(+)-Isolarisiresinol 3a-O-sulphate from leaves of Myrsine seguinii

Article abstract of DOI:10.1016/S0031-9422(98)00256-8

From leaves of Myrsine seguinii, (+)-isolarisiresinol 3a-O-β-D- glucopyranoside and 3a-O-sulphate were isolated. Their structures were elucidated by spectroscopic analyses.

Full text of DOI:10.1016/S0031-9422(98)00256-8

Phytochemistry Vol. 49, No. 6, pp. 1777±1778, 1998
# 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
0031-9422/98/$ - see front matter
PII: S0031-9422(98)00256-8
(+)-ISOLARISIRESINOL 3a-O-SULPHATE FROM LEAVES
OF MYRSINE SEGUINII
XI-NING ZHONG, TOSHINORI IDE, HIDEAKI OTSUKA,* EIJI HIRATA and YOSHIO TAKEDA
Institute of Pharmaceutical Sciences, Hiroshima University School of Medicine, 1±2±3 Kasumi,
Minami-ku, Hiroshima, 734±8551 Japan; Faculty of Agriculture, Ryukyu University, Nishihara-cho,
Nakagami-gun, Okinawa 903±0129, Japan; Faculty of Integrated Arts and Science, The University of
Tokushima, 1±1 Minamijosanjima-cho, Tokushima 770±8502, Japan
(Received in revised form 2 March 1998)
Key Word IndexÐMyrsine seguinii; Myrsinaceae; lignan; (+)-isolarisiresinol 3a-O-sulphate.
AbstractÐFrom leaves of Myrsine seguinii, (+)-isolarisiresinol 3a-O-b-D-glucopyranoside and 3a-O-sul-
phate were isolated. Their structures were elucidated by spectroscopic analyses. # 1998 Elsevier Science
Ltd. All rights reserved
In previous papers, we have reported that phyto- tation, the absolute structure of the lignan moiety
was expected to be (+)-isolarisiresinol (1a) and this
was further con®rmed by measurement of the CD
spectrum [3]. Finally, acid hydrolysis of 2 a€orded
(+)-isolarisiresinol (1a) and a prepicitate of barium
sulphate on addition of barium nitrate (see
Experimental). Therefore, the structure of 2 was
elucidated to be (+)-isolarisiresinol 3a-O-sulphate.
chemical investigation of leaves of Myrsine seguinii
a€orded ¯avonol glycosides [1] and hydroquinone
glycosides [2]. Following further investigation, com-
pounds 1 and 2 were isolated from leaves and their
structures were elucidated to be lignan derivatives.
Compound 1 was identi®ed as (+)-isolarisiresinol
3a-O-b-D-glucopyranoside
evidence [3].
by
spectroscopic
Compound 2 was isolated as a colourless crystal-
line compound. The 13C NMR spectrum was simi-
lar to that of 1 (see Table 1). Although no NMR
signals were observed for the sugar unit, compound
2 showed a much more polar nature on TLC (Rf
0.21) than 1 (Rf 0.33). The negative ion FAB mass
spectrum indicated that the molecular weight of 2
was 440 which was 80 mass units higher than that
calculated for isolarisiresinol (1a). This in increase
in mass corresponded with an esteri®cation of one
of the hydroxyl groups by ±PO(OH)2 (MW 81) or
±SO2OH (MW 81). This was also indicated by the
high polarity of the compound. The acid moiety
was presumed to be sulphate, because no couplings
(JPOC and JPOCC) were observed in the 13C NMR
spectrum. The HR-FAB-mass spectrum further
showed that sulphur was present in compound 2.
The site of esteri®cation was determined to be the
hydroxyl group at the 3a-position, since the 13C
NMR chemical shift of C-3a was shifted down®eld
(dC 67.6), when compared with that of compound
1a (dC 62.5 [4]). From the sign of the optical ro-
EXPERIMENTAL
General
Mps.: uncorr.; 1H NMR and 13C NMR:
400 MHz and 100 MHz, respectively; TLC: Merck,
precoated (0.25 mm thickness) with CHCl3±MeOH±
H2O (15:6:1); prep. TLC: Merck, precoated
(0.25 mm thickness) with CHCl3±MeOH (9:1).
Isolation procedure
The plant material, and a part of the extraction
and isolation procedures, were described in the pre-
ceding paper [1]. Compound 1 was isolated from
the 40% MeOH eluate on highly porous synthetic
resin (Diaion HP-20) column chromatography and
2 from 20% MeOH by successive separation on
silica gel CC, droplet counter-current chromatog-
raphy and HPLC in yields of 14 mg and 82 mg, re-
spectively.
(+)-Isolarisiresinol 3a-O-b-D-glucopyranoside (1).
23
D
Colourless needles (MeOH), mp. 135±1388, ‰aŠ
+45.48 (MeOH, c 0.84) [5], other spectroscopic
*Author to whom all correspondence should be addressed. data were essentially the same as those reported [3].
1777

1778
X.-N. ZHONG et al.
(MeOH, c 7.22 Â10 5 M) D E (nm); 0.60 (228),
Table 1. 13C NMR data for
(CD3OD, 100 MHz)
1 and 2
+1.98 (239), +2.00 (276), 2.97 (292). HR-FAB-
MS (negative centroid) (Xe, matrix: PEG-400) m/z:
439.1049 [M-H] (C20H23O9S requires 439.1062, cf.
C20H24O9P requires 439.1158).
1
2
1
2
33.9
39.6
33.6
39.2
64.9
45.2
67.6
47.9
117.4
145.8
147.2
112.5
129.3
134.5
138.5
114.4
148.8
145.2
116.1
123.1
Acid hydrolysis of 2. Compound 2 (15 mg) was
treated with 2 N HCl (6 ml) at 608 for 48 hr. The
reaction mixture was partitioned between Et2O
(100 ml) and H2O (100 ml). The organic layer was
concentrated and then the residue was puri®ed by
prep. TLC to give (+)-isolarisiresinol (1a, 2.20 mg).
CD (MeOH, c 6.11 Â10 5 M) D E (nm): +7.83
(215), +0.86 (226), +4.80 (238), +0.22 (253),
+2.62 (275), 3.93 (292); NMR spectral data were
essentially the same as those reported for
isolarisiresinol [4]. The aq. layer was concentrated
to about 10 ml and a soln of Ba(NO3)2 was added.
The precipitate was collected by centrifugation.
Since the white precipitate was not soluble on ad-
dition of 2 N HCl solution, it was con®rmed to be
BaSO4.
2a
3
65.3
46.0
3a
4
69.6
48.0
5
6
7
8
117.4
145.9
147.2
112.5
129.2
134.5
138.7
114.4
149.0
145.2
116.1
123.2
9
10
1'
2'
3'
4'
5'
6'
1
2
3
4
5
6
105.2
75.2
78.2
71.7
77.9
62.8
AcknowledgementsÐThe authors are grateful for
the access to the superconductant NMR instrument
in the Research Center for Molecular Medicine of
Hiroshima University School of Medicine.
-OMe
-OMe
56.5
56.6
56.5
56.5
(+)-Isolarisiresinol 3a-O-sulphate (2). Colourless
crystalline state (MeOH), mp. 185±1958 (decomp.),
‰aŠ +11.38 (MeOH, c 0.53). IR ꢀ
cm 1: 3400,
2900, 1600, 1505, 1450, 1365, 1250, 1200, 1120,
23
D
KBr
max
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