Absolute stereostructures of polypodane-type triterpenes, myrrhanol a and myrrhanone A, from guggul-gum resin (the resin of Balsamodendron mukul)

Article abstract of DOI:10.1248/cpb.52.1200

Two new polypodane-type triterpenes, myrrhanol A and myrrhanone A, were isolated from the 50% aqueous methanolic extract of guggul-gum resin [the resin of Balsamodendron (=Commiphora) mukul HOOK.]. The structures of the new constituents, including their a

Full text of DOI:10.1248/cpb.52.1200

1
200
Chem. Pharm. Bull. 52(10) 1200—1203 (2004)
Vol. 52, No. 10
Absolute Stereostructures of Polypodane-Type Triterpenes, Myrrhanol A
and Myrrhanone A, from Guggul-Gum Resin (the Resin of
Balsamodendron mukul)
a
a
a
a
a
Hisashi MATSUDA, Toshio MORIKAWA, Shin ANDO, Hideo OOMINAMI, Toshiyuki MURAKAMI,
b
,a
Ikuko KIMURA, and Masayuki YOSHIKAWA*
a
b
Kyoto Pharmaceutical University; Misasagi, Yamashina-ku, Kyoto 607–8412, Japan: and Department of Clinical
Pharmacology, Graduate School of Clinical Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University;
2
630 Sugitani, Toyama 930–0194, Japan. Received May 24, 2004; accepted July 2, 2004
Two new polypodane-type triterpenes, myrrhanol A and myrrhanone A, were isolated from the 50% aque-
ous methanolic extract of guggul-gum resin [the resin of Balsamodendron (ꢀCommiphora) mukul HOOK.]. The
structures of the new constituents, including their absolute configurations, were determined on the basis of
chemical and physicochemical evidence.
Key words Balsamodendron mukul; myrrhanol; myrrhanone; polypodane-type triterpene; guggul-gum; Ayurvedic traditional
medicine
Guggul-gum resin [the resin of Balsamodendron (ꢀCom- tion was subjected to normal and reversed phase silica gel
miphora) mukul HOOK. (Burseraceae)] is produced by drying column chromatographies, and finally HPLC, to give two
7)
the milky-white sap of the tree (15—20 years old) for one new polypodane-type triterpenes, myrrhanol A (1, 0.036%)
7)
year. This natural medicine is prescribed in the form of direct and myrrhanone A (2, 0.026%), together with four poly-
8)
mixtures with powders or extracts of other natural medicines podane-type triterpenes, myrrhanol B (3, 0.0025%),
8)
for use as anti-obesity, antiinflammatory, antibacterial, anti- myrrhanone B (4, 0.013%), (8R)-3b,8-dihydroxypolypoda-
8)
coagulant, and anti-atherosclerosis agents in Ayurvedic folk 13E,17E,21-triene (5, 0.0084%), and (8R)-3-oxo-8-hydrox-
8)
medicine in India. Previously, the antiinflammatory activity ypolypoda-13E,17E,21-triene (6, 0.0037%) and a lignan,
1
—3)
8)
of guggul has been reported,
stituent of guggul, activates lipolytic enzymes, inhibits he-
patic cholesterol biosynthesis, and reduces the total serum Myrrhanone A (2) Myrrhanol A (1) was isolated as a col-
and guggulsterone, a con- (ꢁ)-diayangambin (7, 0.0007%).
Absolute Stereostructures of Myrrhanol A (1) and
4,5)
27
lipid and total serum cholesterol levels. A similar natural orless oil with positive optical rotation ([a]D ꢁ12.2°). In the
medicine, myrrh [the resin of Balsamodendron (or Com- positive-ion fast atom bombardment (FAB)-MS of 1, a quasi-
miphora) myrrha NEES] was used by the Egyptians for em- molecular ion peak was observed at m/z 483 (MꢁNa) , and
ꢁ
balming, and by the Jews as an anointing oil. The sesquiter- the molecular formula C H O was determined by high-res-
3
0
52
3
pene constituents isolated from myrrh, furanoeudesma-1,3- olution MS measurement. The IR spectrum of 1 showed ab-
ꢂ1
diene and curzarene, have analgesic effects that are blocked sorption bands at 3432 and 1670 cm , suggestive of hy-
1
13
by naloxone, explaining the use of myrrh as a painkiller in droxyl and olefin functions. The H-NMR (CDCl ) and C-
3
6)
ancient times. However, because of its toxicity, myrrh is not NMR (Table 1) spectra of 1, which were assigned by various
27)
used in medicines today, except as a mouthwash in India.
NMR experiments, showed a presence of seven tertiary
In the course of our characterization studies on traditional methyls [d 0.75, 0.79, 0.98, 1.13, 1.65 (s, 24, 25, 23, 26, 29-
7—26)
Ayurvedic medicines,
we found that the 50% aqueous H ), 1.60 (s, 27, 28-H )], a methine bearing an oxygen func-
3 3
methanolic extract of guggul (the resin of B. mukul) showed tion [d 3.21 (dd, Jꢀ4.9, 11.6 Hz, 3-H)], a methylene bearing
an anti-inflammatory effect on adjuvant-induced air pouch an oxygen function [d 3.96 (s, 30-H )], and three trisubsti-
2
granuloma in mice. From the extract, two new polypodane- tuted olefins [d 5.12 (dd, Jꢀ5.8, 6.7 Hz, 17-H), 5.16, 5.38
type triterpenes, myrrhanol A (1) and myrrhanone A (2), (dd-like, 13, 21-H)], together with a quaternary carbon bear-
7
)
were isolated as the active components. Furthermore, the ing an oxygen function (d 73.9, C-8). The planar structure
C
1
1
methanolic extract of this natural medicine was found to ex- of 1 was constructed on the basis of H– H correlation spec-
hibit an inhibitory effect on nitric oxide production in troscopy ( H– H COSY) and heteronuclear multiple bond
lipopolysaccharide-activated mouse peritoneal macrophages. correlation (HMBC) experiments, as shown in Fig. 1. Thus,
From the methanolic extract, we isolated three polypodane- the H– H COSY experiment indicated the presence of par-
type triterpenes named myrrhanol B (3), myrrhanones B (4), tial structures in bold lines (from C-1–C-3, from C-5–C-7,
and A acetate, and an octanordammarane-type triterpene from C-9–C-11–C-13, and so on). In the HMBC experiment
termed epimansumbinol, together with 17 known constitu- of 1, long-range correlations were observed between the fol-
1
1
1
1
8)
ents. This paper presents a full account of the isolation and lowing protons and carbons: 21-H and 30-C; 23-H and 3, 4,
3
characterization of myrrhanol A (1) and myrrhanone A (2).
5, 24-C; 24-H and 3, 4, 5, 23-C; 25-H and 1, 5, 9, 10-C; 26-
3 3
The 50% aqueous methanolic extract (5.68% from natural H and 7, 8, 9-C; 27-H and 13, 14, 15-C; 28-H and 17, 18,
3
3
3
medicine) of the resin of guggul-gum was partitioned in an 19-C; 29-H and 21, 22, 30-C; 30-H and 21-C, so that the
3
2
ethyl acetate (EtOAc) and water mixture to furnish the connectivities of all carbons in 1 were identified. Further-
EtOAc- and H O-soluble fractions. The EtOAc-soluble frac- more, the relative stereostructure of 1 was characterized by a
2
*
To whom correspondence should be addressed. e-mail: shoyaku@mb.kyoto-phu.ac.jp
© 2004 Pharmaceutical Society of Japan

October 2004
1201
Chart 1
1
1
Fig. 1. H– H COSY, HMBC, and NOESY Experiments of 1 and 2
Fig. 2
nuclear Overhauser enhancement spectroscopy (NOESY) ex- the basis of this evidence, the absolute stereostructure of
periment, which showed NOE correlations between the fol- myrrhanol A was determined to be (3S,5R,8R,9R,10S)-
2
9)
lowing protons: 3-H and 5-H, 23-H ; 5-H and 9-H; 12-H
3,8,30-trihydroxypolypoda-13E,17E,21E-triene (1).
Myrrhanone A (2) was also obtained as a colorless oil
3
2
and 27-H ; 16-H and 28-H ; 20-H and 29-H ; 21-H and 30-
3
2
3
2
3
2
8
H ; 24-H and 25-H ; 25-H and 26-H (Fig. 1).
with positive optical rotation ([a] ꢁ11.9°), and its IR spec-
2
3
3
3
3
D
Next, the absolute configuration of 1 was determined by trum showed absorption bands due to hydroxyl, carbonyl,
28)
ꢂ1
application of modified Mosher's method. Namely, 1 was and olefin functions at 3453, 1709, and 1650 cm . In the
treated with (R)- and (S)-a-methoxy-a-trifluoromethyl- positive-ion FAB-MS of 2, a quasimolecular ion peak was
ꢁ
phenylacetic acid (MTPA) in the presence of 1-ethyl-3-(3-di- observed at m/z 481 (MꢁNa) , and the molecular formula
methylaminopropyl)carbodiimide hydrochloride (EDC·HCl) C H O was determined by high-resolution MS measure-
3
0
50
3
1
and 4-dimethylaminopyridine (4-DMAP) to give the 3,30-di- ment. The proton and carbon signals in the H-NMR (CDCl )
R)-MTPA ester (1a) and the 3,30-di-(S)-MTPA ester (1b), and C-NMR (Table 1) spectra of 2 showed signals assign-
3
1
3
27)
(
respectively. As shown in Fig. 2, the proton signals attached able to seven tertiary methyls [d 0.95, 1.02, 1.09, 1.19, 1.65
at the 1, 2, and 25-positions in 1b were observed at higher (3H each, all s, 25, 24, 23, 26, 29-H ), 1.60 (6H, s, 27, 28-
3
fields compared to those of 1a (Dd: negative), while the sig- H )], a methylene bearing an oxygen function [d 3.96 (2H, s,
3
nal due to the 23 and 24-positions in 1b were observed at 30-H )], and three trisubstituted olefins [d 5.12, 5.16, 5.39
2
lower fields as compared to those of 1a (Dd: positive). On (1H each, all dd-like, 17, 13, 21-H)] together with a quater-

1
202
Vol. 52, No. 10
13
Table 1.
C-NMR Data of Myrrhanol A (1) and Myrrhanone A (2)
pressure provided the 50% aqueous methanolic extract (105 g, 5.68%). The
aqueous methanolic extract (96.8 g) was partitioned in an EtOAc–H O (1 : 1,
2
1
2
v/v) mixture. Removal of the solvent from the EtOAc- and H O-soluble frac-
tions under reduced pressure yielded an EtOAc-soluble fraction (34.0 g,
2
C-1
C-2
C-3
C-4
C-5
C-6
C-7
C-8
37.9
27.0
78.6
38.8
55.0
20.2
44.3
73.9
61.1
38.8
25.5
31.3
125.1
135.0
39.6
26.5
124.5
134.6
39.3
26.1
125.7
134.7
28.1
15.4
15.5
23.7
16.2
16.0
13.7
68.6
38.3
33.9
217.0
47.4
55.1
21.3
43.7
73.6
60.3
38.5
25.8
31.2
124.8
135.1
39.6
26.5
124.4
134.6
39.3
26.1
125.7
134.6
26.3
21.3
14.8
23.5
16.2
16.0
13.7
68.6
2.00%) and H O-soluble fraction (62.8 g, 3.68%), respectively.
Normal-phase silica gel column chromatography [BW-200 (Fuji Silysia
Chemical, Ltd., 1 kg), n-hexane–EtOAc (3 : 1Æ1 : 1, v/v)ÆCHCl –MeOH
(10 : 1, v/v)ÆMeOH] of the EtOAc-soluble extract (29.0 g) gave nine frac-
tions [Fr. 1 (1.51 g), 2 (1.13 g), 3 (5.22 g), 4 (4.50 g), 5 (3.60 g), 6 (3.20 g), 7
(4.80 g), 8 (3.80 g), 9 (1.24 g)]. Fraction 2 (1.10 g) was purified by
2
3
reversed-phase silica gel column chromatography [30 g, MeOH–H O
2
(80 : 20Æ90 : 10, v/v)ÆMeOH] and HPLC [MeOH–H O (90 : 10, v/v)] to
2
C-9
give (8R)-3b,8-dihydroxypolypoda-13E,17E,21-triene (5, 118 mg, 0.0084%)
and (8R)-3-oxo-8-hydroxypolypoda-13E,17E,21-triene (6, 52 mg, 0.0037%).
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
Fraction 4 (1.00 g) was purified by HPLC [MeOH–H O (90 : 10, v/v)] to
2
give myrrhanone A (2, 84 mg, 0.026%). Fraction 5 (3.60 g) was separated by
reversed-phase silica gel column chromatography [100 g, MeOH–H O
2
(70 : 30Æ80 : 20, v/v)ÆMeOH] and HPLC [MeOH–H O (85 : 15, v/v)] to
2
give myrrhanol A (1, 523 mg, 0.036%). Fraction 6 (3.20 g) was separated by
reversed-phase silica gel column chromatography [100 g, MeOH–H O
2
(90 : 10, v/v)ÆMeOH] and HPLC [MeOH–H O (75 : 25, v/v)] to give
2
myrrhanol B (3, 36 mg, 0.0025%), myrrhanone B (4, 187 mg, 0.013%), and
(ꢁ)-diayangambin (7, 10 mg, 0.0007%). The known compounds (3—7)
1
were identified by comparison of their physical data ([a] , IR, H-NMR,
D
1
3
8)
C-NMR) with those of authentic samples.
2
7
Myrrhanol A (1): Colorless oil, [a]D ꢁ12.2° (cꢀ1.00, MeOH). High-res-
olution positive-ion FAB-MS: Calcd for C H O Na (MꢁNa) : 483.3814.
ꢁ
3
0
52
3
ꢂ1
1
Found: 483.3830. IR (KBr): 3432, 2936, 1670, 1461, 1387, 1087 cm . H-
NMR (500 MHz, CDCl ) d: 0.75, 0.79, 0.98, 1.13, 1.65 (3H each, all s, 24,
3
25, 23, 26, 29-H ), 0.88 (1H, dd, Jꢀ2.1, 9.5 Hz, 5-H), 1.02 (1H, dd, Jꢀ3.9,
3
3.9 Hz, 9-H), 1.13, 1.70 (1H each, both m, 1-H ), 1.27, 1.45 (1H each, both
2
m, 11-H ), 1.32, 1.65 (1H each, both m, 6-H ), 1.32, 1.87 (1H each, both m,
2
2
7-H ), 1.60 (6H, s, 27, 28-H ), 2.00 (4H, m, 15, 19-H ), 2.08 (4H, m, 12, 16-
2
3
2
H ), 2.12 (2H, m, 20-H ), 3.21 (1H, dd, Jꢀ4.9, 11.6 Hz, 3-H), 3.96 (2H, s,
2
2
3
0-H ), 5.12 (1H, dd, Jꢀ5.8, 6.7 Hz, 17-H), 5.16, 5.38 (1H each, both dd-
2
1
3
1
25 MHz, CDCl3.
like, 13, 21-H). C-NMR (125 MHz, CDCl ) d : given in Table 1. Positive-
3 C
ꢁ
ion FAB-MS: m/z 483 (MꢁNa) .
Myrrhanone A (2): Colorless oil, [a] ꢁ11.9° (cꢀ1.00, MeOH). High-
2
8
D
ꢁ
nary carbon bearing an oxygen function (d 73.6, C-8) and resolution positive-ion FAB-MS: Calcd for
C
H
O
Na (MꢁNa) :
C
30
50
3
4
1
81.3658. Found: 481.3669. IR (KBr): 3453, 2930, 1709, 1650, 1456, 1385,
080 cm . H-NMR (500 MHz, CDCl ) d: 0.95, 1.02, 1.09, 1.19, 1.65 (3H
carbonyl carbon (d 217.0, C-3), which were found to be su-
perimposable on those of 1, except for the signal due to the
carbonyl group. In the HMBC experiment of 2, long-range
C
ꢂ1 1
3
each, all s, 25, 24, 23, 26, 29-H ), 1.13 (1H, dd, Jꢀ4.0, 4.0 Hz, 9-H), 1.30,
3
1
.52 (1H each, both m, 11-H ), 1.37, 1.60 (1H each, both m, 6-H ), 1.46
2
2
correlations were observed between the 23,24-methyl pro- (1H, m, 5-H), 1.46, 1.90 (1H each, both m, 7-H ), 1.52, 1.90 (1H each, both
2
tons and 3-carbonyl carbon (Fig. 1). In addition, reduction of m, 1-H
), 1.60 (6H, s, 27, 28-H
), 2.00 (4H, m, 15, 19-H ), 2.10 (6H, m, 12,
3 2
2
1
5
6, 20-H ), 2.40, 2.60 (1H each, both m, 2-H ), 3.96 (2H, s, 30-H ), 5.12,
2
with sodium borohydride (NaBH ) yielded 1, so that the
2
2
2
4
13
.16, 5.39 (1H each, all dd-like, 17, 13, 21-H). C-NMR (125 MHz, CDCl )
3
absolute stereostructure of myrrhanone A was determined
to be (5R,8R,9R,10S)-3-oxo-8,30-dihydroxypolypoda-13E,
ꢁ
d : given in Table 1. Positive-ion FAB-MS: m/z 481 (MꢁNa) .
C
Preparation of the (R)-MTPA Ester (1a) and the (S)-MTPA Ester (1b)
from Myrrhanol A (1) A solution of 1 (2.0 mg) in CH Cl (1.0 ml) was
29)
1
7E,21E-triene (2).
2
2
treated with (R)-MTPA (10.0 mg) in the presence of EDC·HCl (10.0 mg)
Experimental
and 4-DMAP (5.0 mg), and the mixture was heated under reflux for 2 h. The
The following instruments were used to obtain physical data: specific ro- reaction mixture was poured into ice-water, and the whole was extracted
tations, Horiba SEPA-300 digital polarimeter (lꢀ5 cm); UV spectra, Shi- with EtOAc. The EtOAc extract was successively washed with 5% aqueous
madzu UV-1600 spectrometer; IR spectra, Shimadzu FTIR-8100 spectrome- HCl, aqueous saturated NaHCO , and brine, then dried over MgSO and fil-
3
4
ter; EI-MS and high-resolution MS, JEOL JMS-GCMATE mass spectrome- tered. Removal of the solvent from the filtrate under reduced pressure fur-
ter; FAB-MS and high-resolution MS, JEOL JMS-SX 102A mass spectrom- nished a residue, which was purified by a normal-phase silica gel column
1
13
eter; H-NMR spectra, JNM-LA500 (500 MHz) spectrometer; C-NMR [1.0 g, n-hexane–EtOAc (4 : 1)] to give 1a (1.1 mg, 38%) and 1 (0.5 mg).
spectra, JNM-LA500 (125 MHz) spectrometer with tetramethylsilane as an Through a similar procedure, 1b (1.0 mg, 37%) and 1 (0.6 mg) were pre-
internal standard; and HPLC detector, Shimadzu RID-6A refractive index pared from 1 (2.0 mg) by the use of (S)-MTPA (10.0 mg), EDC·HCl
detector.
The following experimental conditions were used for chromatography: or-
dinary-phase silica gel column chromatography, Silica gel BW-200 (Fuji
Silysia Chemical, Ltd., 150—350 mesh); reverse-phase silica gel column
(10.0 mg), and 4-DMAP (5.0 mg).
1a: Colorless oil. H-NMR (500 MHz, CDCl ) d: 0.78, 0.82, 0.83, 1.13,
1.59 (3H each, all s, 24, 25, 23, 26, 29-H ), 1.61 (6H, s, 27, 28-H ), 1.25,
1
3
3
3
1.79 (1H each, both m, 1-H ), 1.79, 1.88 (1H each, both m, 2-H ), 3.56 (6H,
2
2
chromatography, Chromatorex ODS DM1020T (Fuji Silysia Chemical, Ltd., s, OMeꢃ2), 4.66, 4.71 (2H, ABq, Jꢀ13.1 Hz, 30-H ), 4.73 (1H, dd-like, 3-
2
1
0
00—200 mesh); TLC, precoated TLC plates with Silica gel 60F254 (Merck, H), 5.11, 5.16, 5.51 (1H each, both dd-like, 17, 13, 21-H), 7.39—7.55 (10H,
ꢁ
.25 mm) (ordinary phase) and Silica gel RP-18 F254S (Merck, 0.25 mm) (re- m, Ph-H). Positive-ion FAB-MS: m/z 915 (MꢁNa) .
1
verse phase); reverse-phase HPTLC, precoated TLC plates with Silica gel
RP-18 WF254S (Merck, 0.25 mm); and detection was achieved by spraying
with 1% Ce(SO ) –10% aqueous H SO , followed by heating.
1b: Colorless oil. H-NMR (500 MHz, CDCl ) d: 0.79, 0.80, 0.91, 1.13,
3
1.59 (3H each, all s, 25, 24, 23, 26, 29-H ), 1.24, 1.65 (1H each, both m, 1-
H ), 1.61 (6H, s, 27, 28-H ), 1.65, 1.80 (1H each, both m, 2-H ), 3.56 (6H, s,
3
4
2
2
4
2
3
2
Extraction and Isolation The resin of B. mukul [1.85 kg, collected in
OMeꢃ2), 4.46, 4.71 (2H, ABq, Jꢀ13.1 Hz, 30-H ), 4.73 (1H, dd-like, 3-H),
2
Rajastan, India and purchased from Sharangdhar Pharmaceuticals PTV, Ltd.
(
5.11, 5.16, 5.51 (1H each, both dd-like, 17, 13, 21-H), 7.38—7.51 (10H, m,
Pune, India)] was finely minced and extracted three times with 50% aque- Ph-H). Positive-ion FAB-MS: m/z 915 (MꢁNa) .
ꢁ
ous methanol under reflux for 3 h. Evaporation of the solvent under reduced
NaBH Reduction of Myrrhanone A (2) A solution of 2 (10.0 mg) was
4

October 2004
1203
added to MeOH (2.0 ml) treated with NaBH (4.0 mg each), and the whole
Heterocycles, 47, 397—405 (1998).
4
mixture was stirred at room temperature (25 °C) for 1 h. The reaction mix-
ture was poured into acetone. Removal of the solvent under reduced pressure
gave a product, which was purified by normal-phase silica-gel column chro-
matography [1.0 g, n-hexane–EtOAc (1 : 1)] to give myrrhanol A (1, 7.5 mg,
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26) Yoshikawa M., Shimoda H., Nishida N., Takada M., Matsuda H., J.
Nutr., 132, 1819—1824 (2002).
(2004).
1
13
Murakami N., Murakami T., Kadoya M., Matsuda H., Yamahara J.,
27) The H- and C-NMR spectra of 1 and 2 were assigned with the aid of
Yoshikawa M., Chem. Pharm. Bull., 44, 469—471 (1996).
0) Yoshikawa M., Murakami T., Komatsu H., Murakami N., Yamahara J.,
distortionless enhancement by polarization transfer (DEPT), homo-
and heterocorrelation spectroscopy ( H– H, C– H COSY), and
HMBC experiments.
1
1
13
1
1
1
1
1
1
Matsuda H., Chem. Pharm. Bull., 45, 81—87 (1997).
1) Yoshikawa M., Murakami T., Kadoya M., Li Y., Murakami N., Yama- 28) Ohtani I., Kusumi T., Kashman Y., Kakisawa H., J. Am. Chem. Soc.,
hara J., Matsuda H., Chem. Pharm. Bull., 45, 1671—1676 (1997). 113, 4092—4096 (1991).
2) Yoshikawa M., Murakami T., Matsuda H., Chem. Pharm. Bull., 45, 29) This study was reported in a preliminary communication and the ab-
7)
2
034—2038 (1997).
solute configuration of the 5-positions in myrrhanol A (1) and
myrrhanone A (2) were wrongly reported as S. We devised here the 5S
configurations of 1 and 2 to the 5R configurations, respectively.
3) Yoshikawa M., Murakami T., Shimada H., Matsuda H., Yamahara J.,
Tanabe G., Muraoka O., Tetrahedron Lett., 38, 8367—8370 (1997).
4) Yoshikawa M., Murakami T., Komatsu H., Yamahara J., Matsuda H.,