Four new 9,19-cyclolanostane derivatives from the rhizomes of Cimicifuga yunnanensis hsiao

Article abstract of DOI:10.1002/hlca.200800231

Four new 9,19-cyclolanostane-type triterpenes, 24-O-acetyl-25- anhydroshengmanol-3-O-β-d-xylopyranoside (1), 25-i-butylcimigenol-3-O- β-d-xylopyranoside (2), 12-β-hydrocimigenol-3-one (3), and 12-β-hydrocimigenol-1-en-3-one (4), together with 15 known ana

Full text of DOI:10.1002/hlca.200800231

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Helvetica Chimica Acta – Vol. 92 (2009)
Four New 9,19-Cyclolanostane Derivatives from the Rhizomes of Cimicifuga
yunnanensis Hsiao
by Yin Niana)b), Jian-Chao Chena), Lu Lua)b), Xian-Ming Zhanga), Lin Zhoua), and Ming-Hua Qiu*a)
a) State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of
Botany, Chinese Academy of Sciences, Kunming 650204, Yunnan, P. R. China
(phone: þ 86-871-5223327; fax: þ 86-871-5223255; e-mail: mhchiu@mail.kib.ac.cn)
b) Graduate School of the Chinese Academy of Sciences, Beijing 100039, P. R. China
Four new 9,19-cyclolanostane-type triterpenes, 24-O-acetyl-25-anhydroshengmanol-3-O-b-d-xylo-
pyranoside (1), 25-O-butylcimigenol-3-O-b-d-xylopyranoside (2), 12-b-hydrocimigenol-3-one (3), and
12-b-hydrocimigenol-1-en-3-one (4), together with 15 known analogues were isolated from the rhizome
of Cimicifuga yunnanensis Hsiao. Their structures were determined by spectroscopic and chemical
methods.
Introduction. – The rhizome of several Cimicifuga species (Ranunculaceae), called
ꢀShengmaꢁ in China, is a source of a popular herbal medicine, which has been used as an
antipyretic and analgesic agent since ancient times. In Europe and the United States, a
dietary supplement made from the alcoholic extract of Cimicifuga racemosa, also called
black cohosh, has been reputed to reduce the frequency and intensity of hot flashes and
other menopause symptoms. Cimicifuga yunnanensis is a rare species indigenous to the
north-west of Yunnan Province of China [1]. The rhizome of C. yunnanensis is a very
famous herb drug, which is used by local people such as Tibetan and Naxi people to
relieve fever, headache, and some menopause symptoms. Chemical constituents of
Cimicifuga species like C. racemosa, C. dahurica, C. simplex, and C. foetida have been
investigated, and a series of highly oxygenated triterpene glycosides and aglycons have
been isolated and identified [2 – 25]. However, no work has been reported so far on the
chemical constituents of C. yunnanensis.
The present study on C. yunnanensis resulted in the isolation of four new 9,19-
cyclolanostane triterpenes 1 – 4 (see Fig. 1). The present article deals with the isolation
and structural elucidation of the new 9,19-cyclolanostane triterpenes, based on
spectroscopic analyses and chemical correlations.
Results and Discussion. – Compound 1 was isolated as a white powder. In the
negative-ion HR-ESI-MS, it showed a quasi-molecular ion at m/z 661.3958 ([M ꢀ H]ꢀ),
consistent with a molecular formula C37H58O10. The IR spectrum showed absorptions of
1
OH and C¼O groups at 3433 and 1709 cmꢀ1, respectively. The assignment of the H-
and 13C-NMR spectroscopic data of 1 (Table) was based on HMQC, HMBC data
(Fig. 2), and a 1H,1H-COSY spectrum. The 1H- and 13C-NMR spectra displayed
characteristic signals for a cyclopropane CH2 at d(H/C) 0.26, 0.51; 30.8 (CH2(19)). The
13C-NMR spectrum exhibited 37 signals, of which 30 were attributed to a triterpene
ꢂ 2009 Verlag Helvetica Chimica Acta AG, Zꢃrich

Helvetica Chimica Acta – Vol. 92 (2009)
113
Fig. 1. Structures of compounds 1 – 19
skeleton, five to a pentose unit, and two to an AcO group. A DEPT experiment
permitted differentiation of the 37 13C-NMR resonances into eight quaternary C-atoms,
13 CH, nine CH2, and seven Me groups. All these data suggested that 1 is a 9,19-
cyclolanostane triterpene monoglycoside [16]. The NMR spectroscopic data of 1
showed a close resemblance with those of compound 5 [20], except for the presence of
two downfield signals at d(C) 115.9 and 142.2, and the absence of a quaternary C-atom

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Helvetica Chimica Acta – Vol. 92 (2009)
and a Me signal due to C(25) and C(26), respectively. On the basis of these observations,
it was reasonable to assume that 1 is a 25-dehydrated derivative of 5, which was
supported by the upfield shift of C(27) by 7.2 ppm. The HMBC spectrum showed
correlations of d(H) 1.79 (HꢀC(27)) with d(C) 142.2 (C(25)), 115.9 (C(26)), and 82.8
(C(24)), and a pair of singlets at d(H) 5.18 (HaꢀC(26)) and 4.98 (HbꢀC(26)) with d(C)
82.8 (C(24)) and 18.3 (C(27)) further supported the deduction. The monosaccharide
obtained after acid hydrolysis was identified as d-xylose by comparing its Rf value and
optical rotation with an authentic sample. Significant NOESY (Fig. 3) correlations of
HꢀC(3) with HꢀC(5) suggested a b-orientation of the substituent at C(3), whereas
the associations of HꢀC(15) with HꢀC(8) and Me(18), revealed an a-orientation of
the OH group at C(15). Compound 1 was converted to 25-anhydrocimigenol-3-O-b-d-
xylopyranoside (1a), which was identified by comparison of its spectral data with those
reported in the literature [12], on 2% K2CO3 treatment, followed by 5% AcOH
treatment (Scheme). This conversion suggested the (23R,24R) configuration for 1.
Therefore, the structure of compound 1 was elucidated as 24-O-acetyl-25-anhydrosh-
engmanol-3-O-b-d-xylopyranoside.
Scheme. Conversion of 1 into 1a
Compound 2 was isolated as a white powder. The negative-ion HR-ESI-MS of 2
showed a quasimolecular ion at m/z 675.3672 ([M ꢀ H]ꢀ), corresponding to the
molecular formula C39H64O9. The IR spectrum showed a strong absorption band at
3398 cmꢀ1 for OH groups. The 1H-NMR spectra (Table) showed diagnostic signals due
to a cyclopropane CH2 at d(H) 0.28 and 0.52 (each 1 H, d, J ¼ 3.6, CH2(19)), and an
anomeric H-atom at d(H) 4.86 (d, J ¼ 7.6 ) . The 13C-NMR spectrum (Table) displayed
five C-atoms of a glycosidic moiety (d(C) 107.6, 75.6, 78.7, 71.3, and 67.2). The 1H- and
13C-NMR data of 2 were similar to those of 6 [16][18], except for an additional O-butyl
(d(H/C) 3.38/61.1 (C(1’’)), 1.47/32.9 (C(2’’)), 1.34/19.7 (C(3’’)), 0.87/14.1 (C(4’’))
functionality in 2, which was positioned at C(25), based on the HMBC correlation of
HꢀC(1’’) to C(25). The deduction was also confirmed by the downfield shift of C(25)
by 4.9 ppm. The relative configuration of 2 was assigned on the basis of a NOESY
experiment (Fig. 3). The configurations of C(23) and C(24) were ascribed as (R) and
(S), respectively, by comparing the spectral data of the C(23) signal and the coupling
constants of the HꢀC(24) signal of 2 with those of known 9,19-cyclolanostane
triterpene glycosides [11][23]. Therefore, the structure of compound 2 was identified as
25-O-butylcimigenol-3-O-b-d-xylopyranoside.

Helvetica Chimica Acta – Vol. 92 (2009)
115
Table. The 1H- and 13C-NMR Data for Compounds 1 – 4. In C5D5N; d in ppm, J in Hz. Assignements were confirmed by
1
HMQC, HMBC, and H,1H-COSY experiments.
1
2
3
4
d(C)
d(H)
d(C)
d(H)
d(C)
d(H)
d(C)
d(H)
1
2
32.4 (t) 1.57 – 1.60 (m), 32.4 (t) 1.58 (overlapped),
1.22 – 1.24 (m) 1.22 (overlapped)
33.7 (t) 1.73 (ddd,
J ¼ (4.5),
154.1 (d) 6.80 (d,
J ¼ 10.0)
1.42 (m)
30.2 (t) 2.35 – 2.38 (m), 30.0 (t) 2.36 (br. d, J ¼ 11), 37.6 (t) 2.62 (ddd,
126.7 (d) 6.08 (d,
J ¼ 10.0)
1.93 – 1.96 (m)
1.95 (br. d, J ¼ 11)
J ¼ 6.5),
2.29 (br. d,
J ¼ 10.0)
3
88.5 (d) 3.49 (dd,
J ¼ 4.0, 11.5)
88.6 (d) 3.51 (dd,
J ¼ 4.0, 11.4)
215.0 (s)
50.2 (s)
204.2 (s)
4
5
41.4 (s)
41.4 (s)
47.6 (d) 1.34
(overlapped)
46.2 (s)
45.0 (d) 2.02 – 2.04 (m)
47.6 (d) 1.32 – 1.34 (m)
48.2 (d) 1.58 (dd,
J ¼ 4.0, 12.3)
6
7
21.0 (t) 0.71 – 0.74 (m)
21.1 (t) 0.71 (br. d,
J ¼ 12.4)
21.4 (t) 0.79 – 0.81 (m)
29.9 (t) 1.22 – 1.24 (m)
26.6 (t) 2.01 – 2.04 (m), 26.5 (t) 2.10
26.0 (t) 2.14 (br. d,
J ¼ 12.5),
19.8 (t) 1.41
(overlapped),
1.89
1.07 – 1.09 (m)
(overlapped),
1.19
1.14
(overlapped)
48.7 (d) 1.65 – 1.67 (m)
(overlapped)
47.4 (d) 1.81 (dd,
J ¼ 5, 12.2)
(overlapped)
44.6 (d) 2.09 – 2.12 (m)
8
9
49.1 (d) 1.73 – 1.76 (m)
20.0 (s)
20.0 (s)
26.7 (s)
21.7 (s)
25.1 (s)
30.1 (s)
10 26.7 (s)
26.2 (s)
11 26.7 (t) 2.05 – 2.09 (m), 26.4 (t) 2.10
1.32 – 1.34 (m) (overlapped),
41.1 (t) 2.80 (dd,
J ¼ 9.0, 9.0),
1.48
41.3 (t) 2.70 (dd,
J ¼ 8.0, 8.0),
1.75 – 1.77 (m)
1.05
(overlapped)
(overlapped)
72.7 (d) 4.21 (br. s)
12 34.1 (t) 1.71 – 1.73 (m), 34.1 (t) 1.65 – 1.68 (m),
1.55 – 1.58 (m) 1.52 – 1.54 (m)
71.7 (d) 4.21 (br. s)
13 42.1 (s)
14 46.7 (s)
41.9 (s)
47.3 (s)
41.1 (s)
47.9 (s)
47.9 (s)
48.5 (s)
15 79.6 (s) 4.14
(overlapped)
16 103.5 (s)
80.1 (d) 4.24 (s)
79.9 (d) 4.45 (d, J ¼ 8.0)
79.3 (d) 4.41 (d,
J ¼ 8.0)
111.9 (s)
112.3 (s)
112.1 (s)
17 60.6 (d) 1.79
59.5 (d) 1.44 – 1.47 (m)
59.9 (d) 1.85 (s)
59.5 (s) 1.85 (br. s)
(overlapped)
18 20.5 (q) 1.23 (s)
19 30.8 (t) 0.26 (d,
J ¼ 3.3),
19.5 (q) 1.13 (s)
12.2 (q) 1.45 (s)
11.7 (s) 1.36 (s)
30.9 (t) 0.52 (d, J ¼ 3.6),
30.3 (t) 0.59 (d, J ¼ 4.0), 31.1 (t) 0.78 (d,
0.28 (d, J ¼ 3.6)
0.73 (d, J ¼ 4.0)
J ¼ 4.0),
1.21 (d,
J ¼ 4.8)
0.51 (d,
J ¼ 3.2)
20 27.3 (d) 1.79
24.1 (d) 1.65 – 1.68 (m)
24.1 (d) 1.86
23.9 (d) 1.83
(overlapped)
(overlapped)
21.0 (q) 1.39 (d, J ¼ 6.0)
(overlapped)
21.2 (q) 1.39 (d,
J ¼ 6.0)
38.6 (t) 1.11
21 21.3 (q) 0.97 (d,
J ¼ 3.5)
19.6 (q) 0.84 (br. d,
J ¼ 7.2)
22 32.2 (t) 1.73 – 1.75 (m), 38.2 (t) 0.97 – 0.99 (m),
38.8 (t) 1.14
1.99 – 2.02 (m)
2.22 – 2.26 (m)
(overlapped),
(overlapped),
2.39 – 2.43 (m)
2.38 – 2.41 (m)
23 74.6 (d) 4.13
(overlapped)
71.7 (d) 4.64 (d, J ¼ 8.8)
71.8 (d) 4.78 (d, J ¼ 9.0)
71.7 (d) 4.79 (d,
J ¼ 8.8)

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Helvetica Chimica Acta – Vol. 92 (2009)
Table (cont.)
1
2
3
4
d(C)
d(H)
d(C)
d(H)
d(C)
d(H)
d(C)
d(H)
24
25
26
27
28
29
30
Ac
82.8 (d)
142.2 (s)
115.9 (t)
18.3 (q)
11.9 (q)
25.8 (q)
15.5 (q)
170.4 (s)
21.5 (q)
6.04 (d, J ¼ 9)
88.2 (d)
75.9 (s)
22.9 (q)
20.2 (q)
11.8 (q)
25.8 (q)
15.5 (q)
3.67 (s)
90.1 (d)
71.0 (s)
27.1 (q)
25.6 (q)
11.9 (q)
22.6 (q)
20.8 (q)
3.83 (s)
89.9 (d)
70.9 (s)
27.1 (q)
25.6 (q)
11.4 (q)
21.8 (q)
19.2 (q)
3.83 (s)
5.18 (s), 4.98 (s)
1.79 (s)
1.24 (s)
1.30 (s)
1.02 (s)
1.28 (br. s)
1.29 (br. s)
1.18 (s)
1.31 (br. s)
1.05 (s)
1.51 (s)
1.49 (s)
1.19 (s)
1.09 (s)
0.99 (s)
1.51 (s)
1.49 (s)
1.17 (s)
1.16 (s)
0.93 (s)
1.90 (s)
1’’
61.1 (t)
3.38 (dd,
J ¼ 6, 11.8)
2’’
3’’
4’’
1’
2’
3’
32.9 (t)
19.7 (t)
1.47 (overlapped)
1.34 (overlapped)
0.87 (br. s)
14.1 (q)
107.6 (d)
75.6 (d)
78.7 (d)
71.3 (d)
107.6 (d)
75.6 (d)
78.6 (d)
71.3 (d)
4.86 (d, J ¼ 7.5)
4.03 (t, J ¼ 8.0)
4.15 (overlapped)
4.22 (dd,
4.86 (d, J ¼ 7.6)
4.03 (t, J ¼ 8)
4.17 (overlapped)
4.20 – 4.24 (m)
4’
J ¼ 5.5, 9.3)
5’
67.1 (t)
3.75 (t, J ¼ 11),
67.2 (t)
3.73 (t, J ¼ 10.4),
4.34 (dd,
4.37 (dd,
J ¼ 5.0, 11.5)
J ¼ 5.0, 11.0)
Compound 3 was obtained as colorless needles. In the negative-ion HR-ESI-MS, it
showed a quasi-molecular ion at m/z 501.3217 ([M ꢀ H]ꢀ), consistent with the
molecular formula C30H46O6. The IR spectrum showed OH and C¼O absorptions at
3456 and 1688 cmꢀ1. In the 1H-NMR spectrum of 3 (Table), there were six tertiary Me
at d(H) 0.99, 1.09, 1.19, 1.45, 1.49, and 1.51, a secondary Me at d(H) 1.39 (d, J ¼ 6.0),
and the cyclopropane CH2 at d(H) 0.59 and 0.73 (each 1 H, d, J ¼ 4.0, CH2(19)). The
13C-NMR spectrum showed 30 signals, including a C¼O group at d(C) 215.0, and six O-
bearing C-atom signals at d(C) 90.1 (d), 79.9 (d), 72.7 (d), 71.8 (d), 112.3 (s), and 71.0
(s). The above evidence suggested that compound 3 was a highly oxygenated 9,19-
cyclolanostane triterpene aglycone. The NMR spectrum of 3 resembled the one of 12b-
hydroxycimigenol [4], except that a hydroxymethine C-atom (d(C) 77.7) at C(3) in
12b-hydroxycimigenol was replaced by a C¼O group (d(C) 215.0) in 3, which was in
accordance with the downfield shifts of C(2) and C(4) by 6.7 and 9.4 ppm respectively.
HMBC Correlations of d(H) 1.73 and 1.42 (CH2(1)) and d(H) 2.62 and 2.29 (CH2(2))
with d(C) 215.0 (C(3)) also confirmed above deduction. The relative configuration of 3
was determined to be the same as that of 2 by an analysis of the NOESY data (Fig. 3).
Accordingly, compound 3 was characterized as 12b-hydroxycimigenol-3-one.
Compound 4 was isolated as colorless needles. The negative-ion HR-ESI-MS
established the molecular formula of 4 as C30H44O6. Its NMR data (Table) were similar
to those of 3 except for the signals in ring A. C¼C Signals at d(C) 154.1 and 126.7 were
observed in 4, whereas the signals of two CH2 groups due to C(1) and C(2) were absent.

Helvetica Chimica Acta – Vol. 92 (2009)
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Fig. 2. Major HMBC correlations of compounds 1 – 4
Significant HMBC correlations (Fig. 2) were observed between the C¼O group at
d(C) 204.2 and the olefinic H-atoms at d(H) 6.08 and 6.80 (each 1 H, d, J ¼ 10.0). This
evidence suggested that compound 4 could be transformed from 3 through dehydro-
genation between C(1) and C(2). Therefore, compound 4 was characterized as 12b-
hydroxycimigenol-1-en-3-one.
Experimental Part
General. Column chromatography (CC): Silica gel (SiO2; 200 – 300 mesh, Qingdao Marine Chemical,
P. R. China); Lichroprep RP-18 (40 – 63 mm, Merck, Darmstadt, Germany), and Sephadex LH-20
(Pharmacia Fine Chemical Co. Ltd.). Fractions were monitored by TLC, and spots were visualized by
heating TLC plates sprayed with 10% H2SO4. Optical rotations: Horiba SEAP-300 spectropolarimeter.

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Helvetica Chimica Acta – Vol. 92 (2009)
Fig. 3. Key NOESY correlations of compounds 1 – 4
IR Spectra: Shimadzu IR-450 instrument; in cmꢀ1; KBr pellets. NMR Spectra: Bruker AV-400, or DRX-
500 instruments; chemical shifts (d) in ppm; Me4Si as the internal standard; J in Hz. FAB-MS and HR-
FAB-MS: VG-AUTOSPEC-3000 spectrometer; in m/z (rel. int. in % of the base peak).
Plant Material. Cimicifuga yunnanensis Hsiao rhizomes were collected from Napa lake, Xianggelila
County, Yunnan Province, China, in August 2005. The plant was identified by Prof. Bao-Gui Li,
Xishuangbanna Tropical Botanical Garden, Chinese Academy of Science. A Voucher specimen (KUN
No. 200508025) has been deposited with the State Key Laboratory of Phytochemistry and Plant
Resources in West China, Kunming Institute of Botany, Kunming, P. R. China.
Extraction and Isolation. The dried and milled rhizomes of C. yunnanensis (9 kg) were extracted with
MeOH (3 ꢁ 20 l, 2 d, each) at r.t. to give a residue (903 g) after evaporating in vacuo at 508. This residue
was suspended in H2O and then extracted successively with petroleum ether (PE), AcOEt, and BuOH.
The AcOEt extract (308 g) was chromatographed on SiO2 (CH3Cl/MeOH 1:0 ! 0 :1) to afford fractions
Fr. 1 – 4. Fr. 2 (13 g) was re-subjected to repeated CC (SiO2; CH3Cl/MeOH 60 :1 ! 40 :1, then RP-18,
MeOH/H2O 60 :40) to afford 7 [8] (1460 mg), 12 [3] (22 mg), 3 (9 mg), and 4 (12 mg). Fr. 3 (92 g) was
subjected to CC (SiO2; CH3Cl/MeOH, 30 :1 ! 10 :1) to give Fr. 3.1 – 3.3. Fr. 3.1 (13.6 g) was subjected to
CC (SiO2; CH3Cl/MeOH, 40 :1 ! 30 :1, then RP-18, MeOH/H2O 60 :40 ! 70 :30) to yield 9 [12]
(22 mg), 10 [22] (17 mg), 14 [17] (7 mg), and 2 (19 mg). Fr. 3.2 (9.8 g) was subjected to CC (RP-18;
MeOH/H2O 60 :40 ! 70 :30, then Sephadex LH-20) to afford 8 [21] (3560 mg), 19 [3] (2576 mg), and 13
[2][9][10][16] (1933 mg). Fr. 3.2 (58.9 g) was separated into Fr. 3.2.1 – 3.2.3 by CC (SiO2; CHCl3/Me2CO,
2.5 :1 to 1:2). Compound 11 [21] (20800 mg) was crystallized in MeOH from Fr. 3.2.1 (28.6 g). The
residue of Fr. 3.2.1 (mixture after filtering compound 11) was subjected to CC (RP-18; MeOH/H2O,

Helvetica Chimica Acta – Vol. 92 (2009)
119
65 :35) to yield 15 [14] (37 mg), 16 [20] (42 mg), and 1 (83 mg). Separation of Fr. 3.2.2 (5.2 g) on RP-18
gel (MeOH/H2O, 62 :38) to give 6 [25] (1673 mg) and 5 [20] (2365 mg). Compounds 17 [3] (403 mg) and
18 [4] (36 mg) were obtained from Fr. 3.2.3 (2.0 g) in a similar manner (RP-18; MeOH/H2O, 60 :40).
Acid Hydrolysis and Identification of the Sugar Moieties in Compounds 1 and 2. Compounds 1 and 2
(15 mg) were separately refluxed with 0.5n HCl (3 ml) for 2 h. Each reaction mixture was diluted with
H2O and extracted with CHCl3. The H2O layer was evaporated to dryness under reduced pressure to give
a monosaccharide, which had an Rf value (AcOEt/CHCl3/MeOH/H2O, 3 :2 :2 :1) and a specific rotation
([a]1D5 ¼ þ52.1 (c ¼ 0.16, H2O) of 1 and [a]1D5 ¼ þ24.3 (c ¼ 0.10, H2O) of 2) comparable to those of d-
xylose (Sigma – Aldrich).
Conversion of 1 to 1a. 1 (6 mg) was dissolved in MeOH (5 ml), 2% K2CO3 (5 ml) was added, and
then the soln. was stirred at r.t. overnight. The soln. was neutralized with 5% AcOH, and extracted with
AcOEt (25 ml ꢁ 3). After removal of the solvent, the residue was dissolved in THF (3 ml) and 5%
AcOH (3 ml), and heated on a boiling water bath for 3 h. After evaporation of the solvent in vacco, the
products were chromatographed over SiO2 (30 g). The fractions eluted with CHCl3/MeOH (30 :1) gave
1a (4.6 mg), which was identified by comparison of the spectral data with the reported data [12].
(3b,9b,15a,16b,23R,24R)-15,16-Dihydroxy-3-(b-d-xylopyranosyloxy)-16,23-epoxy-9,19-cyclolanost-
25-en-24-yl Acetate (1). White powder. M.p. 226 – 2288. [a]2D4 ¼ þ17.4 (c ¼ 0.10, MeOH). IR (KBr): 3433,
2941, 1709, 1632, 1044. 1H- and 13C-NMR: Table. FAB-MS (neg.): 661 ([M ꢀ H]ꢀ). HR-ESI-MS:
661.3958 ([M ꢀ H]ꢀ, C37H57O1ꢀ0 ; calc. 661.3952).
(3b,15a,23R,24S)-15-Hydroxy-25-butyl-16,23 :16,24-diepoxy-9,19-cyclolanosta-3-O-b-d-xylopyra-
noside (¼(2S,4aR,5aS,7aR,7bR,11R,12aS,13R,13aS)-11-(2-Butoxypropan-2-yl)-13-hydroxy-1,1,7a,8,13a-
pentamethyloctadecahydro-10,12a-epoxycyclopropa[1’,8a’]naphtho[2’,1’:4,5]indeno[2,1-b]oxepin-2-yl b-
d-xylopyranoside; 2). White powder. M.p. 223 – 2258. [a]2D4 ¼ þ9.5 (c ¼ 0.10, MeOH). IR (KBr): 3398,
2927, 1164, 1086, 1043. 1H- and 13C-NMR: Table. FAB-MS (neg.): 675 ([M ꢀ H]ꢀ). HR-ESI-MS:
675.3672 ([M ꢀ H]ꢀ, C39H63Oꢀ9 ; calc. 675.4472).
(12b,15a,23R,24S)-12,15,25-Trihydroxy-16,23 :16,24-diepoxy-9,19-cyclolanostan-3-one (¼(4aR,5aS,
7aR,7bR,11R,12aS,13R,13aS)-13-Hydroxy-11-(2-hydroxypropan-2-yl)-1,1,7a,8,13a-pentamethylhexade-
cahydro-10,12a-epoxycyclopropa[1’,8a’]naphtho[2’,1’:4,5]indeno[2,1-b]oxepin-2(1H)-one; 3). Colorless
1
needles. M.p. 325 – 3278. [a]2D4 ¼ þ22.5 (c ¼ 0.12, MeOH). IR (KBr): 3456, 2938, 1688, 1379, 1032. H-
and 13C-NMR: Table. FAB-MS (neg.): 501 ([M ꢀ H]ꢀ). HR-ESI-MS: 501.3217 ([M ꢀ H]ꢀ, C30H45Oꢀ6 ;
calc. 501.3216).
(12b,15a,23R,24S)-12,15,25-Trihydroxy-16,23 :16,24-diepoxy-9,19-cyclolanosta-1-en-3-one (¼(4aS,
5aS,7aR,7bR,11R,12aS,13R,13aS)-13-Hydroxy-11-(2-hydroxypropan-2-yl)-1,1,7a,8,13a-pentamethyl-
6,7,7a,7b,8,9,10,11,13,13a,13b,14,15,15a-tetradecahydro-10,12a-epoxycyclopropa[1’,8a’]naphtho[2’,1’:4,5]-
indeno[2,1-b]oxepin-2(1H)-one; 4). Colorless needles. M.p. 334 – 3368. [a]2D4 ¼ þ20.5 (c ¼ 0.10, MeOH).
IR (KBr): 3432, 2929, 1652, 1383, 1031. 1H- and 13C-NMR: Table. FAB-MS (neg.): 499 ([M ꢀ H]ꢀ). HR-
ESI-MS: 499.3055 ([M ꢀ H]ꢀ, C30H43O6ꢀ ; calc. 499.3059).
The project was supported by the National Natural Science Foundation of China (No. 30772636) and
National Science Foundation of Yunnan Province (No. 2005C0010Z), as well as the Program of
Promoting Development for Guizhou (Qian-01-2005-01) and Xibuzhiguang from CAS.
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Received June 13, 2008