Terpenes and lignans from leaves of Chamaecyparis formosensis

Article abstract of DOI:10.1016/S0031-9422(99)00074-6

84 chemical constituents were isolated from the leaves of Chamaecyparis formosensis. These components include 18 sesquiterpenes, 40 diterpenes, 8 flavones, 7 lignans and 11 miscellaneous compounds. Among them 3 sesquiterpenes, 7 diterpenes and one lignan

Full text of DOI:10.1016/S0031-9422(99)00074-6

Phytochemistry 51 (1999) 793±801
Terpenes and lignans from leaves of Chamaecyparis formosensis
Tung-Chieh Lin, Jim-Min Fang*, Yu-Shia Cheng
Department of Chemistry, National Taiwan University, Taipei 106, Taiwan
Received 27 May 1998; accepted 30 November 1998
Abstract
84 chemical constituents were isolated from the leaves of Chamaecyparis formosensis. These components include 18
sesquiterpenes, 40 diterpenes, 8 ¯avones, 7 lignans and 11 miscellaneous compounds. Among them 3 sesquiterpenes, 7 diterpenes
and one lignan are new compounds, the structures of which were determined by chemical and spectral methods. # 1999 Elsevier
Science Ltd. All rights reserved.
Keywords: Chamaecyparis formosensis; Cupressaceae; Leaves; Sesquiterpenes; Diterpenes; Flavones; Lignans; Sterols
1. Introduction
ponents, including 18 sesquiterpenes, 40 diterpenes, 8
¯avones, 7 lignans and 11 miscellaneous compounds
(see Section 3). Among them, 73 components are
known compounds, whose structures were readily
identi®ed by comparison of their physical and spectro-
Chamaecyparis formosensis Matsumura, known as
Taiwan red cypress (Li & Keng, 1994) is indigenous to
the high mountain area of Taiwan. It is called red
cypress since the bark appears to be slightly reddish
brown color. The wood is frequently used in building
and for expensive furniture. The plant is known to
possess strong resistance against wood-decaying fungi
(Saeki, Sumimoto, & Kondo, 1973; Harayama, Cho,
& Inubushi, 1977). The chemical constitution of the
root, bark, wood, pericarps and leaves of this plant
has been investigated (Kafuku & Ichikawa, 1931;
Nozoe, Cheng, & Toda, 1966; Fang, Lai, & Cheng,
1986; Fang, Sheu, & Cheng, 1986; Hsu, Fang, &
Cheng, 1995). The studies of leaves are, however, lim-
ited to its essential oil (Kafuku & Ichikawa, 1931;
Fang et al., 1986). We report herein a more detailed
investigation of the constituents of leaves.
scopic properties (m.p., [a], IR, UV, MS, H and 13C
1
NMR spectra) with authentic samples.
The 84 various compounds (1±84) that were isolated
are described in summary form in Section 3; 73 are
known (see Section 3). Compounds 15±17, 36, 40, 41,
45, 52, 53, 56 and 73, however, have not been reported
thus far. Their structures were determined by chemical
and spectral methods. The molecular formula of 15
(C13H22O2) was deduced from the exact mass measure-
ment of its molecular ion, [M]+ appearing at m/z
1
210.1614. The IR absorptions at 3448 and 1711 cm
were attributable to hydroxyl and carbonyl groups.
The 13C NMR spectrum showed 13 carbons, in which
resonances at d 65.0 (carbinyl), 208.5 (carbonyl), 124.8
and 135.9 (ole®nic) were diagnostic. The 1H NMR
spectra showed four methyl groups at d 0.95 (s), 0.99
(s), 1.57 (s, vinyl) and 2.12 (s, methyl ketone). The car-
binyl proton resonance occurred at d 3.91 (tdd, J=10,
6, 4 Hz), indicating its axial position on a cyclohexane
ring. By assistance of the HMBC and HMQC spectral
analyses, the structure of dinorsesquiterpene 15 was
determined as 3-hydroxymegastigm-5-en-9-one. Com-
2. Results and discussion
The acetone extract of the leaves of C. formosensis
was subjected to chromatography to give 84 com-
* Corresponding author.
0031-9422/99/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved.
PII: S0031-9422(99)00074-6

794
T.-C. Lin et al. / Phytochemistry 51 (1999) 793±801
pound 15 with (3S )-con®guration is dextrorotatory,
[a]2D5 +34.5 (CHCl3;
0.5), whereas the (3R )-
solution (258C, 16 h) yielded an O-methylation pro-
duct identical with compound 36.
The H NMR of compound 40 was similar to that
c
1
enantiomer obtained enzymatically (Miyase, Ueno,
Takizawa, Kobayashi, & Oguchi, 1988) is levorotatory,
[a]2D3 84.4 (MeOH; c 0.48). The (R )-enantiomer was
also previously synthesized (Aakermann, Guillard, &
Liaaen-Jensen, 1993), but no optical rotation was
reported. Treatment of 15 with (2)-2-phenylbutanoic
anhydride according to Horeau's method (Fiaud,
Horeau, & Kagan, 1997) supported the (S )-con®gur-
ation.
of pisiferanol (39) (Hasegawa, Kojima, & Hirose,
1985), except for an additional signal at d 3.76 (3 H, s)
attributable to a methoxy group on a phenyl ring.
Thus, compound 40 was assigned as 12-O-methylpisi-
feranol. An O-methylation product obtained by treat-
ment of pisiferanol 39 with diazomethane in Et2O was
identical with compound 40. The 9(20 4 10)abeo-abie-
tane 40 also showed the two characteristic C-20 pro-
tons as an AB pattern at dH 2.53 (d, J=13.8 Hz) and
2.97 (d, J=13.8 Hz) in the 1H NMR spectrum
(Hasegawa et al., 1985).
Compound 41 (C20H30O3) exhibited an 1H NMR
spectrum similar to that of pisiferanol 39 (C20H30O2),
except for the presence of an additional carbinyl pro-
ton at d 3.69 (m ). The 13C NMR spectrum showed the
corresponding secondary carbinyl carbon occurring at
dC 76.7 and another tertiary carbinyl carbon occurring
at d 72.4. Compound 41 was assigned as 1b-hydroxypi-
siferanol. The diagnostic H-20a and H-20b resonances
occurred at d 2.51 (d, J=14 Hz) and 3.29 (d, J=14
Hz), respectively (Hasegawa et al., 1985). The occur-
rence of H-20b at a lower ®eld, as compared to 40,
was due to the deshielding e€ect of the 1b-OH group.
The NOESY spectrum showed the correlation of H-1a
(at d 3.69) with H-20a (at d 2.51), supporting the
assigned stereochemistry.
Compound 16 (C13H22O2) gave rise to a molecular
ion [M]+ at m/z 210.1614. Compound 16 is a consti-
tutional isomer of compound 15; however, it showed
1
an IR absorption at 1655 cm and a UV absorption
at 261 nm typical for an enone group. The correspond-
ing carbon resonances for enone occurred at d 130.9
(C-5), 164.7 (C-6) and 199.1 (C-4). The H NMR spec-
1
trum also revealed the presence of a carbinyl proton
(H-9) at d 3.84 (m). Compound 16 with [a ]2D5 +8.1
(CHCl3; c 0.4) was thus determined to be (S)-9-hydro-
xymegastigm-5-en-4-one, whose C-9 chirality was
established using Horeau's method (Fiaud et al.,
1997).
Compound 17 (C13H24O2), [M]+ appearing at m/z
212.1771, was assigned as megastigm-5-ene-3,9-diol
according to 1H and 13C NMR analyses. Compound
17 existed as a single isomer as shown by NMR spec-
tra. The two carbinyl protons appeared at d 3.77 (m,
H-9) and 3.91 (tdd, J=10, 6, 4 Hz, H-3). Thus, H-3
was axially oriented and the C-3 hydroxyl group was
equatorially oriented. Compound 17 was levorotatory,
[a]2D5 33.8 (CHCl3; c 0.5), but, its absolute con®gur-
ation was not rigorously determined.
Compound 45 was determined as 10-deoxy-4,18-
epoxy-12-methoxy-4,5-seco-pisiferan-19-ol from the
spectral analyses. The exact mass of molecular ion
[M]+ at m/z 332.2340 was in agreement with a molecu-
1
lar formula C21H32O3. In the H NMR spectrum, two
The molecular formula C21H30O3 of compound 36
was deduced from the exact mass measurement of its
molecular ion [M]+ at m/z 330.2183. The IR absorp-
aromatic protons occurred as two singlets at d 6.60
(H-11) and 6.93 (H-14) indicating their para positions.
The phenyl ring bearing a C-12 methoxy group (at dH
3.77) and a C-13 isopropyl group was typical to pisi-
feranes. A methylene group at d 2.00 (m, H-18) was at-
tributable to an oxirane moiety, whereas another
methylene group occurring as an AB type at d 3.11 (d,
J=10.6 Hz) and d 3.62 (d, J=10.6 Hz) was attribu-
table to a CH2OH group. The structural assignment
was supported by the 13C, COSY and HMBC spectra,
but, the stereochemistry at C-4 and C-10 remains
unknown.
1
tions at 3327 and 1706 cm were attributable to hy-
droxyl and carbonyl groups. The 1H NMR spectrum
indicated the presence of an isopropyl group (occur-
ring at d 1.25 (3 H, d), 1.26 (3 H, d) and 3.19 (1 H,
sept)), three methyl groups on tertiary carbons (occur-
ring at d 1.08 (s), 1.11 (s) and 1.58 (s)) and a methoxy
group on a phenyl ring (occurring at d 3.76 (s)). Based
on this information and the HMQC and HMBC spec-
tral analyses, the structure of 36 was assigned as 3b-
hydroxy-1-oxo-13-O-methyltotarol. The H-3 was axi-
ally oriented as it displayed at d 3.60 as a doublet of
doublets (J=12, 4.8 Hz). The HMBC spectrum
showed correlation of C-13 (at d 156.9) with H-11 (at
d 7.19), H-12 (at d 6.75) and the MeO group (at dH
3.76). The position of the methoxy group on C-13 was
thus established. A chemical correlation of 36 with 3b-
hydroxy-1-oxototarol (37) (Kuo & Chen, 1994) was
carried out to con®rm the structural assignment.
Indeed, treatment of 37 with diazomethane in Et2O
Compounds 51±53 are ester derivatives of labda-
1
13(16),14-diene-8a,19-diol 50 as inferred from their H
and 13C NMR spectra. Compound 51 was previously
isolated from Juniperus thurifera (San Feliciano et al.,
1988). Compound 51 showed proton resonances at d
6.27 (d, J=16.0 Hz), 7.58 (d, J=16.0 Hz), 6.82 (d,
J=8.4 Hz, 2 H) and 7.42 (d, J=8.4 Hz, 2 H) for an
(E )-p-hydroxycinnamic ester. On the other hand, com-
pound 52 displayed proton resonances at d 5.79 (d,
J=12.8 Hz), 6.81 (d, J=12.8 Hz), 6.76 (d, J=8.6 Hz,

T.-C. Lin et al. / Phytochemistry 51 (1999) 793±801
795
2 H) and 7.56 (d, J=8.6 Hz, 2 H) attributable to a
(Z )-p-hydroxycinnamic ester. The coupling constant
(12.8 Hz) for the two ole®nic protons in compound 52
was smaller than that in the E-isomer 51 (16 Hz).
Besides the pertinent proton resonances for the lab-
dadiene moiety, compound 53 also exhibited ®ve pro-
ton resonances at d 6.25 (d, J=15.9 Hz), 7.56 (d,
J=15.9 Hz), 6.89 (d, J=8.1 Hz), 7.00 (d, J=1.7 Hz)
and 7.05 (dd, J=8.1, 1.7 Hz) attributable to an (E)-4-
hydroxy-3-methoxycinnamate moiety. The stereochem-
istry of 53 was established by NOE experiments. For
example, irradiation of the C-3' methoxy group (at dH
3.90) caused an enhancement of H-2' (at dH 7.00).
Irradiation of the 10-Me group (at dH 0.82) caused
enhancements of H-19 (at dH 3.98 and 4.27) and the
8b-Me group (at dH 1.13).
proton (H-10). Compound 73a was determined to be
9'-(b-rhamnopyranosyl)-3-methoxy-3':7,4':8-diepoxy-
neolignan-4,9-diol pentaacetate. Following analysis of
the HMBC spectrum, the core structure of benzodiox-
ane-type neolignan was established and individual pro-
tons and carbons were assigned. The 7,8-trans
relationship was inferred from the relatively large
coupling constant of 7.8 Hz between H-7 (at d 4.87)
and H-8 (at d 4.17) (Fang, Lee, & Cheng, 1992). The
trans isomers of such diepoxyneolignans usually exhi-
bit larger coupling constants J7,8 (ca. 8 Hz) than the
cis isomers (ca. 3 Hz) (Fang et al., 1992). Compound
73a likely has (7R,8R )-con®guration as indicated by
negative CD (y ) values at l=368, 307 and 256 nm, a
common feature of related benzodioxane systems, but
this remains to be proven (Silva, Barbosa-Filho,
Yoshida, & Gottlieb, 1989).
Compound 56a (C22H34O4) was obtained by acety-
lation of the parent alcohol. Compound 56a contained
a carboxylic group as inferred from the characteristic
carbon resonance at dC 181.8 and IR absorptions at
3500±2500 and 1760 cm 1. The signal at dC 170.3 was
attributable to an acetyl group. The 1H NMR spec-
trum showed three singlets at dH 0.72, 1.01 and 1.24
for three methyl groups on tertiary carbons. A vinyl
methyl group occurred at dH 1.72, whereas an acetyl
group occurred at dH 1.91. The conjugated diene moi-
ety was indicated by the proton resonances at dH 4.85
(H-12), 4.87 (H-15), 5.16 (H-15) and 5.73 (H-14), as
well as by the carbon resonances at d 110.3 (C-15),
129.7 (C-12), 135.8 (C-13) and 148.6 (C-14). By com-
3. Experimental
3.1. General
Yanaco MP-500D melting point apparatus, JASCO
DIP-1000 polarimeter, Perkin-Elmer 983G infrared
spectrophotometer, Hitachi U-3210 ultraviolet-visible
spectrophotometer, Bruker AM-300 spectrometer,
Finnigan TSQ-46C mass spectrometer (EI-MS), JEOL
SX-102A spectrometer (FAB-MS), JEOL JMS-HX 110
mass spectrometer (HR-MS) and Waters M501 HPLC
with Lichrosorb Si-60 (7 mm) column (Waters R401 RI
detector) were used. Merck 9385 silica gel (230±400
mesh) was used for ¯ash CC. Merck 5554 Kieselgel 60
F254 sheets were used for TLC analyses.
parison of the H and 13C spectra with those of trans-
1
communic acid 54 (Thomas, 1966; Fang, Hsu, &
Cheng, 1989), compound 56a was assigned as 8a-acet-
oxylabda-12E,14-dien-19-oic acid. The C-10 methyl
group appeared at a high ®eld of dH 0.72 due to the
shielding e€ect of the C-4 carboxyl group. By using a
procedure of oxymercuration-demercuration (Barrero,
Sanchez, Altarejos, Perales, & Torres, 1991), a methyl
ester of trans-communic acid was previously converted
to 8b-hydroxylabda-12,14-dien-19-oic acid methyl
ester, of which C-10 methyl group occurred at a lower
®eld of dH 0.80 due to the deshielding e€ect of the 8b-
hydroxyl group.
Compound 73 was subjected to peracetylation
(Ac2O, pyridine) to give 73a. The 1H and 13C NMR
spectra of 73a indicated the presence of ®ve acetyl
groups. Two diagnostic methyl groups appearing at d
3.83 (s) and d 1.17 (d, J=6.1 Hz) were attributable to
an aromatic methoxy group and a methyl group of
rhamnose. The exact mass measurement of molecular
ion [M]+ at m/z 702.2518 led to a molecular formula
C35H42O15. Thus, 73a was inferred to contain an 18-
carbon core structure of lignan by deduction of 1
methoxy carbon, 6 carbons from rhamnose and 10 car-
bons from 5 acetyl groups. A proton resonance at dH
4.68 (d, J=1.4 Hz) was ascribed to the axial anomeric
3.2. Material
The leaves of C. formosensis Matsumura were col-
lected from mountains in the north part of Taiwan. A
voucher specimen is deposited in the Herbarium of
National Taiwan University. The air-dried leaves (18
kg) were extracted with Me2CO (60 l  3). The extract
was ®ltered through a column of activated charcoal,
concentrated and partitioned between EtOAc and
water (v/v=1:1). The EtOAc-soluble part was concen-
trated (360 g), coated with silica gel (720 g) and chro-
matographed on a silica gel column (2.5 kg) by elution
with gradients of hexane, EtOAc, Me2CO and MeOH.
Every 80±120 ml of eluent was collected in one frac-
tion. Separation of chemical components was moni-
tored by TLC analyses. Appropriate fractions were
combined: (i) the elution with hexane (1.5 l) giving
compounds 2, 10±13, 24±26, 32, 40, 47, 57 and 58; (ii)
the elution with gradients of EtOAc/hexane (1, 2, 3, 5,
10, 20, 30, 40, 50, 60, 70, 80 and 90%, 1 l each) giving
compounds 1, 3±9, 14±23, 27±31, 33±39, 41±46, 48±

796
T.-C. Lin et al. / Phytochemistry 51 (1999) 793±801
55, 67±71, 74±79 and 81±84; (iii) the elution with
EtOAc (1 l) giving compound 59; (iv) the elution with
gradients of Me2CO/EtOAc (10, 20, 30, 40, 50, 60, 70,
80 and 90%, 1 l each) giving compounds 56 (as the
parent alcohol), 60±66, 72 (as the parent triol) and 80
and (v) the elution with Me2CO (0.8 l) followed by a
gradient of Me2CO/MeOH (1:1, 0.8 l) giving com-
pound 73 (as the parent polyhydroxy compound). The
total weight of these components was 238.5 g at this
stage. Puri®cation of the components collected from
the fractions (i)±(iii) was carried out by using ¯ash CC
and HPLC. The fractions (iv) and (v) were subjected
to acetylation (Ac2O, pyridine, 258C, 24 h), respect-
ively, and the products were further separated by ¯ash
CC or HPLC.
lected from CC) are listed as follows: a-cadinol
(Bottini & Garfagnoli, 1987) (1, 7.75 g, 3.25%),
cadina-4(15),9-diene (Andersen et al., 1977) (2, 2.05 g,
0.86%), eudesm-4(15)-ene-1,6-diol (Gutierrez & Herz,
1988) (3, 596 mg, 0.25%), chaenocephalol (Box,
Bardouille, & Chan, 1977) (4, 453 mg, 0.19%),
eudesm-3-en-11-ol (Kutney & Singh, 1984) (5, 1.31 g,
0.55%), eudesm-4-en-11-ol (Beek, Kleis, Posthumus, &
Veldhuizen, 1989) (6, 1.53 g, 0.64%), eudesm-4(15)-en-
5-ol (Humber, Pinder, & Williams, 1967) (7, 1.36 g,
0.57%), cryptomeridol (Dolejs & Herout, 1961) (8, 549
mg, 0.23%), thujopsenol (Norin, 1961) (9, 358 mg,
0.15%), thujopsenic acid (Norin, 1961) (10, 501 mg,
0.21%), a-humulene (Peppard & Sharpe, 1980) (11,
1.62 g, 0.68%), b-sesquiphellandrene (Bohlmann &
Suwita, 1979) (12, 1.07 g, 0.45%), 6,7-epoxycaryo-
phyll-3(15)-ene (Warnhoof & Srinivason, 1973) (13,
The weight and percentage of each puri®ed com-
ponent (based on 238.5 g total weight of material col-

T.-C. Lin et al. / Phytochemistry 51 (1999) 793±801
797
692 mg, 0.29%), cedrol (Breitholle & Fallis, 1978) (14,
2.29 g, 0.96%), 3-hydroxymegastigm-5-en-9-one (15,
22 mg, <0.01%), 9-hydroxymegastigm-5-en-4-one (16,
19 mg, <0.01%), megastigm-5-en-3,9-diol (17, 16 mg,
<0.01%), oplopanone (Takeda, Minato, & Ishikawa,
1966) (18, 859 mg, 0.36%), ferruginol (Fang, Sou,
Chiu, & Cheng, 1993) (19, 763 mg, 0.32%), 12-O-
methylferruginol (Matsumoto & Usui, 1979) (20, 739
mg, 0.31%), abieta-8,11,13-triene (Brieskorn, Fuchs,
Bredenberg, Mcchesney, & Wenkert, 1964) (21, 1.00 g,
0.42%), O-methylpisiferic acid (Yatagai & Takahashi,
1980) (22, 6.80 g, 2.85%), pisiferic acid (Banerjee,
Hurtado, Laya, Acevedo, & Alvarez, 1988) (23, 4.44 g,
1.86%), pisiferol (Matsumoto & Usui, 1982) (24, 2.96
g, 1.24%), 20-acetoxypisiferol (Kobayashi, Nishino,
Tomita, & Fukushima, 1987) (25, 930 mg, 0.39%),
pisiferal (Matsumoto, Endo, & Okimoto, 1983) (26,
692 mg, 0.29%), hinokione (Matsumoto, Usui,
Kawasima, & Mitsuki, 1981) (27, 119 mg, 0.05%),
hinokiol (Su, Fang, & Cheng, 1994) (28, 3.86 g,
1.62%), isohinokiol (Chow & Erdtman, 1962) (29, 382
mg, 0.16%), 12-O-methylisohinokiol (Kutney et al.,
1992) (30, 119 mg, 0.05%), sugiol (Ara, Shaheen,
Faizi, & Siddiqui, 1990) (31, 620 mg, 0.26%), sugiol
methyl ether (Wenkert, Campello, McChesney, &
Watts, 1974) (32, 239 mg, 0.10%), totarol (Ying &
Kubo, 1991) (33, 4.25 g, 1.78%), 3b-hydroxytotarol
(Campello & Fonseca, 1975) (34, 3.79 g, 1.59%), totar-
olone (Ying & Kubo, 1991) (35, 1.29 g, 0.54%), 3b-
hydroxy-1-oxo-13-O-methyltotarol (36, 32 mg, 0.01%),
3b-hydroxy-1-oxototarol (Kuo & Chen, 1994) (37, 1.14
g, 0.48%), sempervirol (Fang, Lee, & Cheng, 1993)
(38, 1.93 g, 0.81%), pisiferanol (Hasegawa et al., 1985)
(39, 4.86 g, 2.04%), 12-O-methylpisiferanol (40, 835
mg, 0.35%), 1b-hydroxypisiferanol (41, 21 mg,
acetoxylabda-12,14-dien-19-oic acid (56a, 382 mg,
0.16%), ent-kaur-16-ene (Hogg & Knox, 1987) (57,
549 mg, 0.23%), beyer-15-ene (Kapadi, Somen, Sobti,
& Dev, 1983) (58, 835 mg, 0.35%), catechin (Nonaka,
Ezaki, Hayashi, & Nishioka, 1983) (59, 6.15 g, 2.58%),
kaemferol (Kingston, 1971) (60, 1.41 g, 0.59%), kaem-
ferol-3-O-a-L-rhamnopyranoside (Agrawal, 1989) (61,
3.20 g, 1.34%), quercetin (Chen, Wan, & Chen, 1988)
(62, 1.29 g, 0.54%), quercetin-3-O-L-rhamnopyranoside
(Looker, Holm, Minor, & Kagai, 1964) (63, 2.34 g,
0.98%), amento¯avone (Markham, Sheppard,
&
Geiger, 1987) (64, 2.91 g, 1.22%), sequoia¯avone
(Markham, Franke, Molloy, & Webby, 1990) (65, 2.41
g, 1.01%), hinoki¯avone (Dora & Edwards, 1991) (66,
2.24 g, 0.94%), pluviatolide (Ganeshpure & Stevenson,
1982) (67, 1.48 g, 0.62%), nortrachelogenin (Nishibe,
Hisada, & Inagaki, 1971) (68, 1.79 g, 0.75%), 7-hydro-
xymatairesinol (Fang, Wei, & Cheng, 1985) (69, 739
mg, 0.31%), hinokinin (Formiga, 1976) (70, 572 mg,
0.24%), savinin (Fang, Jan, & Cheng, 1985) (71, 453
mg, 0.19%), cedrusin tetraacetate (Agrawal, Agrawal,
& Rastogi, 1980) (72a, 24 mg, 0.01%), (7R,8R )-9'-(b-
rhamnopyranosyl)-3-methoxy-3':7,4':8-diepoxyneo-
lignan-4,9-diol pentaacetate (73a, 143 mg, 0.06%),
umbelliferone (Chatterjee, Sarkar, & Shoolery, 1980)
(74, 2.77 g, 1.16%), cis-2,4-dihydroxycinnamic acid
(75, 739 mg, 0.31%), trans-4-hydroxy-3-methoxycin-
namic acid (ferulic acid) (76, 382 mg, 0.16%), 4-hydro-
xycinnamic acid (77, 286 mg, 0.12%), 4-
hydroxycinnamaldehyde (78, 382 mg, 0.16%), b-sitos-
terol (Holland, Diakow, & Taylor, 1978) (79, 5.91 g,
2.48%), sitosterol-3b-D-glucopyranoside (80, 310 mg,
0.13%) (Purushothaman, Sarada,
&
Saraswathy,
1987), stigmasterol (Holland et al., 1978) (81, 835 mg,
0.35%), (Z )-octadec-9-enoic acid (82, 6.82 g, 2.86%),
octadec-9Z,12Z-dienoic acid (83, 5.70 g, 2.39%) and
octadec-9Z,12Z,15Z-trienoic acid (84, 5.77 g, 2.42%).
The peracetates of compounds 61, 63, 65, 66 and 80
were also prepared (Ac2O, pyridine, 258C, 24 h) and
their structures were con®rmed by spectral methods.
<0.01%), 20b-hydroxypisiferanol (Ahn, Wada,
&
Marumo, 1986) (42, 382 mg, 0.16%), pisiferin
(Hasegawa & Hirose, 1984) (43, 477 mg, 0.20%), 1b-
hydroxyisopisiferin (Hasegawa et al., 1985) (44, 358
mg, 0.15%), 10-deoxy-4(18)-epoxy-12-methoxy-4,5-
seco-pisiferan-19-ol (45, 19 mg, <0.01%,), phytol
(Sims & Pettus, 1976) (46, 1.45 g, 0.61%), phytol acet-
ate (Goodman, Old®eld, & Allerhand, 1973) (47, 1.17
g, 0.49%), sandaracopimaric acid (Edwards, Nicolson,
& Rodger, 1960) (48, 1.26 g, 0.53%), isopimaric acid
(Harris & Sanderson, 1948) (49, 405 mg, 0.17%),
labda-13(16),14-diene-8a,19-diol (Thomas, 1966) (50,
404 mg, 0.17%), 8a-hydroxylabda-13(16),14-dien-19-yl
(E)-4-hydroxycinnamate (San Feliciano et al., 1988)
(51, 36 mg, 0.01%), 8a-hydroxylabda-13(16),14-dien-
19-yl (Z )-4-hydroxycinnamate (52, 30 mg, 0.01%), 8a-
3.3. 3-Hydroxymegastigm-5-en-9-one (15)
Oil, [a]2D5 +34.5 (CHCl3; c 0.5). TLC (25% Me2CO
neat
max
1
cm : 3448, 2932, 1711. H
1
in hexane) Rf 0.3. IR n
NMR (CDCl3): d 0.95 (3 H, s, H-11), 0.99 (3 H, s, H-
12), 1.41 (1 H, m, H-2), 1.57 (3 H, s, H-13), 1.63 (2 H,
m, H-7), 1.66 (1 H, m, H-4), 1.74 (1 H, m, H-2), 1.95
(1 H, m, H-8), 2.12 (3 H, s, H-10), 2.22 (1 H, m, H-8),
2.47 (1 H, m, H-4), 3.91 (1 H, tdd, J=10, 6, 4 Hz, H-
3). 13C NMR (CDCl3): d 19.5 (C-13), 21.7 (C-7), 28.2
(C-10), 29.2 (C-11), 29.4 (C-12), 37.7 (C-1), 42.1 (C-8),
44.2 (C-4), 48.3 (C-2), 65.0 (C-3), 124.8 (C-5), 135.9
(C-6), 208.5 (C-9). EI-MS (70 eV) m/z (rel. int.): 210
[M+] (18), 192 (8), 177 (15), 159 (45), 134 (63), 119
(100).
hydroxylabda-13(16),14-dien-19-yl
(E)-4-hydroxy-3-
methoxycinnamate (53, 41 mg, 0.02%), trans-commu-
nic acid (Thomas, 1966; Fang et al., 1989) (54, 453
mg, 0.19%), trans-communol (Kitajima, Noda, Ida,
Komori, & Kawasaki, 1982) (55, 525 mg, 0.22%), 8a-

798
T.-C. Lin et al. / Phytochemistry 51 (1999) 793±801
3.4. 9-Hydroxymegastigm-5-en-4-one (16)
3.7. 12-O-Methylpisiferanol (40)
Oil, [a]2D5 +8.1 (CHCl3; c 0.4). TLC (25% Me2CO
Oil. [a]2D6 +28 (MeOH; c 2.5). TLC (5% EtOAc in
cm 1: 3550, 1605, 1582,
neat
1
cm : 3423, 2962, 1655. H
neat
max
1
in hexane) Rf 0.3. IR n
hexane) Rf 0.35. IR n
max
1
NMR (CDCl3, 300 MHz): d 1.14 (6 H, s, H-11, H-12),
1.23 (3 H, d, J=6.4 Hz, H-10), 1.56 (2 H, m, H-8),
1.75 (3 H, s, H-13), 1.78 (2 H, m, H-7), 2.19 (2 H, m,
H-2), 2.44 (2 H, m, H-3), 3.84 (1 H, m, H-9). 13C
NMR (CDCl3, 75 MHz): d 11.5 (C-13), 23.5 (C-10),
26.8 (C-2), 26.9 (C-11), 27.0 (C-12), 34.2 (C-3), 36.4
(C-1), 37.4 (C-7), 37.9 (C-8), 68.4 (C-9), 130.9 (C-5),
164.7 (C-6), 199.1 (C-4). EI-MS (70 eV) m/z (rel. int.):
210 [M+] (22), 195 (80), 177 (33), 165 (50), 152 (100),
137 (77), 121 (42), 109 (78).
1500. H NMR (CDCl3, 300 MHz): d 0.86 (3 H, s, H-
18), 0.90 (3 H, s, H-19), 1.15 (3 H, d, J=7 Hz, H-16),
1.19 (3 H, d, J=7 Hz, H-17), 1.16-1.70 (8 H, m),
1.67±1.84 (1 H, m), 1.88-2.10 (1 H, m), 2.53 (1 H, d,
J=13.8 Hz, H-20), 2.70 (2 H, m, H-7), 2.97 (1 H, d,
J=13.8 Hz, H-20), 3.23 (1 H, sept, J=7 Hz, H-15),
3.76 (3 H, s, OMe), 6.59 (1 H, s, H-11), 6.91 (1 H, s,
H-14). 13C NMR (CDCl3): d 18.7, 21.6, 22.6, 23.0,
24.1, 26.4, 32.3, 34.4, 35.4, 42.1, 42.5, 51.4, 55.6, 58.0,
70.8, 114.5, 126.3, 133.9, 135.2, 135.7, 155.0. EI-MS
(70 eV) m/z (rel. int.): 316 [M+] (37), 298 (8), 190
(100), 175 (18), 163 (8).
3.5. Megastigm-5-en-3,9-diol (17)
3.8. 1b-Hydroxypisiferanol (41)
Oil, [a]2D5 33.8 (CHCl3; c 0.5). TLC (30% Me2CO
neat
1
cm : 3396, 2920. H NMR
1
in hexane) Rf 0.3. IR n
Needles, [a]2D5 +30.5 (MeOH, c 0.35). TLC (35%
max
(CDCl3, 300 MHz): d 1.01 (3 H, s, H-11), 1.04 (3 H, s,
H-12), 1.19 (3 H, s, H-10), 1.36 (1 H, m, H-2), 1.48 (2
H, m, H-8), 1.60 (3 H, s, H-13), 1.68 (1 H, m, H-2),
1.80 (1 H, m, H-4), 2.20 (2 H, m, H-7), 2.23 (1 H, m,
H-4), 3.77 (1 H, m, H-9), 3.91 (1 H, tdd, J=10.2, 5.7,
4 Hz, H-3). 13C NMR (CDCl3, 75 MHz): d 19.7 (C-
13), 23.4 (C-10), 24.4 (C-7), 28.5 (C-11), 29.7 (C-12),
37.9 (C-1), 39.7 (C-8), 42.3 (C-4), 48.6 (C-2), 65.3 (C-
3), 68.7 (C-9), 124.1 (C-5), 136.9 (C-6). EI-MS (70 eV)
m/z (rel. int.): 212 [M+] (17), 194 (8), 179 (11), 161
(40), 153 (18), 136 (62), 121 (100).
neat
max
Me2CO in hexane) Rf 0.33. IR n
cm 1: 3535, 3357,
1
2934, 2870. H NMR (CDCl3, 300 MHz): d 0.87 (3 H,
s, H-19), 0.94 (3 H, s, H-18), 1.20 (2 H, m, H-2), 1.21
(3 H, d, J=6.8 Hz, H-16), 1.23 (3 H, d, J=6.8 Hz, H-
17), 1.51 (1 H, m, H-6), 1.68 (1 H, m, H-5), 2.04 (2 H,
m, H-3), 2.15 (1 H, m, H-6), 2.51 (1 H, d, J=14 Hz,
H-20), 2.70 (2 H, m, H-7), 3.15 (1 H, sept, J=6.8 Hz,
H-15), 3.29 (1 H, d, J=14 Hz, H-20), 3.69 (1 H, m,
H-1), 6.56 (1 H, s, H-11), 6.91 (1 H, s, H-14). 13C
NMR (CDCl3, 75 MHz): d 21.7 (C-19), 22.5 (C-16),
22.8 (C-17), 23.6 (C-3), 25.9 (C-6), 26.7 (C-15), 32.1
(C-18), 33.9 (C-4), 34.6 (C-2), 34.9 (C-7), 47.7 (C-20),
51.7 (C-5), 72.4 (C-10), 76.7 (C-1), 118.9 (C-11), 126.4
(C-14), 132.8 (C-13), 133.6 (C-9), 136.3 (C-8), 150.9
(C-12). EI-MS (70 eV) m/z (rel. int.): 318 [M]+ (35),
236 (25), 176 (70), 84 (100). HR-MS for C20H30O3
requires 318.2187; found 318.2185.
3.6. 3b-hydroxy-1-oxo-13-O-methyltotarol (36)
Solid, m.p. 179±180.68C, [a]2D5 +3.5 (MeOH; c 1.3).
neat
1
cm :
TLC (25% EtOAc in hexane) Rf 0.33. IR n
max
1
3327, 1706. H NMR (CDCl3, 300 MHz): d 1.08 (3 H,
s, H-19), 1.11 (3 H, s, H-18), 1.25 (3 H, d, J=7.2 Hz,
H-16), 1.26 (3 H, d, J=7.2 Hz, H-17), 1.50 (1 H, m,
H-5), 1.58 (3 H, s, H-20), 1.78 (1 H, m, H-6), 2.00 (1
H, m, H-6), 2.64 (1 H, dd, J=4.8, 11.2 Hz, H-2a),
2.70 (1 H, m, H-7), 2.90 (1 H, m, H-7), 3.10 (1 H, dd,
J=11.2, 12 Hz, H-2b), 3.19 (1 H, sept, J=7.2 Hz, H-
15), 3.60 (1 H, dd, J=4.8, 12 Hz, H-3), 3.76 (s, OMe),
6.75 (1 H, d, J=8.8 Hz, H-12), 7.19 (1 H, d, J=8.8
Hz, H-11). 13C NMR (CDCl3, 75 MHz): d 16.2 (C-19),
18.8 (C-6), 20.2 (C-17), 20.4 (C-16), 25.2 (C-20), 27.7
(C-15), 28.7 (C-18), 29.4 (C-7), 38.9 (C-4), 45.1 (C-2),
48.9 (C-5), 53.6 (C-10), 55.0 (OMe), 78.4 (C-3), 109.1
(C-12), 128.4 (C-11), 132.7 (C-9), 133.1 (C-8), 134.0
(C-14), 156.9 (C-13), 210.4 (C-1). EI-MS (70 eV) m/z
(rel. int.): 330 [M+] (50), 287 (45), 257 (100), 244 (20),
216 (25), 173 (35). HR-MS for C21H30O3 requires
330.2187; found 330.2183.
3.9. 10-Deoxy-4(18)-epoxy-12-methoxy-4,5-seco-
pisiferan-19-ol (45)
Gum, [a]2D5 +25.8 (CHCl3; c 0.03). TLC (30%
neat
max
EtOAc in hexane) Rf 0.32. IR n
cm 1: 3342, 1605,
1
1580, 1268, 840. H NMR (CDCl3, 300 MHz): d 0.83
(2 H, m, H-3), 1.15 (3 H, d, J=6.8 Hz, H-16), 1.19 (3
H, d, J=6.8 Hz, H-17), 1.27 (3 H, m, H-5, H-6), 1.40
(2 H, m, H-1), 1.60 (1 H, m, H-10), 2.00 (3 H, m, H-5,
H-18), 2.13 (2 H, m, H-2), 2.61 (1 H, d, J=13.1 Hz,
H-20a), 3.09 (1 H, d, J=13.1 Hz, H-20b), 2.70 (2 H,
m, H-7), 3.11 (1 H, d, J=10.6 Hz, H-19), 3.24 (1 H,
sept, J=6.8 Hz, H-15), 3.62 (1 H, d, J=10.6 Hz, H-
19), 3.77 (3 H, s, OMe), 6.60 (1 H, s, H-11), 6.93 (1 H,
s, H-14). 13C NMR (CDCl3, 75 MHz): d 19.8 (C-2),
22.5 (C-16), 22.9 (C-17), 24.0 (C-6), 26.4 (C-15), 26.9

T.-C. Lin et al. / Phytochemistry 51 (1999) 793±801
799
(C-1), 27.8 (C-3), 35.4 (C-7), 38.9 (C-5), 41.8 (C-18),
50.4 (C-20), 55.5 (OMe), 58.4 (C-10), 68.9 (C-19), 70.3
(C-4), 114.2 (C-11), 126.5 (C-14), 133.0 (C-8), 135.6
(C-13), 135.7 (C-9), 155.0 (C-12). EI-MS (70 eV) m/z
(rel. int.): 332 [M]+ (8), 314 (3), 190 (100), 175 (28),
161 (15), 149 (20), 133 (18), 81 (22), 69 (25), 55 (40).
HR-MS for C21H32O3 requires 332.2343; found
332.2340.
44.8 (C-7), 55.9 (OMe), 56.7 (C-5), 61.7 (C-9), 66.8 (C-
19), 74.0 (C-8), 109.5, 113.5, 114.7, 115.6, 122.9, 126.9,
138.7, 144.6 (2 C), 146.8, 147.3, 147.9, 167.5. UV
MeOH
l
nm (e): 220 (13 200). EI-MS (70 eV) m/z (rel.
max
int.): 482 [M]+ (1), 384 (0.5), 288 (1), 271 (2), 202 (2),
177 (100). HR-MS for C30H42O5 requires 482.3021;
found 482.3025.
3.12. 8a-Acetoxylabda-12,14-dien-19-oic acid (56a)
3.10. 8a-Hydroxylabda-13(16),14-dien-19-yl (Z )-4-
hydroxycinnamate (52)
neat
Gum, TLC (40% EtOAc in hexane) Rf 0.34. IR n
max
1
1
cm : 3500±2500, 1760, 1600, 887. H NMR (CDCl3,
400 MHz): d 0.72 (3 H, s, H-20), 1.01 (3 H, s, H-18),
1.24 (3 H, s, H-17), 1.24±1.62 (8 H, m), 1.63±1.85 (2
H, m), 1.89 (1 H, m), 1.72 (3 H, s, H-16), 1.91 (3 H, s,
OAc), 1.98±2.08 (2 H, m), 2.24 (1 H, m), 4.85 (1 H, t,
J=6.4 Hz, H-12), 4.87 (1 H, dd, J=10.4, 4.4 Hz, H-
15), 5.16 (1 H, dd, J=17.2, 4.4 Hz, H-15), 5.73 (1 H,
dd, J=10.4, 17.2 Hz, H-14). 13C NMR (CDCl3, 75
MHz): d 11.8 (C-16), 15.1 (C-20), 18.7 (C-2), 21.0 (C-
17), 23.5 (C-11), 26.9 (C-6), 28.5 (C-18), 29.0 (OAc),
35.1 (C-3), 36.4 (C-7), 37.5 (C-1, C-4), 40.6 (C-10),
49.8 (C-5), 50.2 (C-9), 51.9 (C-8), 110.3 (C-15), 129.7
(C-12), 135.8 (C-13), 148.6 (C-14), 170.3 (OAc), 181.8
(C-19). EI-MS (70 eV) m/z (rel. int.): 362 [M]+ (78),
302 (100), 287 (34), 257 (18), 175 (65), 121 (70), 81
(80).
Solid, m.p. 206±2088C, [a]2D5 +6.5 (MeOH; c 1.65).
neat
1
TLC (35% EtOAc in hexane) Rf 0.30. IR n
cm :
max
3483, 3300, 1680, 1620, 1590, 1500, 1260, 1175. 1H
NMR (CDCl3, 300 MHz): d 0.79 (3 H, s, H-20), 0.92
(3 H, s, H-18), 0.97±1.08 (3 H, m), 1.12 (3 H, s, H-17),
1.22±1.26 (1 H, m), 1.32±1.45 (4 H, m), 1.53±1.58 (1
H, m), 1.63±1.75 (4 H, m), 1.86 (1 H, dd, J=9.0, 2.7
Hz, H-9), 2.26 (1 H, td, J=10.8, 7.1 Hz, H-12), 2.31
(1 H, td, J=11.8, 7.1 Hz, H-12), 3.92(1 H, d, J=11.1
Hz, H-19), 4.18 (1 H, d, J=11.1 Hz, H-19), 4.99 (2 H,
br s, H-16), 5.04 (1 H, d, J=10.7 Hz, H-15), 5.27(1 H,
d, J=17.6 Hz, H-15), 5.79 (1 H, d, J=12.8 Hz, H-8'),
6.33 (1 H, dd, J=10.7, 17.6 Hz, H-14), 6.76 (2 H, d,
J=8.6 Hz), 6.81 (1 H, d, J=12.8 Hz, H-7'), 7.56 (2 H,
d, J=8.6 Hz). 13C NMR (CDCl3, 75 MHz): d 15.9 (C-
20), 18.0 (C-2), 36.2 (C-3), 36.9 (C-4), 21.0 (C-6), 23.8
(C-17), 24.6 (C-11), 27.4 (C-18), 34.9 (C-12), 38.9 (C-
10), 39.5 (C-1), 44.5 (C-7), 56.6 (C-5), 61.6 (C-9), 66.9
(C-19), 74.5 (C-8), 113.5 (C-15), 115.1 (2 C), 115.7 (C-
16), 116.7, 126.9, 132.2 (2 C), 138.7 (C-14), 143.8,
147.2 (C-13), 157.3, 167.2. EI-MS (70 eV) m/z (rel.
int.): 452 [M]+ (0.5), 434 (1), 288 (2.5), 270 (4), 189
(20), 147 (100). HR-MS for C29H40O4 requires
452.2916; found 452.2920.
3.13. (7R,8R )-9'-(b-Rhamnopyranosyl)-3-methoxy-
3':7,4':8-diepoxyneolignan-4,9-diol pentaacetate (73a)
Gum, [a]2D5 25 (CHCl3; c 4.0). TLC (35% Me2CO
in hexane) Rf 0.3. CD (MeOH, nm): [y]368.2 346,
[y]326.8 +45, [y]306.8 79, [y]272.1 26, [y ]256.4 61,
neat
1
[y]244.4 3, [y]236.0 +31, [y ]218.0 36. IR n
cm :
max
1
2939, 1747, 1607, 1594, 1507, 1452. H NMR (CDCl3,
300 MHz): d 1.17 (3 H, d, J=6.1 Hz, H-60), 1.86 (2
H, m, H-8'), 1.94 (3 H, s), 1.99 (6 H, s, 2 Ac), 2.09 (3
H, s), 2.26 (3 H, s), 2.59 (2 H, t, J=6.8 Hz, H-7'),
3.40 (1 H, m, H-9'), 3.62 (1 H, m, H-9'), 3.82 (1 H, m,
H-50), 3.83 (3 H, s, OMe), 3.94 (1 H, dd, J=4.4, 12
Hz, H-9), 4.17 (1 H, m, H-8), 4.29 (1 H, dd, J=3.3, 12
Hz, H-9), 4.66 (1 H, d, J=1.4 Hz, H-10), 4.87 (1 H, d,
J=7.8 Hz, H-7), 5.01 (1 H, dd, J=9.9, 9.9, Hz, H-40),
5.20 (1 H, dd, J=1.4, 3.5 Hz, H-20), 5.29 (1 H, dd,
J=3.5, 9.9 Hz, H-30), 6.69 (1 H, dd, J=1.9, 8.2 Hz,
H-6'), 6.76 (1 H, d, J=1.9 Hz, H-2'), 6.85 (1 H, d,
J=8.2 Hz, H-5'), 6.92 (1 H, br d, J=8.0 Hz, H-5),
6.95 (1 H, br s, H-2), 7.02 (1 H, d, J=8.0 Hz, H-6).
13C NMR (CDCl3, 75 MHz): d 17.2 (C-60), 20.4 (Ac),
20.5 (Ac), 20.6 (3 Ac), 30.7 (C-8'), 31.3 (C-7'), 55.8
(OMe), 62.7 (C-9), 66.1 (C-50), 67.1 (C-9'), 69.0 (C-30),
69.8 (C-20), 70.9 (C-40), 75.2 (C-8), 76.2 (C-7), 97.3 (C-
10), 110.9 (C-2), 116.7 (C-2'), 116.8 (C-5'), 119.7 (C-5),
121.7 (C-6'), 122.9 (C-6), 134.7 (C-1), 134.9 (C-1'),
140.2 (C-4), 140.9 (C-4'), 142.9 (C-3'), 151.4 (C-3),
3.11. 8a-Hydroxylabda-13(16),14-dien-19-yl (E )-4-
hydroxy-3-methoxycinnamate (53)
Solid, m.p. 110±1128C, [a ]2D5 +6.2 (MeOH; c 0.7).
neat
1
cm :
TLC (35% EtOAc in hexane) Rf 0.32. IR n
max
1
3490, 3310, 1675. H NMR (CDCl3, 300 MHz): d 0.82
(3 H, s, H-20), 1.01 (3 H, s, H-18), 0.97±1.08 (3 H, m),
1.13 (3 H, s, H-17), 1.22±1.26 (1 H, m), 1.35±1.50 (4
H, m), 1.53±1.65 (2 H, m), 1.70±1.92 (4 H, m), 2.20±
2.42 (2 H, m), 3.90 (3 H, s, OMe), 3.98 (1 H, d, J=11
Hz, H-19), 4.27 (1 H, d, J=11 Hz, H-19), 4.99 (2 H,
br s, H-16), 5.04 (1 H, d, J=10.7 Hz, H-15), 5.27 (1
H, d, J=17.6 Hz, H-15), 6.25 (1 H, d, J=15.9 Hz),
6.33 (1 H, dd, J=10.7, 17.6 Hz, H-14), 6.89 (1 H, d,
J=8.1 Hz), 7.00 (1 H, d, J=1.7 Hz), 7.05 (1 H, dd,
J=1.7, 8.1 Hz), 7.56 (1 H, d, J=15.9 Hz, H-7'). 13C
NMR (CDCl3, 75 MHz): d 15.9 (C-20), 18.0 (C-2),
20.8 (C-6), 23.7 (C-17), 24.7 (C-11), 27.5 (C-18), 35.0
(C-12), 36.4 (C-3), 37.2 (C-4), 38.9 (C-10), 39.6 (C-1),

800
T.-C. Lin et al. / Phytochemistry 51 (1999) 793±801
Fang, J.-M., Lee, C.-K., & Cheng, Y.-S. (1993). Phytochemistry, 33,
1169.
168.6 (OAc), 169.9 (2 Ac), 170.0 (Ac), 170.3 (Ac).
FAB-MS (NBA) m/z: 702 [M]+. HR-MS for
C35H42O15 requires 702.2511; found 702.2518.
Fang, J.-M., Sheu, C.-M., & Cheng, Y.-S. (1986). Journal of Chinese
Chemical Society, 33, 245.
Fang, J.-M., Sou, Y.-C., Chiu, Y.-H.,
Phytochemistry, 34, 1581.
& Cheng, Y.-S. (1993).
Fang, J.-M., Wei, K.-M., & Cheng, Y.-S. (1985). Journal of Chinese
Chemical Society, 32, 75.
Acknowledgements
Fiaud, J. C., Horeau, A., & Kagan, H. B. (1997). Stereochemistry:
fundamentals and methods, Vol. 3; determination of con®gurations
by chemical methods (pp. 52±94).
We thank the National Science Council for ®nancial
support.
Formiga, M. D. (1976). Phytochemistry, 15, 1547.
Ganeshpure, P. A., & Stevenson, R. (1982). Australian Journal of
Chemistry, 35, 2175.
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