Sesquiterpene constituents from the essential oils of the liverworts Mylia taylorii and Mylia nuda

Article abstract of DOI:10.1016/j.phytochem.2004.04.039

The essential oils and extracts of Mylia taylorii and M. nuda were investigated by gas chromatography, mass spectrometry, NMR spectroscopy and chemical correlations. Beside several known compounds 13 new constituents including three new carbon skeletons could be identified. Four hydrocarbons with a molecular formula of C₁₅H₂₂ (m/z 202) were identified as myli-4(15)-ene (1), aromadendra-1(10),4(15)-diene (19), aromadendra-4,10(14)- diene (20) and aromadendra-4,9-diene (21). Three oxaspiro-compounds were identified as 7-epi-bourbon-3-en-5,11-oxide (22), guai-3,10(14)-dien-5,11-oxide (23) and guai-3,9-dien-5,11-oxide (24). The absolute configuration of myli-4(15)-en-3-one (5) could be established by chemical correlation. Together with α-taylorione (7) the corresponding 6,11-seco-compound taylopyran (25) with a new carbon skeleton was identified which serves as a precursor to taylocyclane (26) and taylofuran (27). Taynudol (28) contains a new carbon skeleton with a cyclobutenyl structure.

Full text of DOI:10.1016/j.phytochem.2004.04.039

PHYTOCHEMISTRY
Phytochemistry 65 (2004) 2277–2291
www.elsevier.com/locate/phytochem
Sesquiterpene constituents from the essential oils of the liverworts
Mylia taylorii and Mylia nuda
a,
Stephan H. von Reuß , Chia-Li Wu , Hermann Muhle , Wilfried A. Konig
b
c
a
*
€
a
Institut f€ur Organische Chemie, Universit€at Hamburg, Martin-Luther-King-Platz 6, D-20146 Hamburg, Germany
Department of Chemistry, Tamkang University, Tamsui, Taiwan
b
c
€
Abteilung Systematische Botanik und Okologie, Universit€at Ulm, D-89081 Ulm, Germany
Received 28 January 2004; received in revised form 26 April 2004
Available online 31 July 2004
Abstract
The essential oils and extracts of Mylia taylorii and M. nuda were investigated by gas chromatography, mass spectrometry, NMR
spectroscopy and chemical correlations. Beside several known compounds 13 new constituents including three new carbon skeletons
could be identified. Four hydrocarbons with a molecular formula of C15H22 (m=z 202) were identified as myli-4(15)-ene (1), aro-
madendra-1(10),4(15)-diene (19), aromadendra-4,10(14)-diene (20) and aromadendra-4,9-diene (21). Three oxaspiro-compounds
were identified as 7-epi-bourbon-3-en-5,11-oxide (22), guai-3,10(14)-dien-5,11-oxide (23) and guai-3,9-dien-5,11-oxide (24). The
absolute configuration of myli-4(15)-en-3-one (5) could be established by chemical correlation. Together with a-taylorione (7) the
corresponding 6,11-seco-compound taylopyran (25) with a new carbon skeleton was identified which serves as a precursor to
taylocyclane (26) and taylofuran (27). Taynudol (28) contains a new carbon skeleton with a cyclobutenyl structure.
ꢀ 2004 Elsevier Ltd. All rights reserved.
Keywords: Mylia taylorii; Mylia nuda; Liverworts; Sesquiterpenoids; Structure elucidation
1. Introduction
1988), ())-3-acetoxytaylorione (8), (+)-maali-4(15)-en-
1b-ol (14), (+)-4(15)-dehydroglobulol (15), (+)-ent-
globulol (16) and others (Matsuo and Takaoka, 1990)
(Scheme 1). In addition, the dimeric sesquiterpenoids
myltaylorione A (33), myltaylorione B (34) and bitayl-
orione (35) (Fig. 4) have been described (Takaoka et al.,
1991). For the related M. nuda Inoue and Yang, which is
endemic to Taiwan, the isolation of 3 and 4, together
with the unique nudenal (17) and nudenoic acid (18)
(Liu et al., 1996; Wu, 1997), as well as labdane diterp-
enoids (Wu and Asakawa, 1987) were reported. In
contrast to the former species, the related M. anomala
and M. verrucosa are known to predominantly contain
diterpenoids with the verrucosane skeleton (Asakawa,
1995; Nagashima and Asakawa, 1998).
The liverwort Mylia taylorii (Hook.) S. Gray (Jun-
germanniaceae) is known as a rich source for unique
sesquiterpenoids with rare skeletons like oxygenated ent-
5,10-cyclo-aromadendranes (3, 4) (myliane skeleton),
ent-1,10-seco-aromadendranes (6, 8) (tayloriane skele-
ton), myltaylanes (9) and cyclomyltaylanes (12) (Asak-
awa, 1995; Nagashima and Asakawa, 1998). Continuous
investigations over the last 30 years, mainly by Matsuo
and Takaoka, have resulted in the isolation and identi-
fication of ())-myliol (3) (Benesova et al., 1971, 1973;
Matsuo et al., 1976; Nozaki, 1979), ())-taylorione (6)
(Matsuo et al., 1974, 1979), ())-dihydromylione A (4)
(Matsuo et al., 1977), ())-myltaylenol (9) (Takaoka
et al., 1985), (+)-cyclomyltaylenol (12) (Takaoka et al.,
In order to clarify the phytochemical relationship
between the sesquiterpenoid bearing M. taylorii and M.
nuda we investigated the essential oils and extracts of
both species from different collection sites by GC-MS.
Thirteen new compounds were isolated and identified by
spectroscopic techniques and chemical correlations.
* Corresponding author. Tel.: +49-40-42838-6088; fax: +49-40-
42838-2893.
E-mail address: s.von.reuss@web.de (S.H. von Reuß).
0031-9422/$ - see front matter ꢀ 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.phytochem.2004.04.039

2278
S.H. von Reuß et al. / Phytochemistry 65 (2004) 2277–2291
14
14
10
14
10
14
H
H
10
10
O
O
1
1
1
1
2
3
3
3
3
AcO
R
5
5
4
4
7
7
5
5
6
4
4
6
6
7
6
7
1
R
15
15
13
15
11
13
11
11
11
13
12
13
12
12
12
6: ∆4(15)
7: ∆3
3: R1 = CH2; R2 = OH, H (3S)
4: R1 = CH3, H (4R); R2 = O
5: R1 = CH2; R2 = O
8
1: ∆4(15)
2: ∆3
OH
OH
14
11
14
11
13
13
H
10
6
1
7
7
10
1
5
R
5
R
5
6
6
5
7
4
1
1
4
7
6
4
4
3
3
2
2
H
H
R
11
R
12
12
11
15
9: R = OH; ∆4(12)
10: R = H; ∆4(12)
11: R = H; ∆4
12: R = OH
13: R = H
14
15: R = CH2
16: R = CH3, H (4S)
17: R = CHO
18: R = COOH
Scheme 1. Sesquiterpene constituents from Mylia.
2. Results and discussion
quantity among the hydrodistillation products, while
larger amounts of 1 could be isolated from n-hexane
extracts by a combination of column chromatography
2.1. M. taylorii
1
and semi-preparative GC. The H NMR spectrum of 1
M. taylorii was collected near Reutte, Tyrol, in the
Austrian Alps. Hydrodistillation of the fresh plant ma-
terial afforded a complex mixture of sesquiterpenoids.
Several known constituents could be identified by com-
parison of their mass spectra and retention indices with a
exhibited an exocyclic methylene group at dH 5.09 (1H,
s) and 5.12 (1H, s), in accordance to signals at 104.7 (t)
and 156.7 (s) in the 13C Pendant spectrum. In addition,
three tertiary methyl groups at dH 0.99 (3H, s), 1.02 (3H,
s) and 1.05 (3H, s), corresponding to carbon signals at
dC 15.1 (q), 15.8 (q) and 30.7 (q), as well as one cyclo-
propyl methine proton at dH 0.53 (1H, dt) were identi-
fied. The 13C Pendant and HMQC spectra indicated
four methylene groups at dC 16.6 (t), 23.6 (t), 32.7 (t) and
34.7 (t), three methine groups at dC 20.1 (d), 22.6 (d),
34.9 (d) and three quaternary carbons at dC 18.6 (s), 22.8
(s) and 37.0 (s), which confirmed the presence of a cy-
clopropyl unit. Considering the molecular formula and
one exocyclic double bond a tetracyclic system had to be
assumed. The H,H correlations in the COSY spectrum
exhibited the characteristic pattern of a 5,10-cyclo-aro-
madendrene, whose partial structures could be con-
nected to a myli-4(15)-ene structure (1) by inspection of
the HMBC spectrum. The relative configuration
(1R*,5S*,6R*,7S*,10S*) was derived from a NOESY
spectrum, which exhibited NOEs between 6-H, 7-H and
12-H3 on one side, and between 13-H3 and 1-H on the
other side of the molecule. 1 represents the exocyclic
double bond isomer of the co-occurring (+)-anastrep-
tene (2) which is widely distributed among the liver-
worts, but unknown from higher plants (Andersen et al.,
1977, 1978; Asakawa, 1995).
€
spectral library (Joulain and Konig, 1998; Hochmuth
et al., 2003) established under identical experimental
conditions (Table 1). The remaining unidentified com-
ponents were selected for isolation by a combination of
column chromatography and preparative thin-layer
chromatography, as well as preparative and semi-pre-
parative gas chromatography using different polysilox-
ane- and modified cyclodextrin columns. A total number
of 30 compounds could be identified by one- and two-
dimensional NMR spectroscopy as well as chemical
correlations (Table 1). Isolated sesquiterpenoids consid-
ered to be specific for the Myliioidae include 3, 4, 6, 8, 9,
12 and 14. In addition to 9 and 12 the corresponding
hydrocarbons 10 (Adio et al., 2002), 11 (Adio, 2004) and
13 (Wu and Chang, 1992) were also detected. Thirteen
new sesquiterpene constituents (1, 5, 7, 19–28) could be
obtained, including four with previously unknown car-
bon skeletons (see Scheme 2).
2.1.1. ())-(1R*,5S*,6R*,7S*,10S*)-Myli-4(15)-ene (1)
An early eluting hydrocarbon 1 with the molecular
formula of C15H22 (m=z 202) was observed in very small

S.H. von Reuß et al. / Phytochemistry 65 (2004) 2277–2291
2279
Table 1
Identified sesquiterpene constituents in Mylia taylorii, Mylia nuda and Kurzia trichoclados listed in their order of elution from the unpolar CPSil-5
column
Kurzia trichoc-
lados
Compound
Mylia taylorii
Mylia nuda
Austria
Germany
Canada
Taiwan
Taiwan
Austria
Cyclomyltaylane (13)
Anastreptene (2)
++ *
+ *
+
+
+
++
++
+
+
++
+
+
+
++
+
Myltayl-4-ene (11)
b-Elemene
a-Barbatene
Tritomarene
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
Myli-4(15)-ene (1)
Bourbon-11-ene
+ *
+
++
+
+
+
+
+
c-Maaliene
+
+
++
Aromadendra-4,10(14)-diene (20)
Isobazzanene
Aromadendrene
+ *
+++ *
+
+
++
+
+++
+
+
b-Barbatene
+
+
+++
+
Myltayl-4(12)-ene (10)
Aromadendra-1(10),4-diene (30)
allo-Aromadendrene
7-epi-Bourbon-3-en-5,11-oxide (22)
b-Chamigrene
++ *
+ *
+
+
+
+
+
+
++
+
++
+
+++ *
+
+
+
+
+
++
++
+
+++ *
++
+ *
+
++
+
Taylocyclane (26)
Germacrene D
+
+
+
+
+
+
+
Ledene
ent-Bicyclogermacrene
b-Himachalene
+++ *
+ *
+++
+
++ *
+
+
+
++
a-Chamigrene
+
++
+
Aromadendra-1(10),4(15)-diene (19)
Guai-3,9-dien-5,11-oxide (24)
b-Bazzanene
c-Cuprenene
Aromadendra-4,9-diene (21)
Taylopyran (25)
+++ *
+ *
++
++
+
++
++
+
+
+
+
+ *
++
+++
+
+
+++ *
+
+ *
++
+
+
+
d-Cuprenene
Guai-3,10(14)-dien-5,11-oxide (23)
Spathulenol
+
+
++
++
+
+
4-Dehydroviridiflorol (29)
ent-Globulol (16)
4(15)-Dehydroglobulol (15)
Dihydromylione A (4)
a-Taylorione (7)
+++ *
++ *
++ *
+++ *
++ *
+
++
++
+
+++
++
+
+
+++
++
+ *
+
++
+++ *
++
+
+++
+
+
++
+
Rosifoliol
Myliol (3)
Taylorione (6)
+
+
+
+
+++ *
++ *
++ *
++ *
+++ *
++ *
+ *
+++
++
++
++
+++
+
+++
+++ *
+
++ *
+
+++
+
Myli-4(15)-en-3-one (5)
Maali-4(15)-en-1-ol (14)
Cyclomyltaylenol (12)
Taylofuran (27)
+++ *
+++
+
+
+++
+
+
++
++
+
+
Taynudol (28)
Myltaylenol (9)
3-Acetoxytaylorione (8)
+
+ *
+
+
+++ *
Additional sesquiterpene constituents
+
+
++
+
++
+++
Bold letters designate new compounds; +, ++, +++ represent relative concentrations; *, identified by NMR spectroscopy.
2.1.2. (+)-(5S*,6S*,7S*)-Aromadendra-1(10),4(15)-
diene (19)
Another hydrocarbon with a molecular formula of
C15H22 (m=z 202) was observed as a major constituent in
the hydrodistillation products. However, in n-hexane
extracts rich in 1 the amount of 19 was comparatively
low, suggesting the presence of a rearrangement product
of the highly labile myli-4(15)-ene (1). From the essen-
tial oil the isolation of 19 was achieved by column
chromatography and preparative GC. The 1H NMR

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S.H. von Reuß et al. / Phytochemistry 65 (2004) 2277–2291
14
14
14
14
H
H
H
10
10
10
9
10
6
1
1
1
1
3
3
5
5
5
5
4
7
7
7
7
6
6
4
4
4
H
O
O
H
13
15
11
15
15
15
11
13
13
11
11
13
12
12
12
12
20: ∆10(14)
21: ∆9
19
22
23: ∆10(14)
24: ∆9
14
14
10
OH
H
1
9
14
10
3
9
7
O
10
1
5
1
6
1
3
3
5
12
11
4
5
7
5
6
4
O
7
6
4
7
4
15
6
11
10
O
H
13
12
13
15
15
15
O
13
11
11
12
13
12
14
25
26
27
28
Scheme 2. New sesquiterpene constituents from Mylia.
spectrum showed signals for one exocyclic methylene
group at dH 4.92 (1H, s,br) and 5.02 (1H, d,br) in
agreement with carbon signals at dC 104.9 (t) and 158.2
(s) in the 13C Pendant spectrum which also indicated an
internal double bond at dC 126.8 (s) and 137.3 (s). One
broad singlet signal at dH 1.54 (3H, s,br) could be at-
tributed to an olefinic methyl group, which, together
with two tertiary methyl groups at dH 1.05 (3H, s) and
1.12 (3H, s), corresponded to carbon signals at dC 16.0
(q), 22.0 (q) and 29.1 (q). In addition, two cyclopropyl
methine protons at dH 0.59 (1H, m) and 0.89 (1H, dd)
and one allylic methine group at dH 3.04 (1H, d,br)
could be identified. The 13C Pendant and HMQC spec-
tra indicated the presence of four methylene groups at
dC 23.6 (t), 31.8 (t), 32.9 (t), 37.0 (t), three methine
groups at dC 26.9 (d), 35.2 (d), 42.7 (d) and one qua-
ternary cyclopropyl carbon at dC 19.1 (s). Inspection of
the COSY spectrum indicated an ethylene bridge adja-
cent to three consecutive methine groups, with two of
them being part of the cyclopropyl ring with a geminal
dimethyl substitution. Together with the remaining
ethylene bridge which exhibited a single multiplet signal
in the 1H NMR spectrum and lacked any cross peaks in
the COSY spectrum, the two partial structures could be
connected according to their HMBC correlations to
reveal an aromadendra-1(10),4(15)-diene structure (19).
The relative configuration was obtained from a NOESY
spectrum which exhibited NOEs between the
methyl group 12-H3 and both cyclopropyl methine
protons 6-H and 7-H, indicating a (Z)-fused cyclopropyl
ring. The adjacent methyl group 13-H3 on the opposite
side of the molecule exhibited a NOE with the allylic
methine proton 5-H, leading to the relative
2.1.3. (+)-(1S,6R,7S)-Aromadendra-4,10(14)-diene (20)
Although 20 co-elutes with isobazzanene on various
stationary phases, separation could be achieved by
preparative GC with two different cyclodextrin columns.
1
The H NMR spectrum exhibited an exocyclic methy-
lene group at dH 5.01 (2H, s,br), in agreement with
carbon signals at dC 108.0 (t) and 150.4 (s) in the 13C
NMR spectra, which also indicated an internal double
bond at dC 136.1 (s) and 137.9 (s). One olefinic methyl
group at dH 1.65 (3H, s,br) and two tertiary methyl
groups at dH 0.87 (3H, s) and 1.08 (3H, s) corresponded
to carbon signals at dC 15.1 (q), 16.7 (q), 29.0 (q). Fur-
thermore, one allylic methine group at dH 3.07 (1H, s,br)
could be identified. Inspection of COSY and HMQC
spectra allowed the construction of a consecutive partial
structure that could be connected to afford 20 in
agreement with the long-range COSY, HMBC and
NOESY correlations. The absolute configuration of 20
was determined by a chemical correlation with (+)-de-
hydroviridiflorol (29) of known absolute configuration
(Warmers et al., 1998) as shown in Fig. 1.
2.1.4. (1S,6R,7S)-Aromadendra-4,9-diene (21)
1
The H NMR spectrum of 21 is similar to 20 but
exhibited an olefinic proton at dH 5.73 (1H, t,br) in
agreement with signals for an endocyclic double bond at
dC 124.2 (d) and 138.8 (s) in the 13C NMR spectra which
also indicated another internal double bond at dC 131.7
(s) and 135.4 (s). Two olefinic methyl groups at dH 1.69
(3H, d) and 1.72 (3H, d) and two tertiary methyl groups
at dH 0.96 (3H, s) and 1.09 (3H, s) corresponded to
carbon signals at dC 14.9 (q), 16.7 (q), 21.4 (q) and 29.4
(q). The resulting structure and relative configuration of
21 is in agreement with the COSY, HMBC and NOESY
spectra. In addition to 20 and 21 the corresponding
configuration of
1(10),4(15)-diene (19).
a
(5S*,6S*,7S*)-aromadendra-

S.H. von Reuß et al. / Phytochemistry 65 (2004) 2277–2291
2281
14
14
14
14
OH
ClSO2CH3
pyridine
H
H
H
1
10
10
9
10
10
1
1
1
+
+
5
5
5
5
7
7
7
7
6
6
6
6
4
4
4
4
0 ˚C to rt
15
15
15
15
13
13
13
13
11
11
11
11
12
12
12
12
29
20
21
30
Fig. 1. Dehydration of (+)-4-dehydroviridiflorol (29).
double bond isomer ())-(6R,7S)-aromadendra-1(10),4-
diene (30), previously described (without stereochemical
information) from Myroxylon balsamum, Fabaceae
(Friedel and Matusch, 1987), was obtained. 30 was also
detected as the major dehydration product of the co-
occurring (+)-4-dehydroviridiflorol (29) together with
small amounts of (20) and (21) (Fig. 1). GC-MS inves-
tigations of various liverworts have shown 20, 21 and 30
to be prominent in Diplophyllum plicatum, D. albicans
The relative configurations at C-5 and C-7 were derived
from NOEs between the olefinic methyl group 15-H3,
the methine proton 6-H, the tertiary methyl group 12-H3
and the methine proton 7-H on one side of the molecule
and between the remaining methyl group 13-H3 and the
methine proton 1-H on the opposite side of the mole-
cule. 22 represents the first oxacyclic sesquiterpenoid
with the bourbonane skeleton and exhibits the formerly
unknown 7-epi-configuration.
€
and Barbilophozia species (Konig et al., 2003).
2.1.6.
oxide (23)
(+)-(1S*,5S*,7S*)-Guai-3,10(14)-dien-5,11-
2.1.5. ())-(1S*,5S*,6S*,7S*,10S*)-7-epi-Bourbon-3-en-
5,11-oxide (22)
The first polar fraction afforded two oxacyclic ses-
quiterpenoids (23, 24) present as minor constituents,
which could be isolated by preparative GC. HRMS es-
tablished a molecular formula of C15H22O. The 1H
NMR spectrum of 23 exhibited signals for one olefinic
proton at dH 5.34 (1H, s,br) and one exocyclic methylene
group at dH 4.81 (1H, t) and 4.91 (1H, s,br), in agree-
ment with an endocyclic double bond at dC 124.4 (d) and
144.2 (s) and an exocyclic double bond at dC 110.9 (t)
and 151.8 (s) in the 13C NMR spectra. One olefinic
methyl group at dH 1.73 (3H, m) and two tertiary methyl
groups at dH 1.10 (3H, s) and 1.30 (3H, s) corresponded
to carbon signals at dC 12.9 (q), 23.5 (q) and 31.3 (q). In
addition, one allylic methine group at dH 3.04 (1H, dd)
could be identified, whereas the 13C NMR and HMQC
spectra indicated four methylene groups at dC 31.7 (t),
32.5 (t), 34.7 (t), 35.1 (t), two methine groups at dC 45.6
(d) and 58.7 (d) and two quaternary carbons at dC 82.3
(s) and 94.9 (s). Considering the molecular formula and
the two identified double bonds a tricyclic structure
could be expected, while the chemical shifts of the
quaternary carbons implied an oxacyclic substructure.
By inspection of the COSY spectrum a consecutive
partial structure was elucidated, which could be con-
nected with the remaining two quaternary carbons
according to their HMBC correlations to give a guai-
3,10(14)-diene-5,11-oxide structure (23). The relative
configuration was derived from a NOESY spectrum.
NOEs between the olefinic methyl group 15-H3, a
methylene bridge proton 6-H1, one tertiary methyl
group 12-H3 and the bridgehead proton 7-H indicated
the location of these protons on the same side of the
molecule. The remaining methyl group 13-H3 on the
As a major constituent of the essential oil of
M. taylorii 22 was isolated from an early polar fraction
by preparative GC. HRMS afforded the molecular for-
mula C15H22O. The 1H NMR spectrum allowed the
identification of one olefinic proton at dH 5.42 (1H, s) in
agreement with an endocyclic double bond at dC 128.8
(d) and 141.71 (s) in the 13C Pendant spectrum. One
olefinic methyl group at dH 1.74 (3H, d) and three ter-
tiary methyl groups at dH 0.95 (3H, s), 1.10 (3H, s) and
1.33 (3H, s) corresponded with carbon signals at dC 12.3
(q), 19.9 (q), 24.1 (q) and 31.3 (q). Furthermore the 13C
Pendant spectrum indicated three methylene groups at
dC 27.5 (t), 31.9 (t) and 43.9 (t), three methine groups at
dC 48.2 (d), 54.3 (d) and 58.5 (d) together with three
quaternary carbons at dC 39.8 (s), 85.8 (s) and 91.7 (s).
Considering the molecular formula a tetracyclic com-
pound was assumed, while the chemical shifts of two
quaternary carbons pointed towards the presence of an
oxacyclic substructure.
The COSY spectrum allowed the identification of two
partial structures together with a geminal dimethyl
group derived from intensive 4J-W-H,H-correlations.
From the HMBC spectrum the location of these methyl
groups adjacent to the oxacyclic ring was clarified. Ad-
ditional correlations provided the connectivities of the
three quaternary carbons to reveal a bourbon-3-en-
5,11-oxide structure (22). The 1,10-(E)-fusion of the
4
bourbonane skeleton was evident from the J-W-H,H-
correlation between 1-H and the methyl group 14-H3 in
the COSY spectrum and the spatial interaction between
1-H and 9-H in a NOESY spectrum. Additional NOEs
between 14-H3 and 6-H indicated the 6,10-(Z)-fusion.

2282
S.H. von Reuß et al. / Phytochemistry 65 (2004) 2277–2291
opposite side exhibited a NOE with an allylic methylene
proton 9-H1 which again showed a NOE with the allylic
methine proton 1-H, thus establishing the relative con-
figuration of 23 to be a (1S*,5S*,7S*)-guai-3,10(14)-
dien-5,11-oxide.
with 4 during column chromatographic prefractiona-
tion, 5 could be isolated by preparative GC. HRMS
afforded a molecular formula of C15H20O. In the 1H
NMR spectrum two olefinic protons at dH 5.09 (1H, s)
and 6.28 (1H, s) were identified, which corresponded to
an exocyclic double bond at dC 115.2 (t) and 149.7 (s) in
conjugation to a carbonyl group at dC 204.7 (s) in the
13C NMR spectra. In addition, three tertiary methyl
groups at dH 0.72 (3H, s), 0.88 (3H, s) and 0.97 (3H, s),
in agreement with carbon signals at dC 14.9 (q), 15.2 (q)
and 30.6 (q), could be identified. Three cyclopropyl
methine protons at dH 0.51 (1H, dt), 0.98 (1H, d) and
1.28 (1H, d) corresponded to signals at dC 20.5 (d), 22.1
(d), 25.8 (d) in the 13C NMR and HMQC spectra which
also indicated three additional methylene groups at dC
16.1 (t), 31.9 (t) and 37.0 (t) and three quaternary car-
bons at dC 19.2 (s), 25.5 (s) and 33.0 (s). Considering the
molecular formula, a tetracyclic skeleton had to be as-
sumed. Inspection of the COSY spectrum revealed a
close similarity to the 5,10-cyclo-aromadendranes and
together with the HMBC spectrum structure 5 could be
identified. Its relative configuration was established
from a NOESY spectrum, while the absolute configu-
ration was determined by chemical correlation (Fig. 3)
with 3 and 4 of known absolute configuration (Matsuo
et al., 1976, 1977; Nozaki, 1979). 5 has already been
proposed as a natural precursor for the dimeric myl-
tayloriones 33 and 34 (Fig. 4) (Asakawa, 1995).
2.1.7. ())-(1S*,5S*,7S*)-Guai-3,9-dien-5,11-oxide (24)
The H NMR spectrum of 24 was similar to 23 but
1
exhibited two olefinic protons at dH 5.17 (1H, s,br) and
5.34 (1H, s,br) in agreement with two endocyclic double
bonds at dC 120.6 (d), 123.3 (d), 135.0 (s) and 145.9 (s) in
the 13C Pendant spectrum. Two olefinic methyl groups
at dH 1.63 (3H, d) and 1.77 (3H, t) together with two
tertiary methyl groups at dH 1.18 (3H, s) and 1.32 (3H, s)
corresponded to carbon signals at dC 11.8 (q), 25.7 (q),
26.2 (q) and 31.6 (q). In addition one allylic methine
group at dH 2.85 (1H, t,br) could be identified. The re-
sulting structure of a guai-3,9-dien-5,11-oxide 24 is in
agreement with the COSY and HMBC correlations.
Although the stereochemistry at 5-C and 7-C was evi-
dent from the NOESY spectrum, an unambiguous rel-
ative configuration for 1-C could not be derived due to
missing correlations. The relative configuration of 24
was therefore determined by a chemical correlation with
23 (Fig. 2). Upon palladium catalysed hydrogenation 23
and 24 gave the same guai-3-en-5,11-oxide (31) and
guaiaoxide (32) identified by GC-MS, which implied the
relative configuration at 1-C of 23 and 24 to be identical.
While various guai-5,11-oxides are known from higher
plants (Hirota et al., 1975, 1980; Oyedeji et al., 1998),
their occurrence among the liverworts has not been re-
ported previously.
2.1.9. ())-(6R,7S)-a-Taylorione (7)
In addition to taylorione (6) a second constituent
(7) with a similar mass spectrum was detected in the es-
sential oil of M. taylorii. The isolation of 7 was
troublesome, because it partially rearranged to 6 during
preparative gas chromatography. Therefore, 7 was en-
riched by repeated column chromatography and finally
isolated by preparative thin-layer chromatography. The
1H and 13C NMR spectra of 7 were similar to 6 and
2.1.8. ())-(1S,5R,6R,7S,10S)-Myli-4(15)-en-3-one (5)
In addition to 3, 4 and the corresponding hydrocar-
bons 1 and 2, another oxygenated ent-5,10-cyclo-aro-
madendrane type compound with a molecular ion signal
at m=z 216 (5) could be identified. Co-eluting together
14
H
10
1
3
5
7
14
14
4
O
H
H
H2
Pd / C
H2
Pd / C
15
11
13
10
10
12
1
1
3
23
5
4
5
7
7
4
14
O
O
15
15
11
13
H
11
13
10
9
12
12
1
31
32
3
5
7
4
O
15
11
13
12
24
Fig. 2. Chemical correlation of the guaidien-5,11-oxides (23,24).

S.H. von Reuß et al. / Phytochemistry 65 (2004) 2277–2291
2283
H
pyridinium
dichromate
H
H
10
10
10
H2
Pd / C
1
1
1
3
3
3
HO
O
O
5
5
5
4
4
4
7
7
7
6
6
6
CHCl3
11
11
11
3
5
4
Fig. 3. Chemical correlation of ())-myli-4(15)-en-3-one (5) with ())-myliol (3) and ())-dihydromylione A (4).
H
10
1
3
O
5
10'
4
7
6
10'
O
H
H
10
10
7'
6'
O
1'
11
11'
1
1
3
3
O
O
5'
5
5
14
10
5
4
4
2'
7
7
7'
+
6
Diels-Alder
6
4'
6'
O
11'
4'
5'
H
5'
H
1'
3'
1'
11
11
1
14
3
5
4'
10
11'
4
3'
6
7
O
6'
7'
1
O
15
3
11
13
12
5
10'
6
7
4
15
33
34
35
11
13
12
7
non Diels-Alder reaction
with ∆1,4 isomer
Fig. 4. Proposed biogenesis of dimeric myltayloriones (33,34) by Diels–Alder addition between 5 and 7.
14
14
10
exhibited signals for a (Z)-fused geminal dimethyl cy-
clopropyl unit and a methyl group adjacent to a carbonyl
group. Within the cyclopentyl moiety, however, two
olefinic protons at dH 6.01 (1H, s,br) and 6.04 (1H, s,br)
and one olefinic methyl group at dH 1.95 (3H, d) were
identified, in agreement with the assignment of two en-
docyclic double bonds at dC 127.3 (d), 127.7 (d), 136.6 (s)
and 144.5 (s) in the 13C NMR spectra, respectively. These
data implied a taylori-1(5),3-dien-10-one structure called
a-taylorione (7), which was also supported by the COSY
and HMBC spectra. Compound 7, together with 5, has
already been proposed as a natural precursor for the
dimeric myltayloriones 33 and 34 which are their Diels–
Alder adducts, while the identification of bitaylorione
(35) indicates the presence of additional unidentified
double bond isomers with tayloriane skeleton (Fig. 4)
(Takaoka et al., 1991; Asakawa, 1995). In order to es-
tablish the absolute configuration of 7 we investigated
the acid catalysed rearrangement of ())-(6R,7S)-tayl-
orione (6) with known stereochemistry (Matsuo et al.,
1979; Nakayama et al., 1979) utilizing the acidic ion
exchange resin amberlystꢁ 15. In addition to some un-
known compounds ())-(6R,7S)-a-taylorione (7), identi-
cal to the natural product, could be identified (Fig. 5).
10
O
O
(H+)
1
1
3
4
5
5
6
7
6
6
6
7
4
15
15
11
11
13
13
12
12
6
7
(H+)
9
1
14
(H+)
3
10
1
6
3
5
7
5
12
11
4
O
7
4
15
11
10
13
12
15
13
O
14
26
25
+ H2O (H+)
+ H2O (H+)
14
10
14
10
O
O
1
1
3
3
5
5
6
7
4
7
4
O
O
15
15
13
13
11
11
12
12
36
27
2.1.10. ())-(7S)-(E)-Taylopyran (25)
In addition to 7 a large quantity of an unknown
compound 25 with a molecular ion signal at m=z 218 and
Fig. 5. Chemical correlation and proposed biogenetic pathway from 6
via 7 and 25 to 26, 27 and 36.

2284
S.H. von Reuß et al. / Phytochemistry 65 (2004) 2277–2291
a predominating base peak at m=z 148 was detected
among the acid catalysed rearrangement products of 6,
which was also present in the essential oils of M. taylorii
and M. nuda. Upon chromatographic prefractionation
25 appeared to be highly polar when eluting after the
sesquiterpene alcohols, although its GC retention time
was comparatively low. While 25 was stable to isolation
by preparative GC using polysiloxane SE-30, complete
decomposition to a large number of unknown com-
pounds was observed upon storage at elevated temper-
atures and even at 7 ꢂC in benzene. HRMS confirmed
the molecular formula C15H22O. From the 1H NMR
spectrum two olefinic protons at dH 5.12 (1H, d) and
5.62 (1H, s) were identified in agreement with carbon
signals for two endocyclic double bonds at dC 118.2 (d),
133.9 (d), 140.6 (s) and 148.8 (s). The observed chemical
shifts of a methine group at dH 4.50 (1H, s,br) and dC
93.9 (d), together with two quaternary carbons at dC
76.8 (s) and 149.2 (s), indicated the presence of an
enolether moiety and consequently a bicyclic system had
to be assumed. In addition, two olefinic methyl groups
at dH 1.68 (3H, d) and 1.81 (3H, s,br) and two tertiary
methyl groups at dH 1.23 (3H, s) and 1.34 (3H, s) were
identified which corresponded to carbon signals at dC
13.1 (q), 21.0 (q), 21.3 (q) and 28.0 (q). Furthermore, the
remaining two allylic methylene groups at dH 2.21 (2H,
m) and 2.41 (2H, m), as well as one anisochoric methy-
lene group with the geminal coupling constant 2J ¼ 17:0
Hz at dH 1.91 (1H, ddt) and 2.11 (1H, d,br) adjacent to a
stereogenic methine group at dH 2.48 (1H, dt) could be
identified, in agreement with the assignment of the 13C
Pendant signals at dC 26.5 (t), 27.9 (t), 30.4 (t) and 42.7
(d). The COSY spectrum allowed the construction of
two partial structures, whereas a geminal dimethyl
group was evident from 4J-W-H,H-correlations. In-
spection of the HMBC spectrum confirmed the location
of these methyl groups adjacent to the quaternary car-
bon of the enolether. The resulting structure of 25 is in
accordance with the predominance of the corresponding
Retro-Diels–Alder fragment ion [M–H2C@CHCO-
CH3]þ at m=z 148 as shown by HRMS. The new carbon
skeleton of 25 represents a 6,11-seco-taylori-3,5,9-trien-
10,11-oxide structure which we called taylopyran. The
(E)-configuration was derived from spatial interactions
between the olefinic methine proton 6-H and the cy-
clopentenyl methyl group 15-H3 and between the me-
thine proton of the dihydropyran unit 7-H and the
methylene protons of the cyclopentenyl fragment 1-H2
in the NOESY spectrum (Fig. 6). Additional NOEs in-
dicated the presence of at least two conformers for 25.
NOEs between 8-HðSiÞ,12-H3ðReÞ and 6-H, as well as 13-
H3ðSiÞ and 1-H are specific for an equatorial conforma-
tion at 7-C, while NOEs between 8-HðReÞ and 13-H3ðSiÞ
as well as 12-H3ðReÞ, 7-H and 1-H are specific for an axial
conformation at 7-C. The (E)-configuration of 25 cor-
responds to the preferred conformation of the presumed
Fig. 6. Molecular model (AM1,MOPAC) of ())-25 with relevant
NOEs.
precursors 6 and 7, as shown by inspection of their
NOESY spectra in combination with semi-empirical
molecular modelling using MOPAC. The absolute
configuration of 25 was derived from the identity of the
natural product with ())-(7S)-(E)-taylopyran obtained
by rearrangement of ())-(6R,7S)-taylorione (6) with
known absolute configuration (Matsuo et al., 1979;
Nakayama et al., 1979) (Fig. 5). The dihydropyran
substructure of 25 readily added alcohols under
acidic conditions to form diastereomeric mixtures of
acetals and is believed to react reversibly with free hy-
droxyl functions of the silica gel, thus explaining the
very low retention factor observed during column
chromatography.
2.1.11. ())-(6S,7S,10R)-Taylocyclane (26)
Among the acid catalysed rearrangement products of
6 another constituent, called taylocyclane (26), with a
similar mass spectrum to 6 and 7, was detected by GC-
MS. 26 was also present in small quantities (about 1% of
the total volatiles) among the hydrodistillation products
of M. taylorii and could be isolated from a slightly polar
fraction by preparative GC. HRMS afforded the mo-
lecular formula C15H22O. The 1H and 13C NMR spectra
exhibited some similarities with 7, as far as the methyl-
cyclopentadienyl moiety is concerned, but lacked any
evidence for a cyclopropyl substructure or a carbonyl
1
group. In the H NMR spectrum two olefinic methine
protons at dH 5.89 (1H, s) and 6.00 (1H, s) were iden-
tified in agreement with the assignment of two endocy-
clic double bonds at dC 127.0 (d), 128.1 (d), 143.7 (s) and
144.3 (s). One olefinic methyl group at dH 1.91 (3H, s)
and three tertiary methyl groups at dH 1.24 (3H, s), 1.25
(3H, s) and 1.47 (3H, s) corresponded to carbon signals
at dC 14.6 (q), 19.0 (q), 26.3 (q) and 29.7 (q). In addition,
one methine proton at dH 3.00 (1H, s,br) could be
1
identified in the H NMR spectrum, whereas the 13C
Pendant and HMQC spectra indicated the presence of
three methylene groups at dC 23.3 (t), 34.2 (t) and 39.9
(t), two methine groups at dC 51.2 (d) and 52.4 (d) and
two quaternary carbons at dC 78.0 (s), 86.5 (s). Con-

S.H. von Reuß et al. / Phytochemistry 65 (2004) 2277–2291
2285
sidering the five units of unsaturation for the molecular
docyclic double bond at dC 126.6 (d), 143.4 (s) in the 13
C
Pendant spectrum. Two tertiary methyl groups at dH
0.98 (3H, s), 1.27 (3H, s), one olefinic methyl group at
dH 1.72 (3H, d) and one methyl group at 1.68 (3H, s),
adjacent to a carbonyl group at dC 205.7 (s), corre-
sponded to carbon signals at dC 12.0 (q), 24.3 (q), 29.4
(q) and 29.9 (q), respectively. In addition, the 13C Pen-
dant and HMQC spectra indicated five methylene
groups at dC 24.0 (t), 29.0 (t), 39.7 (t), 41.0 (t), 42.8 (t),
one methine group at dC 48.7 (d) and two quaternary
carbons at dC 81.6 (s) and 92.9 (s). That led to the
molecular formula C15H24O and confirmed that 27 is
not an alcohol. Considering the four units of unsatura-
tion, the identification of one C,C– and one C,O–
double bond implied a bicyclic structure, while the
chemical shifts of the quaternary carbons indicated the
presence of an oxacyclic substructure. From the COSY
spectrum two partial structures could be identified.
HMBC correlations provided the connectivities of the
quaternary carbons to reveal an oxaspiro compound
with a 6,11-seco-taylori-3-en-10-on-5,11-oxide structure
(27) called taylofuran. 27 can be considered as a hy-
dration product of 25 by addition of water to the
enolether group and cleavage of the pyran ring under
formation of the carbonyl group followed by an acid
catalysed cyclisation of the resulting intermediate. The
relative configuration (5S*,7S*) was derived from care-
ful inspection of a NOESY spectrum. A second com-
pound with identical mass spectrum was also detected
by GC-MS and most likely represents the diastereomeric
(5R*,7S*)-taylofuran (36) (Fig. 5). Considering the
probable artificial nature of 7, 25, 26 and 27 we inves-
tigated n-hexane, dichloromethane, diethyl ether and
methanol extracts of crushed and intact M. taylorii and
M. nuda plant material by GC-MS and were able to
identify the questionable components as well. The mild
isolation conditions applied support the authentic
presence of these compounds as natural constituents of
M. taylorii and M. nuda.
formula C15H22O a tricyclic system was assumed, while
the chemical shifts of the two quaternary carbons con-
firmed the presence of an oxacyclic substructure. In-
spection of the COSY spectrum revealed two adjacent
methine groups with a connectivity to an ethylene
bridge. The resulting partial structures were connected
according to their HMBC correlations to reveal a new
carbon skeleton with a 6,11-seco-6,10-cyclo-tayloridien-
10,11-oxide structure (26), that was named taylocyclane.
The relative configuration (6S*,7S*,10R*) was derived
4
from the J-W-H,H-coupling correlations between the
axial protons of the ethylene bridge 8-Hax and 9-Hax and
the allylic methine proton 6-H in the COSY spectrum, in
agreement with spatial interactions between 6-H and the
equatorial methyl group 12-H3 and between the olefinic
proton 1-H, an equatorial proton of the ethylene bridge
9-Heq and the bridgehead methyl group 14-H3 in the
NOESY spectrum (Fig. 7). 26 most likely originates
from cyclisation of 25, present in part as the axial con-
former, which fulfils the stereochemical requirements
(Fig. 5).
2.1.12. (5S*,7S*)-Taylofuran (27)
In addition to 7, 25 and 26 another sesquiterpenoid
(27) was detected in small quantities among the rear-
rangement products of 6, which was also present in the
essential oil of Mylia and could be isolated from an al-
cohol fraction by repeated column chromatography and
semi-preparative GC. Surprisingly the mass spectrum of
27 exhibited a molecular ion signal at m=z 236 and was
attributed the molecular formula C15H24O2 by HRMS.
1
The H NMR spectrum displayed one olefinic methine
proton at dH 5.40 (1H, s,br) in agreement with an en-
2.1.13. (1R*,4S*,5S*,6R*,7S*,9R*)-Taynudol (28)
From an enriched alcohol fraction the tricyclic
taynudol with a 2,5,8-trimethyl-decahydro-cyclobuta-
[e]azulene skeleton (28) was obtained by a combination
of repeated column chromatography and semi-pre-
parative GC. By HRMS the molecular formula
1
C15H22O was established. From the H NMR spectrum
one olefinic methine proton at dH 5.76 (1H, s,br) and
two exocyclic methylene protons at dH 4.81 (1H, s,br)
and 4.83 (1H, s,br) were identified, which corresponded
to an endocyclic double bond with carbon signals at dC
132.3 (d) and 147.6 (s) and an exocyclic double bond
with absorptions at dC 111.4 (t) and 153.7 (s) in the 13C
Pendant spectrum. In addition, one olefinic methyl
group at dH 1.49 (3H, d) and one secondary methyl
group at dH 0.93 (3H, d, J ¼ 7:3 Hz) could be identified
Fig. 7. Molecular model (AM1,MOPAC) of ())-26 with relevant
NOEs.

2286
S.H. von Reuß et al. / Phytochemistry 65 (2004) 2277–2291
in agreement with carbon signals at dC 14.3 (q) and 17.2
(q). Furthermore, the 1H NMR spectrum exhibited a
methine proton at dH 4.03 (1H, dd) which corresponded
to a hydroxy methine group at dC 77.2 (d), as well as two
characteristic broad doublet signals at dH 2.48 (1H, d,br)
and 2.55 (1H, d,br). The 13C Pendant and HMQC
spectra indicated five methine groups at dC 38.2 (d), 41.2
(d), 41.6 (d), dC 44.1 (d), 45.3 (d) and additional three
methylene groups at dC 28.3 (t), 32.7 (t) and 33.6 (t). All
together these CH-fragments added up to the molecular
formula C15H21 which supported the presence of a tri-
cyclic sesquiterpene alcohol. The observation of only
one exocyclic methylene and two methyl groups strongly
suggested an unusual skeleton and from the coupling
correlations of COSY and HMBC spectra the new
2,8-dimethyl-5-methylene-2a,3,4,5,5a,6,7,8,8a,8b-decahy-
dro-cyclobuta[e]azulen-4-ol structure, called taynudol
(28), could be identified. The cyclobutenyl moiety was
evident from the long-range coupling correlations be-
tween the olefinic methyl group 13-H3 and both cy-
clobutenyl methine protons 6-H, 7-H, while the olefinic
cyclobutenyl proton 12-H lacked any coupling correla-
tion except with 13-H3. The position of the olefinic
methyl group was consequently confirmed by the
HMBC correlations to 7-C. The observed chemical
shifts and coupling constants within the cyclobutenyl
moiety are in agreement with reported values (Bernart
et al., 1993). The (Z)-configuration of the cyclobutenyl
ring was evident on the basis of the vicinal coupling
constants of J ¼ 13:9 Hz (6-H, d,br) and J ¼ 12:3 Hz
(7-H, d,br) (Bernart et al., 1993) and could be confirmed
by the spatial interaction between 5-H und 8-HRe in the
NOESY spectrum (Fig. 8). Additional NOEs, observed
between 6-H, 15-H3, 2-HRe and 14-HE, as well as NOEs
between 14-HZ, 9-H and 7-H indicated a (Z)-decahy-
droazulene configuration in (1R*,4S*,5S*,6R*,7S*,
9R*)-taynudol (28). The new carbon skeleton of 28
most likely originates from a guai-11-enyl-6-carbenium
ion.
2.2. M. nuda
M. nuda was collected near Yuen-yang lake, Ilan
county (Taiwan). Hydrodistillation of the fresh plant
material afforded a complex sesquiterpenoid mixture
with similar constituents as M. taylorii (Table 1). This
high similarity in essential oil composition was con-
firmed by a comprehensive GC-MS investigation of
M. taylorii samples from the Austrian Alps (Tyrol),
€
German Alps (Allgau) and Jervis Inlet (Canada), to-
gether with samples of M. nuda from Yuen-yang lake
and Taiping Shan (Taiwan) (Table 1).
Nudenal (17) and nudenoic acid (18), previously
considered as specific markers for M. nuda (Asakawa,
1995, Nagashima and Asakawa, 1998), could not be
detected, while labdane diterpenoids were identified in
varying amounts in additional samples of both M. tayl-
orii and M. nuda from Yuen-yang lake and Taiping
Shan (Taiwan) (data not shown). 8 was only present in
Canadian M. taylorii. Beside quantitative differences in
essential oil composition all the M. nuda samples in-
vestigated were found to lack barbatene-, isobazzanene-,
chamigrene-, cuprenene-, myltaylene- and cyclomyltay-
lane-type compounds (Table 1). A variety of sesquit-
erpenoids formerly believed to be specific markers for
the Myliioidae like 3, 4, 6, 12 and 14, as well as the new
22 and 25 were also detected in the essential oil of Kurzia
trichoclados, Lepidoziaceae (Table 1).
3. Experimental
3.1. General experimental procedures
3.1.1. GC, GC-MS and GC-HRMS
Gas chromatograms were run using a Carlo Erba
HRGC 5300 Mega instrument equipped with 25 m fused
silica capillary columns with polysiloxanes CPSil-5 and
CPSil-19 (Chrompack) or Carlo Erba Fractovap 2150
or 4160 instruments equipped with 25 m fused silica
capillary columns with octakis-(2,6-di-O-methyl-3-O-
pentyl)-c-cyclodextrin or heptakis-(6-O-tert-butyldi-
methylsilyl-2,3-di-O-methyl)-b-cyclodextrin in OV-1701
(1:1; w/w). Hydrogen at 0.5 bar inlet pressure was used
as carrier gas. Split injection at 200 ꢂC (split ratio: 1:30);
flame ionisation detector at 250 ꢂC. Temp. progr. 50–
230 ꢂC at 3 ꢂC/min. Electron impact (70 eV) GC-MS
and GC-HRMS measurements were carried out on a
Hewlett Packard HP 5890 gas chromatograph equipped
Fig. 8. Molecular model (AM1, MOPAC) of ())-28 with relevant
NOEs.

S.H. von Reuß et al. / Phytochemistry 65 (2004) 2277–2291
2287
with a 25 m CPSil-5 CB (Chrompack) fused silica capi-
llary column coupled to a VG Analytical 70-250S mass
spectrometer.
was collected in 2003 near Zillertal (Austria). The liv-
€
erworts were identified by H. Muhle (Universitat Ulm).
The carefully cleaned fresh plant material was homo-
genated in water with a blender and submitted to hyd-
rodistillation for 2.5 h to yield the essential oil which
was collected in n-hexane. Alternatively, air dried plant
material was extracted with organic solvents at 7 ꢂC (n-
hexane, dichloromethane, diethyl ether, methanol) or
powdered under liquid nitrogen prior to extraction.
3.1.2. NMR spectroscopy
NMR measurements were carried out with a Bruker
WM 400 instrument for 1H NMR (400.1 MHz),
broadband decoupled 13C NMR and 13C Pendant
spectra (100.6 MHz) and with WM 500 instrument for
1H NMR, COSY, HMQC, HMBC and gp-NOESY
spectra (1H: 500.1 MHz, 13C: 125.8 MHz). Benzene-d6
was used as solvent and TMS served as internal
standard.
3.3. Isolation of single compounds
After prefractionation of the raw essential oils and
enrichment of the constituents by repeated column
chromatography with silica 60 F254 (Merck) and a
pentane–diethyl ether gradient or n-hexane–ethyl acetate
mixture (8/1), respectively, the compounds were isolated
by a combination of preparative TLC using glass plates
with silica 60 F254 (Merck) with different solvent sys-
tems, preparative GC using polysiloxane SE-30, SE-52,
octakis-(2,6-di-O-methyl-3-O-pentyl)-c-cyclodextrin or
heptakis-(6-O-tert-butyldimethylsilyl-2,3-di-O-methyl)-
b-cyclodextrin columns and semi-preparative GC using
thickfilm capillary columns with DB-1 or DB-1701.
3.1.3. Polarimetry
Measurements were performed with a polarimeter
341 (Perkin–Elmer) at 589 nm and 20 ꢂC. Due to the
small amounts of isolated compounds only the sense of
optical rotation could be determined.
3.1.4. Preparative GC
Preparative GC was carried out with a modified
Varian 1400 gas chromatograph equipped with a stain-
less steel column (1.85 m · 4.3 mm; Silcosteel, Amchro)
with 10% SE 30 on Chromosorb W-HP, 15% SE 52
on Chromosorb W-HP, 5% octakis-(2,6-di-O-methyl-3-
O-pentyl)-c-cyclodextrin in OV-1701 (1:1; w/w) on
Chromosorb W-HP, or 6.4% heptakis-(6-O-tert-butyl-
dimethylsilyl-2,3-di-O-methyl)-b-cyclodextrin in SE-52
(1:1; w/w) on Chromosorb W-HP. Helium was used as
carrier gas at a flow rate of approximately 120 ml/min.
Injector and detector (FID) temperatures were 200 and
250 ꢂC, respectively. Eluting fractions were trapped in
Teflon tubes cooled with liquid nitrogen (Hardt and
3.4. ())-(1R*,5S*,6R*,7S*,10S*)-Myli-4(15)-ene (1)
1,1,3a-Trimethyl-6-methylene-1,1a,2,3,3a,3b,4,5,6,6b-
decahydrocyclopenta[2,3]cyclopropa-[1,2-a]cyclopropa[c]-
benzene. Colorless oil; sense of optical rotation
(benzene): ()); RICPSil-5 1419; 1H NMR (500.1 MHz,
C6D6) d ¼ 0:53 (1H, dt, J ¼ 8:8 Hz, J ¼ 9:2 Hz, 7-H),
0.72 (1H, m, 8-HSi), 0.99 (3H, s, 14-H), 1.02 (3H, s, 12-
HSi), 1.05 (3H, s, 13-HRe), 1.22 (1H, d, J ¼ 9:5 Hz, 6-H),
1.44 - 1.53 (4H, m, 1-H, 2-H, 9-H, 9-H0), 1.62 (1H, m, 8-
€
Konig, 1994).
H
Re), 1.85 (1H, m, 2-H0), 2.16 (1H, m, 3-HSi), 2.51 (1H,
3.1.5. Semi-preparative GC
t,br, J ¼ 14:7 Hz, 3-HRe), 5.09 (1H, s, 15-HE), 5.12 (1H,
s, 15-HZ); 13C NMR (100.6 MHz, C6D6) d ¼ 15:1 (q,
12-CðSiÞ), 15.8 (q, 14-C), 16.6 (t, 8-C), 18.6 (s, 11-C), 20.1
(d, 7-C), 22.6 (d, 6-C), 22.8 (s, 5-C), 23.6 (t, 2-C), 30.7 (q,
13-CðReÞ), 32.7 (t, 9-C), 34.7 (t, 3-C), 34.9 (d, 1-C), 37.0
(s, 10-C), 104.7 (t, 15-C), 156.7 (s, 4-C); MS (EI, 70 eV)
m=z (rel. int.): 202 (29) [M]þ, 187 (35), 173 (4), 159 (89),
145 (49), 131 (77), 117 (55), 105 (74), 91 (93), 77 (48), 65
(29), 53 (37), 41 (100).
Semi-preparative GC was carried out with a HP 6890
gas chromatograph equipped with an autosampler and a
megabore thickfilm capillary column (30 m, i.d. 0.53
mm, film thickness 5 lm) with polysiloxane DB-1 or
DB-1701. Helium was used as carrier gas. Injector and
detector (FID) temperatures were 200 and 250 ꢂC, re-
spectively. Eluting fractions were trapped at )20 ꢂC in
glass tubes using the automatic fraction collector PFC 1
€
from Gerstel, Mulheim, Germany, and a cryostat.
3.5. (+)-(5S*,6S*,7S*)-Aromadendra-1(10),4(15)-di-
ene (19)
3.2. Plant material, essential oils and extracts
Plant material of M. taylorii (Hook.) S. Gray was
collected in October 2002 and in April 2003 near Reutte,
Tyrol (Austria), in December 1994 near Walserschanz,
1,1,4-Trimethyl-7-methylene-1a,2,3,5,6,7,7a,7b-octa-
hydro-1H-cyclopropa[e]azulene. Colorless oil; sense of
optical rotation (benzene): (+); RICPSil-5 1510; 1H NMR
(500.1 MHz, C6D6) d ¼ 0:59 (1H, m, 7-H), 0.89 (1H, dd,
J1 ¼ J2 ¼ 5:6 Hz, 6-H), 1.05 (3H, s, 12-HRe), 1.12 (3H, s,
13-HSi), 1.51 (1H, m, 8-HSi), 1.54 (3H, s,br, 14-H), 1.70
(1H, m, 8-HRe), 2.10 (1H, d,br, J ¼ 18:0 Hz, 9-HRe), 2.21
€
Allgau (Germany) and in 1999 at Jervis Inlet (Canada).
Plant material of M. nuda Inoue and Yang was collected
in March 1998 at Yuen-yang Lake, Hsinchu Hsien and
Taiping Shan (Taiwan). Plant material of K. trichoclados

2288
S.H. von Reuß et al. / Phytochemistry 65 (2004) 2277–2291
(1H, d,br, J ¼ 4:2 Hz, 9-HSi), 2.30 (4H, m, 2-H, 3-H),
3.04 (1H, d.br, J ¼ 3:0 Hz, 5-H), 4.92 (1H, s,br, 15-HZ),
5.02 (1H, d,br, J ¼ 1:3 Hz, 15-HE); 13C NMR (100.6
MHz, C6D6) d ¼ 16:0 (q, 13-CðSiÞ), 19.1 (s, 11-C), 22.0
(q, 14-C), 23.6 (t, 8-C), 26.9 (d, 7-C), 29.1 (q, 12-CðReÞ),
31.8, 32.9 (2t, 2-C, 3-C), 35.2 (d, 6-C), 37.0 (t, 9-C), 42.7
(d, 5-C), 104.9 (t, 15-C), 125.8 (s, 10-C), 137.3 (s, 1-C),
158.2 (s, 4-C); MS (EI, 70 eV) m=z (rel. int.): 202 (27)
[M]þ, 187 (9), 173 (1), 159 (42), 145 (11), 133 (100), 117
(17), 105 (53), 91 (58), 77 (24), 65 (12), 55 (19), 41 (54).
solution was washed with 1 ml water, dried over sodium
sulphate and chromatographed on silica gel (n-hexane)
to give 20, 21 and 30.
3.9. ())-(1S*,5S*,6S*,7S*,10S*)-Bourbon-3-en-5,11-
oxide (22)
Colorless oil; sense of optical rotation (benzene): ());
1
RICPSil-5 1471; H NMR (500.1 MHz, C6D6) d ¼ 0:95
(3H, s, 14-H), 1.10 (3H, s, 12-HRe), 1.33 (3H, s, 13-HSi),
1.38 (1H, dt, J ¼ 6:9 Hz, J ¼ 12:6 Hz, 9-HSi), 1.52 (1H,
dd, 2J ¼ 12:0 Hz, J ¼ 6:6 Hz, 9-HRe), 1.65 (1H, dt,
J ¼ 13:2 Hz, J ¼ 7:9 Hz, 8-HRe), 1.74 (3H, d, J ¼ 1:3
Hz, 15-H), 2.02 (1H, ddt, J ¼ 9:5 Hz, J ¼ 6:6 Hz,
J ¼ 12:9 Hz, 8-HSi), 2.10 (1H, d,br, 2J ¼ 17:3 Hz, 2-
3.6. (+)-(1S,6R,7S)-Aromadendra-4,10(14)-diene (20)
1,1,7-Trimethyl-4-methylene-1a,2,3,4,4a,5,6,7b-octa-
hydro-1H-cyclopropa[e]azulene. Colorless oil; sense of
optical rotation (benzene): (+); RICPSil-5 1440; 1H NMR
(500.1 MHz, C6D6) d ¼ 0:74 (1H, m, 7-H), 0.87 (3H, s,
12-HSi), 1.08 (3H, s, 13-HRe), 1.11 (1H, d,br, 6-H), 1.27
(1H, m, 8-HSi), 1.65 (3H, s,br, 15-H), 1.77 (1H, m, 8-HRe),
1.89 (1H, m, 2-HRe), 2.01 (1H, m, 2-HSi), 2.15 (1H, dd,
J ¼ 15:1 Hz, J ¼ 8:8 Hz, 3-H), 2.30 (1H, m, 3-H), 2.44
(1H, d,br, J ¼ 13:2 Hz, 9-HRe), 2.49 (1H, m, 9-HSi), 3.07
(1H, s,br, 1-H), 5.01 (2H, s,br, 14-H); 13C NMR (100.6
MHz, C6D6) d ¼ 15:1 (q, 15-C), 16.7 (q, 12-CðSiÞ), 20.1 (s,
11-C), 21.4 (t, 8-C), 24.7 (d, 6-C), 27.6 (d, 7-C), 29.0 (q,
13-CðReÞ), 29.3 (t, 2-C), 36.4 (t, 3-C), 36.4 (t, 9-C), 50.7 (d,
1-C), 108.0 (t, 14-C), 136.1 (s, 4-C), 137.9 (s, 5-C), 150.4
(s, 10-C); MS (EI, 70 eV) m=z (rel. int.) : 202 (59) [M]þ,
187 (46), 173 (9), 159 (87), 145 (57), 131 (100), 117 (39),
105 (38), 91 (49), 77 (29), 65 (15), 53 (20), 41 (55).
H
Re), 2.17 (1H, d, J ¼ 10:1 Hz, 1-H), 2.19 (1H, t, J ¼ 8:5
Hz, 7-H), 2.44 (1H, ddt, 2J ¼ 17:3 Hz, J ¼ 9:2 Hz,
J ¼ 2:2 Hz, 2-HSi), 2.54 (1H, d, J ¼ 7:9 Hz, 6-H), 5.42
(1H, s, 3-H); 13C NMR (100.6 MHz, C6D6) d ¼ 12:3 (q,
15-C), 19.9 (q, 14-C), 24.1 (q, 13-CðSiÞ), 27.5 (t, 8-C), 31.3
(q, 12-CðReÞ), 31.9 (t, 2-C), 39.8 (s, 10-C), 43.9 (t, 9-C),
48.2 (d, 1-C), 54.3 (d, 7-C), 58.5 (d, 6-C), 85.8 (s, 11-C),
91.7 (s, 5-C), 128.8 (d, 3-C), 141.7 (s, 4-C); MS (EI, 70
eV) m=z (rel. int.) : 218 (96) [M]þ, 203 (30), 189 (4), 175
(22), 161 (23), 145 (21), 136 (66), 123 (100), 107 (30), 91
(30), 81 (31), 67 (18), 55 (19), 41 (53); HRMS
m=z ¼ 218:1681 [M]þ (calc. for C15H22O: 218.1671).
3.10. (+)-(1S*,5S*,7S*)-Guai-3,10(14)-dien-5,11-oxide
(23)
3.7. (1S,6R,7S)-Aromadendra-4,9-diene (21)
2,2,9-Trimethyl-6-methylene-3,4,5,6,6a,7-hexahydro-
2H-3,9a-methanocyclopent[b]oxocine. Colorless oil;
sense of optical rotation (benzene): (+); RICPSil-5 1554; 1H
NMR (500.1 MHz, C6D6) d ¼ 1:10 (3H, s, 12-HRe), 1.30
1,1,4,7-Tetramethyl-1a,2,4a,5,6,7b-hexahydro-1H-cy-
clopropa[e]azulene. Colorless oil; sense of optical rota-
tion: (n.d.); RICPSil-5 1533; 1H NMR (500.1 MHz, C6D6)
d ¼ 0:95 (1H, m, 7-H), 0.96 (3H, s, 12-HSi), 1.09 (3H, s,
13-HRe), 1.19 (1H, d,br, J ¼ 8:8 Hz, 6-H), 1.69 (3H, d,
J ¼ 0:9 Hz, 15-H), 1.72 (3H, d, J ¼ 1:0 Hz, 14-H), 1.88
(2H, m, 3-H), 2.03 (1H, m, 8-HRe), 2.20–2.26 (3H, m, 2-
H, 8-HSi), 3.38 (1H, s,br, 1-H), 5.73 (1H, t,br, J ¼ 7:6
Hz, 9-H); 13C NMR (100.6 MHz, C6D6) d ¼ 14:9 (q, 15-
C), 16.7 (q, 12-CðSiÞ), 21.4 (q, 14-C), 21.9 (s, 11-C), 22.9
(t, 8-C), 25.0 (d, 6-C), 26.6 (d, 7-C), 26.9 (t, 2-C), 29.4 (q,
13-CðReÞ), 37.1 (t, 3-C), 50.2 (d, 1-C), 124.2 (d, 9-C),
131.7 (s, 5-C), 135.4 (s, 4-C), 138.8 (s, 10-C); MS (EI, 70
eV) m=z (rel. int.) : 202 (83) [M]þ, 187 (35), 173 (12), 159
(100), 145 (47), 131 (50), 117 (20), 105 (38), 91 (30), 77
(20), 65 (10), 53 (13), 41 (33).
(3H, s, 13-HSi), 1.36 (1H, m, 8-HRe), 1.70 (2H, m, 6-HRe
,
7-H), 1.73 (3H, m, 15-H), 1.78 (1H, m, 8-HSi), 1.92 (1H,
2
ddd, J ¼ 12:8 Hz, J ¼ 7:1 Hz, J ¼ 1:1 Hz, 6-HSi), 2.19
(2H, m, 2-H), 2.29 (1H, ddd, J ¼ 12:9 Hz, J ¼ J ¼ 4:1
Hz, 9-HSi), 2.59 (1H, ddd, J ¼ J ¼ 13:2 Hz, J ¼ 4:1 Hz,
9-HRe), 3.04 (1H, dd, J ¼ J ¼ 8:4 Hz, 1-H), 4.81 (1H, t,
J ¼ 2:1 Hz, 14-HZ), 4.91 (1H, s,br, 14-HE), 5.34 (1H,
s,br, 3-H); 13C NMR (100.6 MHz, C6D6) d ¼ 12:9 (q, 15-
C), 23.5 (q, 13-CðSiÞ), 31.3 (q, 12-CðReÞ), 31.7 (t, 2-C), 32.5
(t, 8-C), 34.7 (t, 9-C), 35.1 (t, 6-C), 45.6 (d, 7-C), 58.7 (d, 1-
C), 82.3 (s, 11-C), 94.9 (s, 5-C), 110.9 (t, 14-C), 124.4 (d, 3-
C), 144.2 (s, 4-C), 151.8 (s, 10-C); MS (EI, 70 eV) m=z (rel.
int.) : 218 (98) [M]þ, 203 (49), 189 (33), 175 (28), 160 (30),
145 (53), 131 (29), 123 (42), 105 (46), 91 (71), 77 (48), 67
(26), 53 (38), 41 (100); HRMS m=z ¼ 218:1692 [M]þ
(C15H22O; required: 218.1671).
3.8. Dehydration of (+)-4-dehydroviridiflorol (29)
A
solution of 100 lg (+)-4-dehydroviridiflorol
3.11. ())-(1S*,5S*,7S*)-Guai-3,9-dien-5,11-oxide (24)
(29) (isolated from M. taylorii) in 500 ll n-hexane was
treated with 200 ll pyridine and 100 ll methanesulfonyl
chloride at 0 ꢂC. After 4 h at room temperature the
2,2,6,9-Tetramethyl-3,4,6a,7-tetrahydro-2H-3,9a-meth-
anocyclopent[b]oxocine. Colorless oil; sense of optical

S.H. von Reuß et al. / Phytochemistry 65 (2004) 2277–2291
2289
1
rotation (benzene): ()); RICPSil-5 1518; H NMR (500.1
MHz, C6D6) d ¼ 1:18 (3H, s, 12-HRe), 1.32 (3H, s, 13-
HSi), 1.63 (3H, d, J ¼ 1:3 Hz, 14-H), 1.77 (3H, t, J ¼ 1:2
Hz, 15-H), 1.81 (2H, m, 2-HSi, 7-H), 1.87 (1H, d,
J ¼ 12:3 Hz, 6-HRe), 1.95 (1H, dd, J ¼ 11:9 Hz, J ¼ 8:4
Hz, 6-HSi), 2.06 (1H, m, 8-HRe), 2.22 (1H, m, 8-HSi), 2.35
(1H, m, 2-HRe), 2.85 (1H, t,br, J ¼ 8:6 Hz, 1-H), 5.17
(1H, s,br, 9-H), 5.34 (1H, s,br, 3-H); 13C NMR (100.6
MHz, C6D6) d ¼ 11:8 (q, 15-C), 25.7 (q, 13-CðSiÞ), 26.2
(q, 14-C), 31.6 (q, 12-CðReÞ), 32.7 (t, 8-C), 33.9 (t, 6-C),
34.8 (t, 2-C), 44.6 (d, 7-C), 57.2 (d, 1-C), 83.0 (s, 11-C),
94.3 (s, 5-C), 120.6 (d, 9-C), 123.3 (d, 3-C), 135.0 (s, 10-
C), 145.9 (s, 4-C); MS (EI, 70 eV) m=z (rel. int.) : 218
(21) [M]þ, 203 (13), 200 (31), 185 (17), 175 (27), 157 (53),
150 (41), 145 (44), 135 (30), 120 (100), 105 (42), 91 (39),
77 (27), 65 (12), 53 (19), 41 (44).
n-hexane. From an enriched fraction 1 mg of 5, identical
to the natural product, was isolated by preparative GC
using a heptakis-(6-O-tert-butyldimethylsilyl-2,3-di-O-
methyl)-b-cyclodextrin column.
3.15. Hydrogenation of ())-myli-4(15)-en-3-one (5)
To a solution of 100 lg ())-myli-4(15)-en-3-one (5) in
500 ll n-hexane 50 lg Pd/C (10%) was added and H2
bubbled through the solution After 4 h the solution was
filtered to give ())-dihydromylione A (4) identical to the
natural product isolated from M. taylorii.
3.16. ())-(6R,7S)-a-Taylorione (7)
4-[2,2-Dimethyl-3-(5-methylcyclopenta-1,4-dien-1-yl)-
cyclopropyl]-butan- 2-one. Colorless oil; sense of optical
1
3.12. Hydrogenation of guaidien-5,11-oxides (23, 24)
rotation (benzene): ()); RICPSil-5 1586; H NMR (500.1
MHz, C6D6) d ¼ 0:70 (1H, dt, J ¼ 6:3 Hz, J ¼ 8:5 Hz,
7-H), 0.95 (3H, s, 12-HSi), 1.09 (3H, s, 13-HRe), 1.27
(1H, dd, J ¼ 8:7 Hz, J ¼ 1:9 Hz, 6-H), 1.61 (1H, m, 8-H)
1.67 (3H, s, 14-H), 1.88 (1H, m, 8-H0), 1.95 (3H, d,
J ¼ 1:0 Hz, 15-H), 2.12 (2H, m, 9-H) 2.76 (2H, t, J ¼ 1:7
Hz, 2-H), 6.01 (1H, s,br, 3-H), 6.04 (1H, s,br, 1-H); 13C
NMR (100.6 MHz, C6D6) d ¼ 14:3 (q, 15-C), 15.8 (q,
12-CðSiÞ), 19.4 (s, 11-C), 20.7 (t, 8-C), 26.3 (d, 6-C), 28.7
(d, 7-C), 29.2 (q, 13-CðReÞ), 29.4 (q, 14-C), 40.0 (t, 2-C)
44.0 (t, 9-C), 127.3 (d, 1-C), 127.7 (d, 3-C), 136.6 (s, 4-
C), 144.5 (s, 5-C), 206.1 (s, 10-C); MS (EI, 70 eV) m=z
(rel. int.) : 218 (19) [M]þ, 203 (5), 185 (9), 175 (23), 160
(34), 147 (89), 145 (87), 131 (27), 119 (63), 105 (66), 91
(70), 77 (33), 65 (16), 55 (29), 43 (100).
A solution of 100 lg 23 or 24 in 500 ll n-hexane was
treated with 100 lg Pd/C (10%) and hydrogen bubbled
through the solution for 10 min. After 2 h the solution
was filtered and investigated by GC and GC-MS.
3.13. ())-(1S,5R,6R,7S,10S)-Myli-4(15)-en-3-one (5)
1,1,3a-Trimethyl-6-methylene-5-oxo-1,1a,2,3,3a,3b,4,-
5,6,6b-decahydrocyclopenta[2,3]cyclopropa[1,2-a]cyclo-
propa[c]benzene. Colorless oil; sense of optical rotation
(benzene): ()); RICPSil-5 1617; 1H NMR (500.1 MHz,
C6D6) d ¼ 0:51 (1H, dt, J ¼ 8:8 Hz, J ¼ 9:2 Hz, 7-H),
0.60 (1H, m, 8-HSi), 0.72 (3H, s, 14-H), 0.88 (3H, s, 12-
HSi), 0.97 (3H, s, 13-HRe), 0.98 (1H, d, J ¼ n:d:, 6-H),
1.28 (1H, d, J ¼ 6:6 Hz, 1-H), 1.35 (2H, m, 9-H), 1.55
3.17. Rearrangement of ())-taylorione (6)
2
(1H, m, 8-HRe), 2.11 (1H, d, J ¼ 19:6 Hz, 2-H), 2.28
2
2
(1H, dd, J ¼ 19:6 Hz, J ¼ 6:3 Hz, 2-H0), 5.09 (1H, s,
15-HZ), 6.28 (1H, s, 15-HE); 13C NMR (100.6 MHz,
C6D6) d ¼ 14:9 (q, 12-CðSiÞ), 15.2 (q, 14-C), 16.1 (t, 8-C),
19.2 (s, 11-C), 20.5 (d, 7-C), 22.1 (d, 6-C), 25.5 (s, 10-C),
25.8 (d, 1-C), 30.6 (q, 13-CðReÞ), 31.9 (t, 9-C), 33.0 (s, 5-
C), 37.0 (t, 2-C), 115.2 (t, 15-C), 149.7 (s, 4-C), 204.7 (s,
3-C); MS (EI, 70 eV) m=z (rel. int.) : 216 (73) [M]þ, 201
(42), 188 (7), 173 (100), 160 (30), 159 (30), 145 (76), 131
(52), 117 (48), 105 (58), 91 (72), 77 (42), 69 (33), 53 (33),
41 (74); HRMS m=z ¼ 216:1515 [M]þ (calc. for
C15H20O: 216.1514).
A solution of 3 mg ())-6 (isolated from M. taylorii) in
1 ml n-hexane was treated with 0.5 mg Amberlystꢁ 15.
After 5 min the solution was filtered and submitted to
GC-MS. Approx. 1 mg ())-7, 1 mg ())-25 and 0.5 mg
())-26, identical to the natural products, were isolated
by preparative GC using a heptakis-(6-O-tert-butyl-
dimethylsilyl-2,3-di-O-methyl)-b-cyclodextrin column.
3.18. ())-(7S)-(E)-Taylopyran (25)
2,2,6-Trimethyl-3-[(E)(2-methylcyclopenta-2-en-1-ylid-
ene)methyl]-3,4-dihydro-2H-pyran. Colorless oil; sense
of optical rotation (benzene): ()); RICPSil-5 1536; 1H
NMR (500.1 MHz, C6D6) d ¼ 1:23 (3H, s, 12-HRe), 1.34
(3H, s, 13-HSi), 1.68 (3H, d, J ¼ 1:3 Hz, 15-H), 1.81
3.14. Partial synthesis of ())-myli-4(15)-en-3-one (5)
A solution of 2 mg ())-myliol (3) isolated from
M. taylorii in 1 ml trichloromethane was treated with
ꢀ
50 mg molecular sieve 3 A and 50 mg pyridinium di-
chromate. After 4 h at 7 ꢂC the reaction mixture was
washed two times with 2 ml water and 2 ml diluted
hydrochloric acid. The organic phase was dried over
sodium sulphate and chromatographed on silica gel with
2
(3H, s,br, 14-H), 1.91 (1H, ddt, J ¼ 17:0 Hz, J ¼ 9:1
Hz, J ¼ 2:2 Hz, 8-HRe), 2.11 (1H, d,br, 2J ¼ 16:7 Hz, 8-
HSi), 2.21 (2H, m, 2-H), 2.41 (2H, m, 1-H), 2.48 (1H, dt,
J ¼ 6:0 Hz, J ¼ 9:8 Hz, 7-H), 4.50 (1H, s,br, 9-H), 5.12
(1H, d, J ¼ 10:1 Hz, 6-H), 5.62 (1H, s, 3-H); 13C NMR
(100.6 MHz, C6D6) d ¼ 13:1 (q, 15-C), 21.0 (q, 14-C),

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S.H. von Reuß et al. / Phytochemistry 65 (2004) 2277–2291
21.3 (q, 12-CðReÞ), 26.5 (t, 8-C), 27.9 (t, 1-C), 28.0 (q, 13-
CðSiÞ), 30.4 (t, 2-C), 42.7 (d, 7-C), 76.8 (s, 11-C), 93.9 (d,
9-C), 118.2 (d, 6-C), 133.9 (d, 3-C), 140.6 (s, 4-C), 148.8
(s, 5-C), 149.2 (s, 10-C); MS (EI, 70 eV) m=z (rel. int.) :
218 (24) [M]þ, 175 (10), 160 (5), 148 (100), 133 (40), 120
(16), 105 (33), 91 (30), 77 (19), 69 (14), 53 (11), 43 (38);
HRMS m=z ¼ 218:1681 [M]þ (calc. for C15H22O:
218.1671).
MHz, C6D6) d ¼ 0:93 (3H, d, J ¼ 7:3 Hz, 15-H), 1.31
(1H, m, 3-HSi), 1.49 (3H, d, J ¼ 1:3 Hz, 13-H), 1.53–1.64
(3H, m, 2-HSi, 3-HRe, 8-HRe), 1.78 (1H, m, 2-HRe), 2.03
(1H, ddd, J ¼ 13:1 Hz, J ¼ 7:1 Hz, J ¼ 3:2 Hz, 8-HSi),
2.11 (1H, m, 4-H), 2.16 (1H, m, 5-H), 2.48 (1H, d.br,
J ¼ 13.9 Hz, 7-H), 2.55 (1H, d,br, J ¼ 12:3 Hz, 6-H),
3.03 (1H, m, 1-H), 4.03 (1H, dd, J ¼ 7:3, J ¼ 9:5 Hz, 9-
H), 4.81 (1H, s.br, 14-HE), 4.83 (1H, s,br, 14-HZ), 5.76
(1H, s,br, 12-H); 13C NMR (100.6 MHz, C6D6) d ¼ 14:3
(q, 13-C), 17.2 (q, 15-C), 28.3 (t, 2-C), 32.7 (t, 8-C), 33.6
(t, 3-C), 38.2 (d, 4-C), 41.2 (d, 1-C), 41.6 (d, 6-C), 44.1
(d, 7-C), 45.3 (q, 5-C), 77.2 (d, 9-C), 111.4 (t, 14-C),
132.3 (d, 12-C), 147.6 (s, 11-C), 153.7 (s, 10-C); MS (EI,
70 eV) m=z (rel. int.): 218 (4) [M]þ, 203 (10), 200 (23),
185 (44), 171 (12), 157 (34), 143 (70), 129 (50), 119 (46),
105 (75), 91 (100), 77 (62), 67 (31), 55 (38), 41 (51);
HRMS m=z ¼ 218:1683 [M]þ (calc. for C15H22O:
218.1671).
3.19. ())-(6S,7S,10R)-Taylocyclane (26)
1,3,3-Trimethyl-7-(5-methylcyclopenta-1,4-dien-1-yl)-
2-oxabicyclo[2.2. 1]heptane. Colorless oil; sense of op-
1
tical rotation (benzene): ()); RICPSil-5 1477; H NMR
(500.1 MHz, C6D6) d ¼ 1:24 (3H, s, 12-HSi), 1.25 (3H, s,
13-HRe), 1.47 (3H, s, 14-H), 1.52 - 1.59 (1H, m, 8-HRe),
1.61–1.67 (1H, m, 9-HRe), 1.67–1.73 (1H, m, 8-HSi),
1.76–1.83 (1H, m, 9-HSi), 1.91 (4H, s, 15-H, m, 7-H),
2.72 (2H, s,br, 2-H), 3.00 (1H, s,br, 6-H), 5.89 (1H, s,br,
1-H), 6.00 (1H, s, 3-H); 13C NMR (100.6 MHz, C6D6)
d ¼ 14:6 (q, 15-C), 19.0 (q, 14-C), 23.2 (t, 8-C), 26.3 (q,
12-CðSiÞ), 29.7 (q, 13-CðReÞ), 34.2 (t, 9-C), 39.9, (t, 2-C),
51.2 (d, 7-C), 52.4 (d, 6-C), 78.0 (s, 11-C), 86.5 (s, 10-C),
127.0 (d, 1-C), 128.1 (d, 3-C), 143.7 (s, 4-C), 144.3 (s, 5-
C); MS (EI, 70 eV) m=z (rel. int.) : 218 (34) [M]þ, 203 (6),
185 (11), 175 (28), 160 (48), 147 (100), 145 (179), 131
(22), 119 (44), 105 (43), 91 (43), 77 (20), 65 (10), 55 (16),
43 (56); HRMS m=z ¼ 218:1680 [M]þ (calc. for
C15H22O: 218.1671).
Acknowledgements
We are grateful to DAAD for financial support
(Projektbezogener Personenaustauch mit Taiwan) and
€
to Professor R. Mues, Universitat des Saarlands, for a
sample of M. taylorii from Canada. We also thank
Dr. V. Sinnwell, University of Hamburg, for his support
in the NMR and Mrs. A. Meiners and Mr. M. Preusse
for GC-MS and GC-HRMS measurements.
3.20. (5S*,7S*)-Taylofuran (27)
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