Huangqiyenins G - J, four new 9,10-secocycloartane (=9,19-Cyclo-9,10- secolanostane) triterpenoidal Saponins from Astragalus membranaceus Bunge leaves

Article abstract of DOI:10.1002/hlca.201100174

Four new 9,10-secocycloartane (=9,19-cyclo-9,10-secolanostane) triterpenoidal saponins, named huangqiyenins G-J (1-4, resp.), were isolated from Astragalus membranaceus Bunge leaves. The acid hydrolysis of 1-4 with 1M aqueous HCl yielded D-glucose, which was identified by GC analysis after treatment with L-cysteine methyl ester hydrochloride. The structures of 1-4 were established by detailed spectroscopic analysis as (3β,6α,10α, 16β,24E)-3,6-bis(acetyloxy)-10,16-dihydroxy-12-oxo-9,19-cyclo-9, 10-secolanosta-9(11),24-dien-26-yl β-D-glucopyranoside (1), (3β,6a,10α,24E)-3,6-bis(acetyloxy)-10-hydroxy-12,16-dioxo-9, 19-cyclo-9,10-secolanosta-9(11),24-dien-26-yl β-D-glucopyranoside (2), (3β,6α,9α,10α,16β,24E)-3,6-bis(acetyloxy)-9,10, 16-trihydroxy-9,19-cyclo-9,10-secolanosta-11,24-dien-26-yl β-D- glucopyranoside (3), and (3β,6α,10α,24E)-3,6-bis(acetyloxy)-10- hydroxy-16-oxo-9,19-cyclo-9,10-secolanosta-9(11),24-dien-26-yl β-D-glucopyranoside (4). Copyright

Full text of DOI:10.1002/hlca.201100174

Helvetica Chimica Acta – Vol. 94 (2011)
2239
Huangqiyenins G – J, Four New 9,10-Secocycloartane (¼ 9,19-Cyclo-9,10-
secolanostane) Triterpenoidal Saponins from Astragalus membranaceus
Bunge Leaves
a
a
a
a
b
by Hai-Xue Kuang* ), Qiu-Hong Wang ), Bing-You Yang ), Zhi-Bin Wang ), Yoshihito Okada ), and
b
Tohru Okuyama )
a) Key Laboratory of Chinese Materia Medica, Heilongjiang University of Chinese Medicine, Ministry of
Education, No. 24 Heping Road, Xiangfang District, Harbin 150040, P. R. China
(
phone: þ 86-451-82193001; fax: þ 86-451-82110803; e-mail: hxkuang@hotmail.com)
b
)
Meiji Pharmaceutical University, 2-522-1 Noshio, Kiyose, Tokyo 204-8588, Japan
Four new 9,10-secocycloartane (¼ 9,19-cyclo-9,10-secolanostane) triterpenoidal saponins, named
huangqiyenins G – J (1 – 4, resp.), were isolated from Astragalus membranaceus Bunge leaves. The acid
hydrolysis of 1 – 4 with 1m aqueous HCl yielded d-glucose, which was identified by GC analysis after
treatment with l-cysteine methyl ester hydrochloride. The structures of 1 – 4 were established by de-
tailed spectroscopic analysis as (3b,6a,10a,16b,24E)-3,6-bis(acetyloxy)-10,16-dihydroxy-12-oxo-9,19-
cyclo-9,10-secolanosta-9(11),24-dien-26-yl b-d-glucopyranoside (1), (3b,6a,10a,24E)-3,6-bis(acetyl-
oxy)-10-hydroxy-12,16-dioxo-9,19-cyclo-9,10-secolanosta-9(11),24-dien-26-yl b-d-glucopyranoside (2),
(
3b,6a,9a,10a,16b,24E)-3,6-bis(acetyloxy)-9,10,16-trihydroxy-9,19-cyclo-9,10-secolanosta-11,24-dien-
2
9
6-yl b-d-glucopyranoside (3), and (3b,6a,10a,24E)-3,6-bis(acetyloxy)-10-hydroxy-16-oxo-9,19-cyclo-
,10-secolanosta-9(11),24-dien-26-yl b-d-glucopyranoside (4).
Introduction. – Astragalus membranaceus Bunge belongs to the family Legumi-
nosae and has long been one of the most important tonic herbs used in traditional
Chinese medicine. Pharmacological investigations demonstrated that extracts of the
leaves possess biological activities, including antioxidation, anti-aging, and anti-
inflammatory activity [1], and protection against pancreatic injury [2]. The dried leaves
of A. membranaceus (named beiqishengcha) has been authorized as a functional food
by the State Food and Drug Administration of P. R. China in 1998.
Known biologically active components of A. membranaceus are triterpenoidal
saponins, flavonoids, and polysaccharides. Chemical studies on Astragalus saponins
have reported the presence of cycloartane-type triterpenoid glycosides which were
found to exert many biological activities (e.g., hepatoprotection, cardioprotection,
antidiabetic nephropathy, anti-inflammatory, gastroprotection, and neuroprotection
against ischemic brain injury) [3 – 8].
In the earlier investigations of A. membranaceus leaves, we have reported four
cycloartane-type and two secocycloartane triterpenoid saponins named huangqiyenins
A – F [9 – 12] (cycloartane ¼ 9,19-cyclolanostane). As a continuing phytochemical
study on this natural medicine, we further isolated four new 9,10-secocycloartane
(
¼ 9,19-cyclo-9,10-secolanostane ¼ 9(10)a-homo-19-norlanostane) triterpenoidal sap-
onins, huangqiyenins G – J (1 – 4, resp.). It is worth mentioning that 9,10-secocycloar-
tanes are less common than their cycloartane counterparts. They represent a small
group of compounds comprising ca. 20 representatives in the Ranunculaceae,
ꢀ
2011 Verlag Helvetica Chimica Acta AG, Zꢁrich

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Helvetica Chimica Acta – Vol. 94 (2011)
Buxaceae, and Leguminosae families [13 – 15]. This article deals with the isolation and
structure elucidation of these newly isolated triterpenoids.
Results and Discussion. – Compound 1, named huangqiyenin G, was obtained as a
white amorphous powder (MeOH). The molecular formula was determined as
þ
C H O by HR-FAB-MS ([M þ Na] at m/z 773.4087), indicating ten degrees of
40
62 13
1
unsaturation. The H-NMR spectrum of 1 (Table 1) showed seven Me s at d(H) 0.91,
1
.08, 1.20, 1.55, 1.78, 2.06, and 2.08, a Me d at d(H) 1.38 (J ¼ 6.5 Hz), an olefinic H-atom
s at d(H) 5.92, and an olefinic H-atom t at d(H) 5.72 (J ¼ 6.4 Hz). No signals due to H-
atoms of a cyclopropane ring were observed. The typical downfield CH d at d(H) 4.90
(
J ¼ 7.8 Hz) was assigned to the anomeric H-atom of the b-d-glucopyranosyl moiety.
The acid hydrolysis of 1 with 1m aqueous HCl yielded d-glucose, which was identified
by GC analysis after treatment with l-cysteine methyl ester hydrochloride in pyridine
13
[
16]. The C-NMR data (Table 2) showed the presence of 40 C-atoms that were sorted
by a DEPT experiment as eight Me, nine CH , and 14 CH groups, as well as nine
2
quaternary C-atoms, including four olefinic C-atoms at d(C) 128.3, 129.5, 131.9, and
1
13
1
57.6, and three C¼O groups at d(C) 170.4, 170.5, and 203.8. The H- and C-NMR
1 1
signals were assigned by HSQC, H, H-COSY, and HSQC-TOCSY data. The full
connectivity was deduced from the HMBC data (Fig.). In particular, the key long-
range correlations H ꢀC(19)/C(5), C(8), C(9), C(10), and C(11), and H ꢀC(19)/C(8),
a
b
C(9), C(10), and C(11) showed that the CH (19) group must be located between C(9)
2
and C(10), and the coupling constants J ¼ 14.7 and 1.2 Hz of H ꢀC(19) indicated that
a
C(19) was connected to two quaternary C-atoms (C(9) and C(10)), and H ꢀC(19)
a
showed allylic coupling with HꢀC(11). The HMBCs Me(18)/C(12), C(13), C(14), and
C(17), and HꢀC(11)/C(8), C(9), C(12), C(13), and C(19) indicated that the C¼O
group at d(C) 203.8 must be located at C(12). Furthermore, the correlation from the
1)
Trivial atom numbering; for systematic names, see Exper. Part.

Helvetica Chimica Acta – Vol. 94 (2011)
2241
anomeric H-atom of the glucosyl moiety at d(H) 4.90 to d(C) 75.2 could also be
observed, which confirmed that the glucosyloxy group should be attached to C(26). In
addition, in the HMBC spectrum of 1, HꢀC(3) and HꢀC(6) showed connectivity with
the C¼O of the AcO groups at d(C) 170.4 and 170.5, respectively. Compound 1 was thus
determined to represent a 9,19-cyclo-9,10-secolanostane-type triterpenoid with two Ac
groups and a glucosyl group.
1
1
Figure. Key HMBC (H ! C) and H, H-COSY (—) features of 1 and 3
1
1
The relative configuration of 1 was determined on the basis of H, H-coupling
constants, NOESY experiments, and comparison of NMR data with those of
huangqiyenin F [12], a compound previously isolated from A. membranaceus which
13
possessed a (24E) side-chain moiety. In particular, the C-NMR data of the side chain
were almost identical in both compounds, and the correlations between HꢀC(23) and
Me(27) were observed in the NOESYexperiment, which enabled the assignment of the
C(24)¼C(25) bond configuration as (E) in 1. The configuration at C(3) of 1 could be
assigned as b, according to the coupling constant of HꢀC(3) at d(H) 4.93 (dd, J ¼ 10.4,
2
.0 Hz). The NOESY correlations Me(30)/HꢀC(6), Me(29)/HꢀC(5), Me(29)/
HꢀC(3), Me(28)/HꢀC(16), Me(28)/HꢀC(17), Me(18)/HꢀC(8), HꢀC(5)/HꢀC(3),
HꢀC(6)/H ꢀC(19), HꢀC(6)/HꢀC(8) were observed. From these data, HꢀC(3),
b
HꢀC(5), HꢀC(16), HꢀC(17), and H ꢀC(19) could be placed in a-position, HꢀC(6),
a
and HꢀC(8), and H ꢀC(19) in b-position. Furthermore, the interaction Me(30)/
b
H ꢀC(19) indicated that the CH (19) group was in b-position with respect to ring A,
b
2
and hence OHꢀC(10) was in a-position. In addition, The NOESY correlations Me(18)/
HꢀC(20), HꢀC(17)/CH (22), HꢀC(16)/CH (22) confirmed the configuration at C(20)
2
2
as (R) [17 – 19]. Thus, the structure of 1 was established as (3b,6a,10a,16b,24E)-3,6-

2
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Helvetica Chimica Acta – Vol. 94 (2011)
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Helvetica Chimica Acta – Vol. 94 (2011)
Table 2. 13C-NMR Data (125 MHz, C D N) of Compounds 1 – 4. d in ppm.
5
5
1
2
3
4
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
44.5 (t)
25.3 (t)
79.5 (d)
39.5 (s)
57.9 (d)
76.0 (d)
32.9 (t)
45.8 (d)
157.6 (s)
72.3 (s)
128.3 (d)
203.8 (s)
58.0 (s)
44.2 (t)
25.2 (t)
79.4 (d)
39.5 (s)
57.8 (d)
75.5 (d)
33.3 (t)
44.4 (d)
30.1 (t)
25.3 (t)
80.0 (d)
40.4 (s)
60.8 (d)
75.6 (d)
27.9 (t)
42.3 (d)
76.0 (s)
73.2 (s)
133.4 (d)
136.7 (d)
47.5 (s)
49.9 (s)
45.1 (t)
71.4 (d)
52.2 (d)
21.8 (q)
49.9 (t)
31.1 (d)
18.5 (q)
36.5 (t)
25.6 (t)
129.4 (d)
132.0 (s)
75.3 (t)
14.3 (q)
21.3 (q)
44.5 (t)
25.0 (t)
79.7 (d)
39.5 (s)
58.0 (d)
76.6 (d)
33.0 (t)
42.5 (d)
137.4 (s)
72.3 (s)
123.9 (d)
36.4 (t)
44.4 (s)
42.5 (s)
48.9 (t)
217.6 (s)
60.5 (d)
16.2 (q)
48.7 (t)
31.9 (d)
18.8 (q)
35.6 (t)
C(9)
159.9 (s)
72.3 (s)
127.7 (d)
201.8 (s)
57.3 (s)
46.2 (s)
48.6 (t)
216.0 (s)
55.8 (d)
15.6 (q)
48.5 (t)
32.3 (d)
20.9 (q)
34.9 (t)
26.4 (t)
128.4 (d)
132.5 (s)
75.2 (t)
14.2 (q)
18.2 (q)
27.9 (q)
18.4 (q)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
AcOꢀC(3)
AcOꢀC(6)
C(1’)
50.7 (s)
46.7 (t)
70.3 (d)
49.5 (d)
14.3 (q)
48.4 (t)
30.6 (d)
19.7 (q)
36.9 (t)
26.0 (t)
25.8 (t)
129.5 (d)
131.9 (s)
75.2 (t)
128.7 (d)
132.7 (s)
75.2 (t)
14.2 (q)
19.4 (q)
28.4 (q)
18.9 (q)
21.7 (q), 170.4 (s)
21.1 (q), 170.5 (s)
103.6 (d)
75.2 (d)
78.7 (d)
71.8 (d)
14.2 (q)
18.2 (q)
28.4 (q)
18.8 (q)
21.7 (q), 170.4 (s)
21.1 (q), 170.5 (s)
103.6 (d)
75.5 (d)
78.8 (d)
71.8 (d)
78.5 (d)
62.9 (t)
27.1 (q)
18.0 (q)
21.5 (q), 170.5 (s)
21.0 (q), 170.0 (s)
103.9 (d)
75.3 (d)
78.7 (d)
71.9 (d)
21.6 (q), 170.4 (s)
21.0 (q), 170.5 (s)
103.8 (d)
75.3 (d)
78.6 (d)
72.0 (d)
78.6 (d)
62.8 (t)
C(2’)
C(3’)
C(4’)
C(5’)
78.5 (d)
62.9 (t)
78.7 (d)
63.0 (t)
C(6’)
bis(acetyloxy)-10,16-dihydroxy-12-oxo-9,19-cyclo-9,10-secolanosta-9(11),24-dien-26-yl
1
b-d-glucopyranoside ).
Compound 2, named huangqiyenin H, was obtained as a white amorphous powder,
with a molecular formula C H O based on the HR-FAB-MS (m/z 771.3936 ([M þ
4
0
60 13
þ
1
Na] )). The H-NMR spectrum (Table 1) showed seven Me s, a Me d, and two
13
olefinic H-atom signals at d(H) 6.03 (br. s) and 5.66 (J ¼ 6.6 Hz). The C-NMR
spectrum (Table 2) revealed 40 C-atoms including two ketonic C¼O groups at d(C)
2
16.0 and 201.8, four olefinic C-atoms at d(C) 127.7, 128.4, 132.5, and 159.9, two Ac

Helvetica Chimica Acta – Vol. 94 (2011)
2245
groups at d(C) 21.6, 170.4, 21.0, and 170.5, and a glucosyl group at d(C) 103.8, 75.3, 78.6,
2.0, 78.6, and 62.8. The acid hydrolysis of 2 gave d-glucose [16]. Detailed comparison
7
1
13
of the H- and C-NMR data of 2 and 1 indicated they have identical rings A – C and
side chain but a different ring D. The appearance of a C¼O signal at d(C) 216.0 in the
1
3
C-NMR spectrum of 2 and the disappearance of the signal of HꢀC(16) in the
1
H-NMR spectrum revealed the presence of a C¼O group at C(16), which was further
confirmed by the HMBC data. The HMBCs H ꢀC(15)/C(13), C(14), C(16), and
a
C(17), and HꢀC(20)/C(13), C(16), and C(17) confirmed the connectivity of ring D.
Therefore, 2 was elucidated as (3b,6a,10a,24E)-3,6-bis(acetyloxy)-10-hydroxy-12,16-
1
dioxo-9,19-cyclo-9,10-secolanosta-9(11),24-dien-26-yl b-d-glucopyranoside ).
Huangqiyenin I (3) was obtained as a white amorphous powder, and the molecular
formula was determined as C H O , on the basis of the HR-FAB-MS (m/z 775.4249
4
0
64 13
þ
(
[M þ Na] )). The acid hydrolysis of 3 liberated d-glucose, which was identified by GC
1
analysis [16]. The H-NMR spectrum (Table 1) showed the presence of three olefinic
H-atoms at d(H) 6.40 (J ¼ 9.9 Hz), 5.75 (J ¼ 9.9 Hz), and 5.72 (J ¼ 6.4 Hz), of seven
tertiary Me groups at d(H) 1.05, 1.15, 1.27, 1.43, 1.80, 2.03, and 2.08, and of a secondary
13
Me group at d(H) 1.19 (J ¼ 6.6 Hz). In the C-NMR spectrum (Table 2), the 40 C-
atoms were assigned to eight Me, nine CH , and 15 CH groups and to eight quaternary
2
C-atoms by a DEPT experiment. The spectroscopic data of 3 were similar to those of
huangqiyenin F [12]. However, olefinic H-atoms of a disubstituted C¼C bond were
1
observed in the H-NMR spectrum of 3. In the HMBC spectrum, the correlation of the
olefinic HꢀC(12) to C(9), C(11), C(13), and C(14), of HꢀC(11) to C(8), C(9), C(12),
and C(13), and of Me(18) to C(12), C(13), C(14), and C(17) indicated that the C¼C
bond is located between C(11) and C(12) (Fig.). The key NOE correlations H ꢀC(19)/
b
Me(30), H ꢀC(19)/HꢀC(6), H ꢀC(19)/HꢀC(8), and HꢀC(6)/HꢀC(8) indicated that
b
b
CH (19) was in b-orientation with respect to ring A, and the OH groups at C(9) and
2
C(10) were a-orientated. The configuration at C(20) was determined as (R) by the
NOESY correlations Me(18)/HꢀC(20), HꢀC(17)/CH (22), and HꢀC(12)/Me(21)
2
[
17 – 19]. Accordingly, compound 3 was assigned as (3b,6a,9a,10a,16b,24E)-3,6-
bis(acetyloxy)-9,10,16-trihydroxy-9,19-cyclo-9,10-secolanosta-11,24-dien-26-yl b-d-glu-
1
copyranoside ).
Huangqiyenin J (4) was obtained as a white amorphous powder. The molecular
formula was determined as C H O by positive-mode HR-FAB-MS (m/z 757.4114
4
0
62 12
þ
1
(
1
[M þ Na] )). The H-NMR spectrum of 4 (Table 1) showed seven Me s at d(H) 0.93,
.04 (6 H), 1.21, 1.83, 2.06, and 2.08, a Me d at d(H) 1.01 (J ¼ 6.8 Hz), and two olefinic
13
H-atom signals at d(H) 5.46 (J ¼ 3.8, 1.2 Hz) and 5.71 (J ¼ 6.3 Hz). The C-NMR
spectrum (Table 2) exhibited 40 C-atoms including four olefinic C-atoms at d(C) 123.9,
1
28.7, 132.7, and 137.4, and three C¼O groups at d(C) 170.4, 170.5, and 217.6. The acid
1 13
hydrolysis of 4 gave d-glucose [16]. Comparison of the H- and C-NMR data of 4
with those of huangqiyenin F [12] and 2 showed that 4 has the same rings A – C as
huangqiyenin F, and the same ring D and side-chain moiety as 2, which was further
established by the key HMBC, HSQC-TOCSY, and NOESY features. The key HMBC
cross-peaks Me(18)/C(12), C(13), C(14), and C(17), and Me(28)/C(8), C(13), C(14),
and C(15) indicated the connection between ring C and D. Thus, 4 was established
as (3b,6a,10a,24E)-3,6-bis(acetyloxy)-10-hydroxy-16-oxo-9,19-cyclo-9,10-secolanosta-
1
9
(11),24-dien-26-yl b-d-glucopyranoside ).

2
246
Helvetica Chimica Acta – Vol. 94 (2011)
Experimental Part
General. Column chromatography (CC): silica gel 60 (SiO ; 200 – 300 mesh; Merck, Germany).
2
HPLC: Waters-Delta-600 pump and Waters-2414 refractive-index detector; TSK-gel ODS-120T column
(
0
10 mm, 40 ꢁ 300 mm; Tosoh, Japan). GC: Fuli-9790 H flame detector; DM-5 column (0.25 mm, 30 m ꢁ
2
ꢀ1
.25 mm; Dikma, China). IR Spectra: Shimadzu FI-IR-8100 spectrometer; ˜n in cm . NMR Spectra:
JNM-LA-500 spectrometer; d in ppm rel. to Me Si as internal standard, J in Hz. HR-FAB-MS: Jeol-JMS-
4
DX-302 mass spectrometer; in m/z.
Plant Material. The leaves of A. membranaceus Bunge were collected in Daxingꢂanling,
Heilongjiang Province, P. R. China, in August 1995, and identified by Prof. Zhenyue Wang, Heilongjiang
University of Chinese Medicine, P. R. China. A voucher specimen (No. 19950026) is deposited with the
Herbarium of Heilongjiang University of Chinese Medicine, P. R. China.
Extraction and Isolation. The dried leaves of A. membranaceus Bunge (1.2 kg) were defatted with
petroleum ether (2 ꢁ 5 l) for 2 h each time (808). Then, the residue was extracted with MeOH under
reflux (3 ꢁ 5 l) for 3 h each time, and the extract was concentrated to a syrup. A suspension of the MeOH
extract (310 g) in H O (5 l) was extracted with BuOH (3 ꢁ 5 l) sat. with H O. The BuOH layer was
2
2
concentrated to give the BuOH extract (119 g). The BuOH extract (60 g) was subjected to CC (SiO ,
2
CHCl /MeOH/H O 6 :1:0.1 and then CHCl /MeOH/H O 3 :1:0.1): Fractions I – X, in order of elution.
3
2
3
2
Fr. IV (6.8 g) was resubjected to CC (SiO , CHCl /MeOH/H O 5 :1:0.1) and separated further by HPLC
2
3
2
(
TSK-gel ODS-120T, flow-rate 8 ml/min, MeOH/H O 3 :7): 1 (123 mg; t 9.0 min), 2 (42.1 mg; tR
2
R
1
4.5 min), 4 (30.4 mg; tR 19.3 min), and 3 (80.8 mg; tR 25.1 min).
Acid Hydrolysis of 1 – 4. Each of compounds 1 – 4 (each 4 mg) was hydrolyzed in 1m HCl (1.0 ml) for
h at 858. The mixture was cooled and partitioned between CHCl (2.0 ml) and H O (2.0 ml). The aq.
2
3
2
layer was washed with CHCl (3 ꢁ 3.0 ml), neutralized with Ba(OH) , filtered, and evaporated. The
3
2
residue was dissolved in pyridine (1.0 ml), and 0.1m l-cysteine methyl ester hydrochloride in pyridine
2.0 ml) was added. The mixture was heated at 608 for 1 h. An equal volume of Ac O was added under
(
2
heating, and incubation was continued for 1 h. The acetylated thiazolidine derivatives was compared with
authentic samples by GC (DM-5 column; injector and detector temp. 2808; temp. gradient for the oven
from at 1608 to 1958 at a rate of 58/min). The sugar unit in compounds 1 – 4 was determined by the
retention time tR of the peak of the hydrolysates and that of an authentic sample of d-glucose (tR
1
5.1 min).
Huangqiyenin G (¼(3b,6a,10a,16b,24E)-3,6-Bis(acetyloxy)-10,16-dihydroxy-12-oxo-9,19-cyclo-
9
1
,10-secolanosta-9(11),24-dien-26-yl b-d-Glucopyranoside ¼ (2E,6R)-6-[2S,3R,3aR,6aR,9S,10aR,11S,
2aR,12bS)-9,11-Bis(acetyloxy)-1,2,3,3a,4,6,6a,7,8,9,10,10a,11,12,12a,12b-hexadecahydro-2,6a-dihy-
droxy-3a,10,10,12b-tetramethyl-4-oxobenzo[4,5]cyclohept[1,2-e]inden-3-yl]hex-2-en-1-yl b-d-Glucopyra-
2
1
noside; 1): White amorphous powder. [a] ¼ þ55.1 (c ¼ 1.0, MeOH). IR (KBr): 3430, 2959, 1729, 1713,
D
1
13
ꢀ
1
658, 1371, 1078, 1022. H- and C-NMR: Tables 1 and 2. FAB-MS (neg.): 749 ([M ꢀ H] ). HR-FAB-
þ þ
MS (pos.): 773.4085 ([M þ Na] , C H NaO ; calc. 773.4088).
40
62
13
Huangqiyenin H (¼(3b,6a,10a,24E)-3,6-Bis(acetyloxy)-10-hydroxy-12,16-dioxo-9,19-cyclo-9,10-se-
colanosta-9(11),24-dien-26-yl b-d-Glucopyranoside ¼ (2E,6R)-6-[3R,3aR,6aR,9S,10aR,11S,12aR,12bS)-
9
,11-Bis(acetyloxy)-1,2,3,3a,4,6,6a,7,8,9,10,10a,11,12,12a,12b-hexadecahydro-6a-hydroxy-3a,10,10,12b-
tetramethyl-2,4-dioxobenzo[4,5]cyclohept[1,2-e]inden-3-yl]hex-2-en-1-yl b-d-Glucopyranoside; 2):
2
1
White amorphous powder. [a] ¼ þ61.5 (c ¼ 1.0, MeOH). IR (KBr): 3425, 2945, 1745, 1729, 1713,
D
1
13
þ
þ
1
650, 1078, 1022. H- and C-NMR: Tables 1 and 2. FAB-MS (pos.): 748 (M ), 771 ([M þ Na] ). HR-
þ þ
FAB-MS (pos.): 771.3936 ([M þ Na] , C H NaO ; calc. 771.3932).
40
60
13
Huangqiyenin I (¼(3b,6a,10a,16b,24E)-3,6-Bis(acetyloxy)-9,10,16-trihydroxy-9,19-cyclo-9,10-seco-
lanosta-11,24-dien-26-yl b-d-Glucopyranoside ¼ (2E,6R)-6-[2S,3R,3aR,5aR,6aR,9S,10aR,11S,12aR,
1
3
2bS)-9,11-Bis(acetyloxy)-1,2,3,3a,5a,6,6a,7,8,9,10,10a,11,12,12a,12b-hexadecahydro-2,5a,6a-trihydroxy-
a,10,10,12b-tetramethylbenzo[4,5]cyclohept[1,2-e]inden-3-yl]hex-2-en-1-yl b-d-Glucopyranoside; 3):
2
1
White amorphous powder. [a] ¼ þ65.3 (c ¼ 1.0, MeOH). IR (KBr): 3440, 2943, 1719, 1709, 1079,
D
1
13
ꢀ
1
(
026. H- and C-NMR: Tables 1 and 2. FAB-MS (neg.): 751 ([M ꢀ H] ). HR-FAB-MS (pos.): 775.4249
þ þ
[M þ Na] , C H NaO ; calc. 775.4245).
40
64
13

Helvetica Chimica Acta – Vol. 94 (2011)
2247
Huangqiyenin J (¼(3b,6a,10a,24E)-3,6-Bis(acetyloxy)-10-hydroxy-16-oxo-9,19-cyclo-9,10-secola-
nosta-9(11),24-dien-26-yl b-d-Glucopyranoside ¼ (2E,6R)-6-[3R,3aR,5aR,6aR,9S,10aR,11S,12aR,
1
1
2bS)-9,11-Bis(acetyloxy)-1,2,3,3a,4,6,6a,7,8,9,10,10a,11,12,12a,12b-hexadecahydro-5a-hydroxy-3a,10,
0,12b-tetramethyl-2-oxobenzo[4,5]cyclohept[1,2-e]inden-3-yl]hex-2-en-1-yl b-d-Glucopyranoside; 4):
21
White amorphous powder. [a]
D
¼ þ69.6 (c ¼ 1.0, MeOH). IR (KBr): 3441, 2938, 17.44, 1720, 1715,
1
13
ꢀ
1
7
080, 1026. H- and C-NMR: Tables 1 and 2. FAB-MS (neg.): 733 ([M ꢀ H] ). HR-FAB-MS (pos.):
þ
þ
57.4143 ([M þ Na] , C H NaO ; calc. 757.4139).
40
62
12
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Received April 28, 2011