2
50.5
48.9
47.7
68.2
96.6
41.8
56.9
19.3
35.5
42.0
51.9
39.0
22.3
26.8
40.0
43.7
30.8
33.1
58.2
50.5
48.7
47.7
68.2
96.6
41.8
56.8
19.4
35.3
42.1
51.8
39.0
22.1
26.5
39.0
43.9
28.3
30.7
48.5
50.0
49.3
47.7
68.2
96.6
41.8
56.8
19.3
35.1
42.2
51.8
39.0
22.1
26.6
38.7
43.9
28.2
30.4
48.5
50.0
49.0
47.7
68.2
96.6
41.8
56.8
19.4
35.4
42.1
51.8
38.9
22.1
26.5
38.9
43.9
28.3
30.8
48.1
50.0
49.3
40.0
69.8
84.4
40.5
56.8
19.5
35.5
42.0
52.0
39.5
22.2
26.8
39.6
43.6
30.8
33.4
57.5
50.5
48.7
152.0
31.7
38.2
29.1
17.2
17.9
16.7
15.1
180.0
110.1
19.5
27.3
91.1
40.4
57.1
19.3
35.5
42.1
51.8
38.0
22.0
26.6
39.0
43.8
28.3
30.7
48.1
50.0
49.3
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
151.4
31.7
37.9
28.4
17.4
17.9
16.8
15.1
175.6
110.6
19.5
151.4
31.7
37.9
28.4
17.3
17.9
16.7
15.1
175.6
110.6
19.5
151.4
31.7
37.9
28.4
17.4
17.9
16.8
15.1
175.6
110.6
19.5
151.7
31.2
36.1
28.4
17.4
17.9
16.6
15.2
67.4
110.5
19.4
151.9
30.9
35.1
28.4
17.4
17.9
16.5
15.2
60.4
110.3
19.4
151.7
31.2
36.2
28.7
17.4
17.9
16.6
15.2
67.3
110.5
19.3
151.7
31.2
36.1
28.3
16.5
16.6
16.7
15.2
67.3
110.4
19.2
3.7. Compound 2
3.10. Compound 5
Amorphous powder; ½a D25
ꢁ
ꢀ1.18 (c 0.10, MeOH); IR nmax (film)
Amorphous powder; ½a D25
ꢁ
ꢀ1.78 (c 0.10, MeOH); IR
n
max (film)
cmꢀ1: 3390 (OH), 2947 (CH), 1727 (C55O); 1H NMR (500 MHz,
cmꢀ1: 3388 (OH), 2943 (CH); 1H NMR (500 MHz, CD3OD):
d 4.68
CD3OD):
d
4.75 and 4.62 (each 1H, br s, H2-29), 3.70 (1H, ddd,
and 4.57 (each 1H, br s, H2-29), 3.73 and 3.28 (each 1H, ABq,
J = 10.9 Hz, H2-28), 3.70 (1H, ddd, J = 11.3, 9.4, 4.6 Hz, H-2), 2.74
(1H, d, J = 9.4 Hz, H-3), 1.68 (3H, s, Me-30), 1.09 (3H, s, Me-23), 1.07
(3H, s, Me-26), 1.00 (3H, s, Me-27), 0.92 (3H, s, Me-25), 0.87 (3H, s,
J = 12.7, 9.4, 4.5 Hz, H-2), 2.95 (1H, d, J = 9.4 Hz, H-3), 1.70 (3H, s,
Me-30), 1.08 (3H, s, Me-23), 1.01 (3H, s, Me-27), 0.94 (3H, s, Me-
26), 0.92 (3H, s, Me-25), 0.86 (3H, s, Me-24); For 1H NMR data of the
sugar moiety, see Table 1; for 13C NMR (125 MHz, CD3OD)
spectroscopic data, see Tables 1 and 2; HRESI-TOFMS m/z:
1045.5582 [M+H]+ (calculated for C52H85O21, 1045.5583).
Me-24); For 1H NMR data of the sugar moiety, see Table 1; for 13
C
NMR (125 MHz, CD3OD) spectroscopic data, see Tables 1 and 2;
HRESI-TOFMS m/z: 1017.5709 [M+H]+ (calculated for C51H85O20
,
1017.5634).
3.8. Compound 3
3.11. Compound 6
Amorphous powder; ½a D25
ꢀ1.68 (c 0.10, MeOH); IR nmax (film)
ꢁ
cmꢀ1: 3389 (OH), 2940 (CH), 1737 (C55O); 1H NMR (500 MHz,
Amorphous powder; ½a D25
ꢁ
ꢀ31.68 (c 0.10, MeOH); IR
n
max (film)
CD3OD):
d
4.75 and 4.62 (each 1H, br s, H2-29), 3.70 (1H, ddd,
cmꢀ1: 3365 (OH), 2925 (CH); 1H NMR (500 MHz, CD3OD):
d 4.71
J = 11.8, 9.3, 4.4 Hz, H-2), 2.94 (1H, d, J = 9.3 Hz, H-3), 1.70 (3H, s,
Me-30), 1.09 (3H, s, Me-23), 1.01 (3H, s, Me-27), 0.94 (3H, s, Me-
26), 0.92 (3H, s, Me-25), 0.86 (3H, s, Me-24); For 1H NMR data of the
sugar moiety, see Table 1; for 13C NMR (125 MHz, CD3OD)
spectroscopic data, see Tables 1 and 2; HRESI-TOFMS m/z:
1177.5925 [M+H]+ (calculated for C57H93O25, 1177.6006).
and 4.58 (each 1H, br s, H2-29), 3.70 (1H, m, H-2), 3.55 and 3.38
(each 1H, ABq, J = 9.2 Hz, H2-28), 2.93 (1H, d, J = 9.3 Hz, H-3), 1.69
(3H, s, Me-30), 1.09 (3H, s, Me-23), 1.07 (3H, s, Me-26), 1.00 (3H, s,
Me-27), 0.93 (3H, s, Me-25), 0.86 (3H, s, Me-24); For 1H NMR data
of the sugar moiety, see Table 1; for 13C NMR (125 MHz, CD3OD)
spectroscopic data, see Tables 1 and 2; HRESI-TOFMS m/z:
1493.7139 [M+Na]+ (calculated for C69H114O33Na, 1493.7140).
3.9. Compound 4
3.12. Compound 7
Amorphous powder; ½a D25
ꢁ
ꢀ26.38 (c 0.10, MeOH); IR
n
max (film)
cmꢀ1: 3375 (OH), 2935 (CH); 1H NMR (500 MHz, CD3OD):
d
4.71
Amorphous powder; ½a D25
ꢁ
ꢀ29.28 (c 0.10, MeOH); IR
n
max (film)
and 4.59 (each 1H, br s, H2-29), 3.71 (1H, ddd, J = 11.9, 9.4, 4.3 Hz,
H-2), 3.55 and 3.41 (each 1H, ABq, J = 9.4 Hz, H2-28), 2.94 (1H, d,
J = 9.4 Hz, H-3), 1.69 (3H, s, Me-30), 1.08 (3H, s, Me-23), 1.07 (3H, s,
Me-26), 1.01 (3H, s, Me-27), 0.92 (3H, s, Me-25), 0.87 (3H, s, Me-
24); For 1H NMR data of the sugar moiety, see Table 1; for 13C NMR
(125 MHz, CD3OD) spectroscopic data, see Tables 1 and 2; HRESI-
cmꢀ1: 3367 (OH), 2927 (CH); 1H NMR (500 MHz, CD3OD):
d 4.70
and 4.57 (each 1H, br s, H2-29), 3.54 and 3.42 (each 1H, ABq,
J = 13.7 Hz, H2-28), 3.11 (1H, dd, J = 11.2, 5.3 Hz, H-3), 1.68 (3H, s,
Me-30), 1.03 (3H, s, Me-23), 1.07 (3H, s, Me-26), 1.00 (3H, s, Me-
27), 0.86 (3H, s, Me-25), 0.80 (3H, s, Me-24); For 1H NMR data of the
sugar moiety, see Table 1; for 13C NMR (125 MHz, CD3OD)
spectroscopic data, see Tables 1 and 2; HRESI-TOFMS m/z:
1477.7146 [M+Na]+ (calculated for C69H114O32 Na, 1477.7191).
TOFMS m/z: 1163.6212 [M+H]+ (calculated for C57H95O24
1163.6213).
,

266
A. Yokosuka et al. / Phytochemistry Letters 4 (2011) 259–266
Haraguchi, M., Yokosuka, A., Kawakami, S., Rodrigues, A.S., Chaves, N.S.T., Brum,
3.13. Acid hydrolysis of 2–7
K.B., Raspantini, P.C., Gorniak, S.L., Mimaki, Y., 2006. New saponins isolated from
Stryphnodendron fissuratum bean pods. LabCiencia con Noticias Tecnicas del
Laboratorio 14, 6–8.
Compounds 2 (6.1 mg), 3 (14.2 mg), 4 (10.4 mg), 5 (6.8 mg), 6
(8.0 mg), and 7 (6.0 mg) were independently subjected to acid
hydrolysis as described for 1 to give aglycones (1a: 0.7 and 0.8 mg
from 2 and 3, respectively) and sugar fractions (2: 3.5 mg, 3:
6.1 mg, 4: 5.4 mg, 5: 2.1 mg, 6: 2.4 mg, and 7: 3.2 mg). The aglycons
of 4–7 were decomposed under acidic conditions. HPLC analysis of
the sugar fractions under the same conditions as in the case of 1
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