Iridoids and Sesquiterpenoids from the Roots of Valeriana officinalis

Abstract

Two new iridoids, volvaltrates A and B (1 and 2), and three new sesquiterpenoids, E-(-)-3beta,4beta-epoxyvalerenal (3), E-(-)-3beta,4beta-epoxyvalerenyl acetate (4), and mononorvalerenone (5), together with five known iridoids and two known sesquiterpenoids were isolated from the roots of Valeriana officinalis. The structures and relative configurations of 1-5 were elucidated by spectroscopic evidence. Compound 1 was an unusual iridoid with an oxygen bridge connecting C-3 and C-10, forming a cage-like structure, and compound 5 was a mononorsesquiterpenoid.

Full text

Iridoids and Sesquiterpenoids from the Roots of Valeriana officinalis
Peng-Cheng Wang,
†,‡
Jiang-Miao Hu,
†
Xin-Hui Ran,
†
Zhong-Quan Chen,
†
He-Zhong Jiang,
†
Yu-Qing Liu,
†
Jun Zhou,*
,†
and
You-Xing Zhao*
,†
State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences,
Kunming 650204, People’s Republic of China, and Graduate School of the Chinese Academy of Sciences, Beijing 100039, People’s Republic of China
ReceiVed June 4, 2009
Two new iridoids, volvaltrates A and B (1and 2), and three new sesquiterpenoids, E-(-)-3β,4β-epoxyvalerenal (3),
E-(-)-3β,4β-epoxyvalerenyl acetate (4), and mononorvalerenone (5), together with five known iridoids and two known
sesquiterpenoids were isolated from the roots of Valeriana officinalis. The structures and relative configurations of 1-5
were elucidated by spectroscopic evidence. Compound 1was an unusual iridoid with an oxygen bridge connecting C-3
and C-10, forming a cage-like structure, and compound 5was a mononorsesquiterpenoid.
The genus Valeriana (Valerianaceae) comprises about 200
species and is widely distributed throughout the world.
1
Valerian
is an herb native to Europe and Asia and has been used in mild
sedatives and tranquilizers for centuries.
2
Previous phytochemical
investigations on this genus revealed the presence of iridoids,
sesquiterpenoids, flavone glycosides, ligans, and alkaloids.
3-8
Valeriana officinalis is the official species used in Europe and is
commonly referred to as valerian. Valerian is known for its
pharmacological properties, including sedative, anxiolytic, antide-
pressant, and antispasmodic activities.
9-12
A recent report has also
revealed the anti-HIV activity of valtrate as a new rev-transport
inhibitor.
13
V. officinalis is still an object of research aimed at
establishing the chemical and pharmacological basis of the activity
demonstrated in previous studies.
14
Our phytochemical investigation of the roots of V. officinalis
has led to the isolation of two new iridoids (1and 2) and three
new sesquiterpenoids (3,4, and 5), together with seven known
compounds. The known compounds were identified as IVHD-
valtrate,
15
1,5-dihydroxy-3,8-epoxyvalechlorine,
16
valeteriotriate
B,
17
jatamanvaltrate B,
18
jatamanvaltrate C,
18
valerenic acid,
4
and
acetoxyvalerenic acid
4
by comparison of their spectroscopic data
with those reported in the literature.
Compound 1was isolated as a colorless oil. Its molecular formula
was determined to be C17H24O8, with six degrees of unsaturation,
by HRESIMS (m/z379.1362 [M +Na]+). The IR spectrum
indicated the presence of OH (3448 cm-1), carbonyl (1737 cm-1),
and double-bond (1626 cm-1) groups. The 1H NMR spectrum of
compound 1showed three methyl [δH2.17 (3H, s), 0.95 (3H, d, J
)6.5 Hz), 0.94 (3H, d, J)6.5 Hz)] and two terminal olefinic
protons [δH5.39 and δH5.15 (each 1H, s)]. The 13C NMR and
DEPT data (Table 1) revealed the presence of three methyl, four
methylene, five methine, and five quaternary carbons. Comparison
of the 1D NMR and 2D NMR data with compounds reported in
the literature
16
suggested that 1had a skeleton similar to that of
1,5-dihydroxy-3,8-epoxyvalechlorine A, with an exocylic olefinic
bond at C-4 (δC149.9), an acetate group linked to C-7 (δC79.0),
and an additional isovalerate moiety. The isovalerate group was
attached to C-1 on the basis of a comparison of 1D NMR data
with those reported.
16-20
The oxygen bridge between C-3 (δC96.3)
and C-10 (δC66.7) in compound 1was different from that of 1,5-
dihydroxy-3,8-epoxyvalechlorine A, which was established by the
key HMBC correlations from H-3 (δH5.41), H-7 (δH4.95), and
H-9 (δH2.67) to C-10, and H-10 (δH4.00, 3.67) to C-9 (δC57.3),
C-8 (δC79.4), and C-3 (δC96.3) as shown in Figure 1. HMBC
correlations from H-7 (δH4.95) to C-1′′′′ (δC170.9) and H-11 (δH
5.15) to C-3 and 1H-1H COSY cross-peaks of H-6/H-7 and H-1/
H-9 further supported this presumption. Finally, the two oxygenated
groups were adjacent to C-5 (δC74.4) and C-8 (δC79.4) as
established by 1D and 2D NMR analyses.
The relative configuration of 1was elucidated by a ROESY
experiment and by comparison of the NMR data with those reported
for valepotriates. Comparing NMR data indicated that the 5-OH
and H-9 were both β-oriented.
3,16-20
H-1should be R-oriented since
all the naturally occurring valepotriates exhibit R-orientation.
3,16-20
The key ROESY correlations of H-10b/H-1 and H-10a/H-7, as
shown in the molecular model (Figure 2), indicated β-orientation
of 8-OH and R-orientation of H-7. No correlations were observed
between H-7 and H-9 and between H-9 and H-10. The R-orientation
of C-10 was confirmed by NOEs between H-1/H-10b and between
H-7/H-10a in 1D NOE experiments. Thus, the structure of 1was
determined, and it was named volvatrate A.
Compound 2possessed a molecular formula of C27H41O11Cl as
established by HRESIMS (m/z599.2243 [M +Na]+). The IR
spectrum had absorption bands at 3447 cm-1(OH), 1742 cm-1
(CdO), and 1638 cm-1(CdC). The 1H and 13C NMR spectra
(Table 1) had signals that were characteristic of valepotriates.
3,16-20
The signals at δH6.56 and δC89.3 were assigned to H-1 and C-1
attached to two oxygen atoms. The two olefinic carbons at δC144.7
(CH) and 112.8 (qC) were assigned to C-3 and C-4 as in usual
iridoid compounds. Comparison of the NMR data (Table 1) with
jatamanvaltrate B showed that compound 2had a similar skeleton,
except for a downfield shift of δC49.7 (C-10, ∆)-17.6 ppm),
17
which suggested that C-10 was connected with a polar atom.
19
The
presence of a chlorine atom was confirmed by HRESIMS and the
appearance of a [M +Na +2]+ion peak at 601 due to the chlorine
isotopes present in the ESI mass spectrum. Further analysis of its
1H and 13C NMR data and comparison with those of the reported
valpotriates indicated the presence of an acetate, an isovalerate
group, and an isovaleroyloxyisovaleryl moiety in the molecule.
3,16-20
The correlations from H-2′(δH4.77) to C-1′′ (δC173.2) and C-1′
(δC169.9) in the HMBC spectrum supported the presence of an
isovaleroyloxyisovaleryl moiety in 2. Attachments of acyloxy
* To whom correspondence should be addressed. Tel.: +86-871-5223264.
Fax: +86-871-5223261. E-mail: yxzhao@mail.kib.ac.cn.
†
Kunming Institute of Botany.
‡
Graduate School of the Chinese Academy of Sciences.
J. Nat. Prod. XXXX, xxx, 000 A
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substituents to the iridoid nucleus were assigned by the HMBC
correlations as shown in Figure 1. The isovalerate group was
attached to C-1 by the HMBC correlation from H-1 (δH6.56) to
C-1′′′ (δC170.7). The acetate group linked to C-7 and the
isovaleroyloxyisovaleryl moiety to C-11 were established by the
HMBC correlations from H-7 (δH4.97) to C-1′′′′ (δC170.6) and
from H-11 (δH4.90, 4.67) to C-1′(δC169.9), respectively. The
relative configurations of 2at C-1, C-5, C-7, C-8, and C-9 were
the same as those in compound 1, which were determined by the
key ROESY correlations of H-1/H-10 and H-10/H-7 as shown in
Figure 2. Thus, the structure of compound 2was established, and
it was named volvatrate B.
Compounds 3,4, and 5were obtained as colorless oils from the
petroleum ether extract. The molecular formula of 3was deduced
as C15H22O2by HRESIMS (m/z257.1524 [M +Na]+). The 13C
NMR and DEPT spectra of 3(Table 2) showed a total of 15 carbon
signals, including three methyl, four methlene, five methine, and
three quaternary carbons, indicating a valerenane sesquiterpenoid
skeleton, often reported in this plant.
4
The IR spectrum revealed
the presence of a conjugated group consisting of an aldehyde
function (1688 cm-1) and a double bond (1640 cm-1), which was
confirmed by the HMBC correlation from H-14 (δH9.45) to C-11
(δC153.7) and C-12 (δC140.2). Comparison of the NMR
spectroscopic data with those reported for valerenal
4
indicated that
3had a structure similar to that of valerenal, except for upfield
shifts of C-3 (δC70.4) and C-4 (δC71.2) in 3. This suggested that
the double bond between C-3 and C-4 in valerenal was a 3,4-epoxy
analogue in 3, similar to that in (-)-3β,4β-epoxyvalerenic acid.
21
HMBC correlations (Figure 1) from H-10 (δH1.43) to C-3 and
C-4 confirmed the 3,4-epoxy group in 3. The HMBC correlations
from H-11 (δH6.87) to C-4, C-5 (δC34.7), C-6 (δC24.3), and
C-14 (δC195.4) and correlations from H-5 (δH2.76) to C-11 and
C-12 indicated that the R,β-unsaturated aldehyde function was
attached to C-5 as in valerenal. The relative configuration of 3was
elucidated by the ROESY experiment and comparison with other
naturally occurring valerenane sesquiterpenoids possessing a β-ori-
entation of H-9 and H-8 and an R-orientation of H-5.
4,21
The
orientations were further confirmed by ROESY correlations of H-8/
H-9 and H-9/H-11 (Figure 2). The ROESY correlations of H-5 with
H-10 established the R-orientation of 10-CH3, and H-11 with H-14
(δH9.45) indicated the Econfiguration of the double bond between
C-11 and C-12. The specific rotation was negative ([R]20D-83.3,
c0.25, MeOH). Therefore, compound 3was determined to be
E-(-)-3β,4β-epoxyvalerenal.
The molecular formula of compound 4was determined as
C17H26O3by HRESIMS. The IR spectrum indicated the presence
of a carbonyl (1740 cm-1) and a double bond (1628 cm-1). The
Table 1. NMR Data
a
for Volvatrate A (1) and Volvatrate B (2) in CDCl3
volvatrate A (1) volvatrate B (2)
position δC, mult δH(Jin Hz) δC, mult δH(Jin Hz)
1 91.2, CH 6.56, d (2.2) 89.3, CH 6.56, s
3 96.3, CH 5.41, s 144.7, CH 6.60, s
4 149.9, qC 112.8, qC
5 74.4, qC 70.1, qC
6a (β-H) 47.1, CH22.28, d (16.0) 40.7, CH22.07, m
6b (R-H) 2.60, dd (16.0, 6.6) 2.60, dd (13.6, 6.1)
7 79.0, CH 4.95, t (6.4) 79.7, CH 4.97, t (7.0)
8 79.4, qC 70.1, qC
9 57.3, CH 2.67, s 54.1, CH 2.71, s
10a 66.7, CH23.67, 1H, AB, (12.3) 49.7, CH23.67, 1H, AB (11.5)
10b 4.00, 1H, AB, (12.3) 3.73, 1H, AB (11.5)
11a 110.5, CH25.15, s 61.9, CH24.67, 1H, AB (12.4)
11b 5.39, s 4.90, 1H, AB (12.4)
1′169.9, qC
2′76.7, CH 4.77, d (4.8)
3′29.8, CH 2.22, m
4′17.3, CH31.00, d (6.6)
5′18.6, CH30.99, d (6.6)
1′′ 173.2, qC
2′′ 43.0,
e
CH22.24,
i
m
3′′ 25.6,
h
CH 2.07,
j
m
4′′ 22.3,
f
CH30.96,
k
d, (6.6)
5′′ 22.3,
f
CH30.96,
k
s, (6.6)
1′′′ 170.9,
b-k
qC 170.7,
g
qC
2′′′ 43.3, CH22.19, m 43.0,
e
CH22.24,
i
m
3′′′ 25.7, CH 2.05, m 25.7,
h
CH 2.07,
j
m
4′′′ 22.3,
c
CH30.96,
d
d (6.5) 22.4,
f
CH30.95,
k
d, (6.6)
5′′′ 22.3,
c
CH30.94,
d
d (6.5) 22.4,
f
CH30.95,
k
d, (6.6)
1′′′′ 170.9,
b-k
qC 170.6,
g
qC
2′′′′ 21.1, CH32.17, s 20.8, CH32.09, s
a
1H NMR at 500 MHz, 13C NMR at 125 MHz, and multiplicities inferred from DEPT and HSQC experiments.
b-k
Assignments bearing the same
superscript may be interchanged in each column.
Figure 1. Key HMBC correlations for 1-5.
BJournal of Natural Products,XXXX, Vol. xxx, No. xx Notes
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13C NMR and DEPT spectra of 4(Table 2) indicated that the
molecule contained four methyl, five methlene, four methine, and
four quaternary carbons. The 1H NMR spectrum showed four
methyl groups (δH1.40, 1.67, 0.85, 2.07) and an olefinic methine
(δH5.89). The 1H and 13C NMR spectra of 4were similar to those
of 3except that the aldehydic function (δC195.4) in 3was replaced
by a -CH2OOCCH3(δC70.3, 171.0, 21.0) group in 4, which was
confirmed by the HMBC correlations from H-14 (δH4.49) to C-16
(δC171.0), C-11 (δC129.2), C-12 (δC131.3), and C-13 (δC14.3).
The relative configuration of 4was consistent with that of 3.
ROESY correlation of H-11 (δH5.89) with H-14 (δH4.49)
established the Econfiguration of the double bond at C-11 and
C-12. The optical activity of 4was negative; thus, compound 4
was identified as E-(-)-3β,4β-epoxyvalerenyl acetate.
Compound 5had the molecular formula C14H22O2, by HRESIMS,
with 4 degrees of unsaturation. The 13C NMR and DEPT spectra
(Table 2) showed only14 carbon signals in accordance with the
HRESIMS, including three methyl, five methylene, three methine,
and three quaternary carbons. The NMR spectra of 5were similar
to those of 3and 4except that the side chain at C-5 only had three
carbons in 5. The five methylene signals were assigned to C-1,
C-2, C-6, C-7, and C-11, respectively, and the two quaternary
carbon signals were assigned to C-3 and C-4 by comparison of
the 1D NMR and 2D NMR spectra with those of 3and 4. The
appearance of a quaternary carbon at δC208.3 (C-12) revealed the
presence of a ketonic carbonyl in the molecule, which was
confirmed by the IR absorption at 1714 cm-1. HMBC correlations
from H-13 (δH2.16) to C-12 and C-11 (δC43.7) and from H-11
(δH2.70) to C-12, C-4 (δC72.0), C-5 (δC30.4), and C-6 (δC22.6)
indicated that there was a -CH2COCH3group attached to C-5.
The two methyl groups were attached to C-3 and C-8, respectively,
which was established by the HMBC correlations from H-10 (δH
1.38) to C-3 and C-2 (δC32.8) and from H-14 (δH0.81) to C-7
(δC26.6), C-8 (δC32.7), and C-9 (δC40.9). H-H COSY
correlations of H-1/H-2, H-6/H-7, H-8/H-9, H-9/H-1, and H-8/H-
14 confirmed the carbon linkages in the molecule. The relative
configuration of 5was also consistent with 3and 4, which was
supported by a ROESY experiment. The ROESY correlations of
H-9/H-11 and H-5/H-14 verified the R-orientation of H-5 and
β-orientation of H-8 as shown in Figure 2. The 10-CH3was
determined to be R-oriented by comparison of the NMR data with
compounds 3,4, and (-)-3β,4β-epoxyvalerenic acid.
21
Thus, the
structure of 5was assigned, and it was named mononorvalerenone.
Experimental Section
General Experimental Procedures. Optical rotations were taken
on a Horiba SEAP-300 polarimeter. UV spectra were obtained on a
Hitachi UV 210A spectrophotometer. IR spectra were measured with
a Bio-Rad FTS-135 spectrometer with KBr pellets. Mass spectra were
obtained on a VG Auto Spec-3000 mass spectrometer (VG, Manchester,
England). 1D and 2D NMR spectra were recorded on a Bruker AM-
400 or a DRX-500 NMR spectrometer (Karlsruhe, Germany). Semi-
preparative HPLC were performed on an Agilent 1100 liquid chro-
matograph with a Zorbax SB-C18 (9.4 mm ×25 cm) column. Column
chromatography was performed either on silica gel (200-300 mesh,
Figure 2. Key ROESY correlations for 1-3and 5.
Table 2. NMR Data
a
for Compounds 3-5in CDCl3
compound 3compound 4compound 5
position δC, mult δH(Jin Hz) δC, mult δH(Jin Hz) δC, mult δH(Jin Hz)
1a 23.9, CH21.35, m 23.9, CH21.27, m 23.9, CH21.49, m
1b 1.60, m 1.59, m 1.76, m
2a 32.7, CH21.63, m 32.9, CH21.62, m 32.8, CH21.60, m
2b 1.86, m 1.84, m 1.82, m
3 70.4, qC 70.3, qC 71.8, qC
4 71.2, qC 72.1, qC 72.0, qC
5 34.7, CH 2.76, m 33.3, CH 2.50, m 30.4, CH 1.25, m
6a 24.3, CH21.64, m 24.9, CH21.53, m 23.6, CH21.27, m
6b 1.96, m 1.83, m 1.53, m
7a 27.5, CH21.45, m 27.1, CH21.36, m 26.6, CH21.33, m
7b 1.80, m 1.79, m 1.68, m
8 32.7, CH 2.09, m 32.9, CH 2.06, m 32.7, CH 1.99, m
9 41.0, CH 2.45, t, (7.5) 40.9, CH 2.36, t (7.4) 40.9, CH 2.25, m
10 15.2, CH31.43, s 5.2, CH31.40, s 15.0, CH31.38, s
11 153.7, CH 6.87, d (9.4) 129.2,CH 5.89, d (9.2) 43.7, CH22.70, d, (7.0)
12 140.2, qC 131.3, qC 208.3, qC
13 9.5, CH31.77, s 14.3, CH31.67, s 30.1, CH32.16, s
14 195.4, CH 9.45, s 70.3, CH24.49, dd (15.6, 12.2) 13.8, CH30.81, d, (7.3)
15 13.8, CH30.89, d (7.3) 14.0, CH30.85, d, (7.2)
16 171.0, qC
17 21.0, CH32.07, s
a
1H NMR at 400 MHz, 13C NMR at 100 MHz, and multiplicities inferred from DEPT and HSQC experiments.
Notes Journal of Natural Products,XXXX, Vol. xxx, No. xx C
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Qindao Marine Chemical Inc., Qingdao, People’s Republic of China)
or RP-18 gel (LiChroprep, 40-63 µm, Merck, Darmstadt, Germany).
Sephadex LH-20 for chromatography was purchased from Amersham
Biosciences. Fractions were monitored by TLC, and spots were
visualized by heating silica gel plates sprayed with 10% H2SO4in EtOH.
Plant Material. The plant, cultivated from the seeds of V. officinalis
(purchased from Germany) at Songhuaba in Kunming, Yunnan
Province, P. R.China, in March 2007, was collected in January 2008
and identified as V. officinalis Linn. by Prof. Hu-Biao Chen, School of
Pharmaceutical Sciences, Peking University, P. R. China. A voucher
specimen (KIB-XC0701) was preserved at the State Key Laboratory
of Phytochemistry and Plant Resources in West China, Kunming
Institute of Botany, the Chinese Academy of Sciences, P. R. China.
Extraction and Isolation. Dried root powder of V. officinalis (5
kg) was extracted with 95% EtOH at room temperature to give a residue
(1 kg) after removal of solvent under reduced pressure. The EtOH
extract was suspended in H2O (3 L) and then partitioned successively
with petroleum ether (3 ×2 L), EtOAc (3 ×2 L), and n-BuOH (3 ×
2 L). The petroleum ether extract (106 g) was subjected to silica gel
column chromatography (CC) eluted with petroleum ether-acetone
(from 100:1 to 1:1) to afford fractions A-H. Fraction B (15 g) was
subjected to CC over silica gel (200-300 mesh) eluted with petroleum
ether-EtOAc (from 50:1 to 1:1) to give four fractions, Ba-Bd.
Valerenic acid (387 mg) was crystallized from a Me2CO solution of
fraction Ba. Fraction Bb was chromatographed over a Sephadex LH-
20 column, using CHCl3-MeOH (1:1) as solvent, and then purified
by semipreparative HPLC (CH3CN-H2O, 40:60) to yield 3(5 mg), 4
(8 mg), and 5(5 mg). Fraction C (5 g) was subjected to CC over silica
gel eluted with petroleum ether-EtOAc (10:1 to 1:1) to afford three
fractions, Ca-Cc. Fraction Ca was chromatographed over an RP-18
column eluted with a MeOH-H2O gradient system (60%-100%) to
afford acetoxyvalerenic acid (50 mg). The EtOAc extract (80 g) was
subjected to CC over silica gel eluted with petroleum ether-EtOAc
(from 50:1 to 1:1) to give six fractions, Fr1-Fr6. Fraction 3 was
chromatographed over silica gel eluted with petroleum ether-EtOAc
(from 10:1 to 1:1) to afford four fractions, Fr3a-Fr3d. Fr3a was purified
over a Sephadex LH-20 column eluted with CHCl3-MeOH (1:1) to
obtain IVHD-valtrate (180 mg). Fr3b was purified by a RP-18 column
eluted with a MeOH-H2O gradient system (50%-100%) and repeated
chromatography over silica gel using petroleum ether-EtOAc (5:1 to
1:1) and then chromatographed over a Sephadex LH-20 column eluted
with CHCl3-MeOH (1:1) and purified by semipreparative HPLC
(CH3CN-H2O, 35:65) to afford 1(3 mg), 2(7 mg), 1,5-dihydroxy-
3,8-epoxyvalechlorine (38 mg), valeteriotriate B (8 mg), jatamanvaltrate
B (6 mg), and jatamanvaltrate C (12 mg).
Volvatrate A (1): colorless oil; [R]20D-34.9 (c0.18, CH3OH); IR
(KBr) νmax 3448, 2961, 2874, 1737, 1626, 1374, 1248, 1104 cm-1;1H
NMR (CDCl3, 500 MHz) and 13C NMR (CDCl3, 125 MHz) data, see
Table 1; ESIMS m/z379 [M +Na]+; HRESIMS m/z379.1362 [M +
Na]+(calcd for C17H24O8Na, 379.1368).
Volvatrate B (2): colorless oil; [R]20D-72.3 (c0.30, CHCl3); IR
(KBr) νmax 3447, 2965, 2926, 1742, 1638, 1374, 1242 cm-1;1H NMR
(CDCl3, 500 MHz) and 13C NMR (CDCl3, 125 MHz) data, see Table
1; positive ESIMS m/z599 [M +Na]+; HRESIMS m/z599.2243 [M
+Na]+(calcd for C27H41O11ClNa, 599.2235).
E-(-)-3β,4β-Epoxyvalerenal (3): colorless oil; [R]20D-83.3 (c0.25,
MeOH); IR (KBr) νmax 2931, 1688, 1640, 1422, 1107 cm-1;1H NMR
(CDCl3, 400 MHz) and 13C NMR (CDCl3, 100 MHz) data, see Table
2; positive ESIMS m/z257 [M +Na]+; HRESIMS m/z257.1524 [M
+Na]+(calcd for C15H22O2Na, 257.1517).
E-(-)-3β,4β-Epoxyvalerenyl acetate (4): colorless oil; [R]20D
-52.63 (c0.19, MeOH); IR (KBr) νmax 3070, 2929, 1740, 1628, 1456,
1379, 1290, 1235, 1047, 1024, 959 cm-1;1H NMR (CDCl3, 400 MHz)
and 13C NMR (CDCl3, 100 MHz) data, see Table 2; positive ESIMS
m/z301 [M +Na]+; HRESIMS m/z301.1773 (calcd for C17H26O3Na
301.1779).
Mononorvalerenone (5): colorless oil; [R]20D-39.29 (c0.28.
MeOH); IR (KBr) νmax 2926, 2861, 1714, 1454, 1385, 1284, 1084 cm-1;
1H NMR (CDCl3, 500 MHz) and 13C NMR (CDCl3, 125 MHz) data,
see Table 2; positive ESIMS m/z245 [M +Na]+; HRESIMS m/z
245.1511 (calcd for C17H26O3Na 245.1517).
Acknowledgment. This work was supported by the fund (P2008-
ZZ22) of State Key Laboratory of Phytochemistry and Plant Resources
in West China and Natural Science Foundation of Yunnan (2008CD159).
The authors thank Dr. X.-H. Cai for initial proofreading of the document
and the members of the analytical group of the State Key Laboratory
of Phytochemistry and Plant Resources in West China, Kunming
Institute of Botany, for the spectral measurements.
Supporting Information Available: 1D and 2D NMR spectra of
compounds 1-5. This material is available free of charge via the
Internet at http://pubs.acs.org.
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NP9003382
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