Volatile components from European liverworts Marsupella emarginata, M. aquatica and M. alpina

Phytochemistry 61 (2002) 79–91

www.elsevier.com/locate/phytochem

Volatile components from European liverworts Marsupella

emarginata, M. aquatica and M. alpina

Adewale Martins Adio^a, Claudia Paul^a, Wilfried A. Konig^a,*, Hermann Muhle^b

^aInstitut fur Organische Chemie, Universitat Hamburg, Martin-Luther-King Platz-6, D-20146 Hamburg, Germany

¨

Abteilung Systematische Botanik und Okologie, Universitat Ulm, D-89091 Ulm, Germany

¨

b

¨

Received 27 March2002; received in revised form 31 May 2002

Abstract

The hydrodistillation products of the liverworts Marsupella emarginata, M. aquatica and M. alpina were investigated by spec-

troscopic methods. A number of new compounds could be isolated by preparative gas chromatography (GC) and identiﬁed by

spectroscopic techniques including GC-mass spectrometry, NMR and chemical correlations in conjunction with enantioselective

GC. From M. emarginata, in addition to many known compounds, the sesquiterpene hydrocarbon (À)-7-epi-eremophila-1(10),8,11-

triene (1) and the sesquiterpene derivatives (À)-4-epi-marsupellol (2), (À)-marsupellol acetate (18), (À)-4-epi-marsupellol acetate (4),

(+)-5-hydroxymarsupellol acetate (5) and (À)-9-acetoxygymnomitr-8(12)-ene (24) could be identiﬁed. In M. aquatica the sesqui-

terpene hydrocarbons (À)-myltayl-8(12)-ene (7), ent-(+)-amorpha-4,11-diene (8), (À)-amorpha-4,7(11)-diene (9), the sesquiterpene

alcohol (+)-9-hydroxyselina-4,11-diene (10) and (À)-2-acetoxyamorpha-4,7(11)-diene (11) were identiﬁed. In M. alpina (À)-trans-

selina-4(15),11-dien-5-ol (12), (+)-8,9-epoxyselina-4,11-diene (13) and (+)-cis-selina-4(15),11-dien-5-ol (14) were found as new

Keywords: Marsupella emarginata; M. aquatica; M. alpina; Liverworts; Sesquiterpene hydrocarbons; Oxygenated sesquiterpenes

1. Introduction

reported for (À)-marsupellone (16) and 9-acetox-

ymarsupellone (17) (Nagashima et al., 1992).

The chemical composition of the liverwort Marsupella

emarginata, which is common in areas of moderate ele-

vation and mainly growing on water ﬂooded rocks in

small mountain rivers in Europe and in other continents

has been investigated several times (Matsuo et al., 1979;

Harrison et al., 1992; Nagashima et al., 1993, 1994). A

review on the chemistry of M. emarginata is given by

Asakawa (1995). The longipinane type sequiterpenes

(À)-b-longipinene (15), (À)-marsupellone (16), its 9-

acetoxy derivative (17) and (+)-marsupellol (3) are the

major constituents (Matsuo et al., 1979). In addition,

9,14a-diacetoxymarsupellone (19) and 9,11a,14a-tri-

acetoxymarsupellone (20) (Nagashima et al., 1993), 9-

acetoxy-marsupellol (21) (Nagashima et al., 1994) and

eremophila-9,11-dien-8a-ol (22) (Harrison et al., 1992)

have been characterized. Antitumor activity has been

M. aquatica is closely related to M. emarginata as

indicated by the predominance of ent-longipinane type

constituents. However, the two species clearly diﬀer in

their morphological properties (Frahm and Frey, 1992)

and chemical composition (Asakawa, 1995).

2. Results and discussion

2.1. Marsupella emarginata

GC–MS of a hydrodistillation product of M. emargi-

nata, collected in early March2001 near Altenau, Harz

mountains, (Germany), revealed traces of monoterpenes

(tricyclene, a-pinene, camphene, b-pinene, limonene),

aliphatic and aromatic compounds (octan-3-one, oct-1-

en-3-ol, oct-1-en-3-yl acetate, benzaldehyde, phenylace-

taldehyde) and a complex mixture of sesquiterpenes,

including a-longipinene (0.3%), (À)-b-longipinene

(9.4%; ¹³C NMR data are reported for the ﬁrst time, see

* Corresponding author. Tel.: +49-40-42838 2824; fax: +49-40-

42838-2893.

E-mail address: wkoenig@chemie.uni-hamburg.de (W.A. Konig).

PII: S0031-9422(02)00214-5

80

A. Martins Adio et al. / Phytochemistry 61 (2002) 79–91

experimental part), longifolene (1.5%), b-ylangene

(1.5%), b-barbatene (1.7%), a-himachalene (0.4%),

2-epi-b-caryophyllene (0.7%), b-chamigrene (0.75%),

aristolochene (0.9%), valencene (0.9%) and traces of

anastreptene, a-ylangene, gymnomitra-3(15),4-diene

(Warmers and Konig, 1999), aristola-1(10),8-diene,

thujopsene, isobazzanene, alloaromadendrene, g-muur-

olene, trans-b-bergamotene, a-muurolene, cuparene,

a-cuprenene, and d-cadinene could be identiﬁed by

comparison of their mass spectra and retention indices

witha spectral library establisehd under identical

experimental conditions (Joulain and Konig, 1998). An

unknown sesquiterpene hydrocarbon (À)-7-epi-eremo-

phila-1(10),8,11-triene (1; 2%), eluting just after valen-

cene from a non-polar CPSil-5 GC column, was isolated

by preparative GC and investigated by NMR.

In the region of the oxygenated sesquiterpenes mar-

supellol (3; 12.3%), marsupellone (16; 47.8%), (+)-

lemnalol (23; 2.6%), enantiomeric to a compound pre-

viously identiﬁed as a constituent of the soft coral

Lemnalia tenuis by Kikuchi et al. (1982), together with

gymnomitr-8(12)-en-9b-ol (6; 1.2%), also previously

Table 1

NMR coupling correlations of (À)-7-epi-eremophila-1(10),8,11-triene (1)

Proton

¹H–¹H COS correlations

NOESY correlations

H-1

H-2a, H-2b, H-3a /4, H-6b H-8, H-9,

H-1, H-3a / 4, H-3b,

H-1, H-2a, H-2b, H-3b, H-15

H-2a, H-2b, H-3a / 4

H-6b, H-7

H-2a, H-2b

H-3a / H-4*

H-3b

H-3a / H-4, H-1

H-2a, H-2b, H-6a

H-14, H-15

H-6a

H-6b

H-3a / H-4, H-6b, H-13

H-6a, H-7, H-14, H-15

H-6b, H-8, H-12b, H-13, H-14

H-9, H-13

H-1, H-6a, H-7, H-8, H-14

H-6a, H-6b, H-8, H-9

H-1, H-6b, H-7, H-9

H-1, H-7, H-8

H-7

H-8

H-9

H-1, H-8

H-13

H-7, H-8

H-12a

H-12b

H-13

H-12b, H-13

H-12a, H-13

H-12a, H-12b

H-6a, H-6b

H-4

H-6a, H-6b, H-8, H-12a, H-12b

H-3b, H-6b, H-7

H-3b, H-6b

H-14

H-15

* Unresolved signals.

A. Martins Adio et al. / Phytochemistry 61 (2002) 79–91

81

identiﬁed by Nagashima et al. (1994), were the major

constituents. In addition, as new constituents, (À)-4-epi-

marsupellol (2; 1.6%), (À)-marsupellol acetate (18;

1.1%), (À)-4-epi-marsupellol acetate (4; 0.7%) and (+)-

5-hydroxymarsupellol acetate (5; 0.2%) could be iden-

tiﬁed by NMR after isolation by preparative GC.

2.1.1. (À)-7-epi-Eremophila-1(10),8,11-triene (1)

The new sesquiterpene hydrocarbon 1 was isolated

from the hydrodistillation product of M. emarginata by

preparative GC. The mass spectrum exhibits a mole-

cular ion signal at m/z 202 and an elemental composi-

tion of C₁₅H₂₂. Th e¹H NMR spectrum showed signals

of one doublet and one singlet for methyl groups at

ꢀ=0.80 (3H, d, J=6.6 Hz) and 0.94 (3H, s), respec-

tively. The downﬁeld shifted methyl singlet (ꢀ 1.68)

indicated that this methyl group is attached to a double

bond. The oleﬁnic carbon signals at ꢀ 149.4 (s) and

110.7 (t) suggested an exomethylene double bond, which

1

was conﬁrmed by two signals in the H NMR spectrum

at ꢀ=4.84 (1H, t, J=1.6 Hz) and 4.92 (1H, s). The

vinylic proton at ꢀ =5.56 (1H, d, J=9.8 Hz) coupled

withanother vinylic proton at ꢀ=6.08 (1H, dd, J=2.5,

9.8 Hz). The third vinylic proton at ꢀ=5.41 (1H, t,

J=3.5 Hz) coupled with the neighbouring methylene

group at ꢀ=2.01 (2H, br.d, J=4.0 Hz). All this infor-

mation from ¹³C NMR and DEPT as well as from

¹H–¹H-COSY, HMQC and HMBC led to structure 1

for this compound. Its relative conﬁguration resulted

from the NOESY spectrum (Table 1). The absolute

conﬁguration was derived by comparison of the fully

hydrogenated products of (+)- and (À)-valencene

(Fricke, 1999) with 1 by enantioselective GC on a mod-

iﬁed cyclodextrin stationary phase. The tetrahydro

derivatives of 1 and ent-(À)-valencene are identical

(Fig. 1).

Fig. 1. Chemical correlation (À)-7-epi-eremophila-1(10),8,11-triene (1)

with( À)-valencene.

Table 2

NOESY correlations of compounds 3, 4, 5 and 18

Proton

3

18

4

5

H-1

H-1/5a

H-2

H-5a/6, H-12, H-13

–

H-1, H-8a, H- 8b, H-9a, H-9b,

–

H-4, H-12, H-13

–

H-5, H-6, H-12, H-13

–

H-1, H-8a/ H-9a/9b, H-10a,

H-5b, H-12, H-13

H-1/5a, H-8a, H- 8b, H-9a,

H-9b, H-10a,H-10b, H-15a

H-5b, H-14, H-15b

H-4, H-14

H-1, H-8a, H-8b, H-9a, H-9b,

H-10a, H-10b, H-13, H-15a

H-1, H-2, H-5a, H-6, H-15b

H-1, H-4, H-5a, H-6

–

H-10a, H-10b, H-15a

H-5b, H-15b

H-14

H- 10b, H-15a

H-5, H-14, H-15a, H-15b

H-4

H-5b

H-5

H-6

–

H-1, H-4, H-6

–

H-8a, H-8b, H-10a,H-10b,

H-12, H-13

H-1, H-8a, H-8b / H-9a/9b,

H-10a, H-10b, H-12,

–

H-1, H-5, H-8a / 9a/9b,

H-12

–

H-5a /6

H-12

H-1, H-8a, H-8b, H-9a, H-9b,

H-10a, H-10b, H-12

–

H-1,H-2, H-5a/6, H-8a, H-8b,

H-9a, H-9b, H-10a,

H-1/5a, H-2, H-9a, H-9b,

H-10a, H-10b

H-1, H-6, H-8a, H-8b/H-9a/9b,

H-10a, H-10b

H-1, H-6, H-10a, H-10b

H-13

H-1, H-2, H-5a /6, H-8a, H-8b,

H-9a, H-9b

H-1, H-6, H-9a, H-9b,

H-10a, H- 10b,

H-1, H-2 /H-5b, H-8b,H-10a,

H-10b

H-5a, H-8a, H-8b / H-9a, 9b

H-1, H-2, H-9a, H-9b,

H-10a, H-10b

H-14

H-2, H-4, H-5b, H-8a, H-8b,

H-9a, H-9b

H-2, H-4, H-5b, H-8a, H-8b,

H-9a, H-9b, H-10a, H-10b

H-2, H-4, H-8a, H-8b, H-9a,

H-9b, H-10a, H-10b

82

A. Martins Adio et al. / Phytochemistry 61 (2002) 79–91

2.1.2. Marsupellol acetate (18)

lowﬁeld shifted signal at ꢀ 5.99–6.03 (1H, m, H-4) for

the oxygenated methine proton was observed. By

examination of the 2D ¹H–¹H COSY, HMQC and

HMBC spectra the structure was identiﬁed as 4. Th e

relative conﬁguration of 4 was derived from a NOESY

spectrum (Table 2). As expected, compounds 4 and 18,

having the same skeleton and elemental composition

C₁₇H₂₆O₂, show almost identical mass spectrometric

fragmentation patterns (EI and CI), except that their

chromatographic retention times on diverse GC pha-

ses diﬀer, suggesting that structures 4 and 18 are

stereoisomers. Compound 4, an epimer of 18, upon

saponification yielded a corresponding 4-epi-marsu-

pellol 2, which was also isolated as a minor component

of M. emarginata. The relative conﬁguration of 2 is thus

correlated withcompound 4. Marsupellol (3) and 4-epi-

18 is the acetate of the well known sesquiterpene

marsupellol (3) and was isolated from the essential oil of

M. emarginata by preparative GC. The mass spectrum

exhibits a molecular ion signal at m/z 262 and an ele-

mental composition C₁₇H₂₆O₂. Th e¹H NMR spectrum

of 18 shows four singlets corresponding to methyl

groups at ꢀ=0.60, 0.89, 0.92 and 1.70. The latter signal

corresponds to an acetoxy methyl group. Two protons

belonging to an exocyclic double bond absorb at ꢀ

=4.86 (1H, s) and 5.17 (1H, s). A signal at ꢀ 5.90 (1H,

dd, J₁=1.3, J₂=8.8 Hz, H-4) indicated a methine pro-

ton connected to an acetoxy group. The low ﬁeld shifted

signal at ꢀ 68.7 was assigned to a tertiary carbon bonded

to an oxygen of the acetoxy group. The strongly low

ﬁeld shifted signals at ꢀ 112.3 (t) and 153.2 (s) indicated

the presence of an exocyclic double bond. The H–¹H

marsupellol (2) showed also similar H NMR data and

1

COSY, HMQC and HMBC spectra conﬁrmed the

structure of compound 18. The relative conﬁguration,

particularly of C-4 carrying the acetoxy group, was

determined from a NOESY spectrum (Table 2). Treat-

ment of 18 with sodium hydroxide in methanol gave a

product identical (same GC–MS characteristcs and

same retention times on achiral polysiloxane and chiral

cyclodextrin derived GC phases) with marsupellol,

which is a major constituent of M. emarginata.

MS fragmentation patterns but diﬀerent retention times

on bothachiral polysiloxane and cihral cyclodextrin

derived GC phases.

2.1.4. (+)-5-Hydroxymarsupellol acetate (5)

5 has the same tricyclic sesquiterpene backbone as 4

and 18 but the mass spectrum exhibits a molecular ion

peak at m/z 278 corresponding to an elemental compo-

sition of C₁₇H₂₆O₃. Th e¹H NMR and ¹³C NMR spec-

tra of 5 were also similar to those of 4 and 18 except for

the signals at ꢀ 4.97 (1H, t, J=1.3 Hz, H-15b), 5.44 (1H,

d, J=1.9 Hz, H-4) and 3.99 (1H, s, H-5). The latter was

assigned to the proton adjacent to the hydroxy group.

Also the ¹³C NMR indicated a lowﬁeld shifted signal at

ꢀ 80.1 (d) which was assigned to the carbon attached to

the hydroxy group. The relative conﬁguration of 5 was

derived from a NOESY spectrum (Table 2). Sodium

hydroxide hydrolysis of 5 gave a diol witha molecular

ion peak at m/z 236, suggesting an elemental composi-

tion of C₁₅H₂₄O₂.

2.1.3. (À)-4-epi-Marsupellol acetate (4)

The mass spectrum of 4-epi-marsupellol acetate (4)

from M. emarginata exhibits a molecular ion peak at

m/z 262 and an elemental composition of C₁₇H₂₆O_2.The

¹³C NMR spectrum revealed the presence of 17 carbon

1

resonances. H NMR and HMBC demonstrated that a

total of 26 protons were directly attached to the carbon

skeleton. In addition, the molecular mass of 262 was

1

conﬁrmed by chemical ionization MS. The H and ¹³C

NMR spectral patterns of 4 were almost identical to

those of 18, except for the NMR absorptions at ꢀ 4.85

(1H, d, J=1.3 Hz) and 5.02 (1H, dd, J₁=0.6 and

J₂=1.9 Hz) corresponding to the exomethylene pro-

tons. Also a chemical shift diﬀerence in the strongly

2.1.5. (À)-Gymnomitr-8(12)-en-9ꢁ-yl acetate (24)

The mass spectrum of 24 showed a molecular ion sig-

nal at m/z 262 and an elemental composition of

Table 3

NMR coupling correlations of (À)-gymnomitr-8(12)-en-9b-yl acetate (24)

Proton

^IH–¹H COSY correlations

NOESY correlations

H-3a

H-3b

H-4a

H-3b, H-4a, H-5a

H-3b, H-4a, H-4b, H-5a, H-14

H-3a, H-7 / 10b

H-3a, H-4a, H-4b, H-13 / 14

H-3a, H-3b, H-4b, H-5a, H- 5b,

H-3b, H-4a, H-5b, H-11a

H-3a, H-4a, H-5b

H-3a, H-4b, H-5a, H-13 /14, H-15

H-4a, H-5a

H-5b, H-15, H-4a

H-4b

H-5a

H-5b

H-7/10b

H-9

H-4a, H-4b, H-5a, H-15

H-9, H-10a, H-11a, H-11b

H-12a, H-12b, H-7 /10b, H-10a

H-3b, H-15, H-10a / 11a

H-5b

H-3b, H-5a

H-3b, H-9, H-10a, H-13 /14, H-15

H-3b, H-5b, H-7 /10b, H-12a, H-12b

H-3a, H-4a, H-7 /10b, H- 10a, H-11a / 11b, H-15

H-4a, H-5a, H-7 / 10b, H-11b, H-14

H-13 /14

H-15

A. Martins Adio et al. / Phytochemistry 61 (2002) 79–91

83

C₁₇H₂₆O₂. In th e¹H NMR spectrum four methyl sing-

lets at ꢀ 0.75 (6H), 0.90 and 1.75 were observed, the

latter indicating an acetoxy methyl group. The oleﬁnic

carbon signals at d 107.6 (t) and 149.2 (s) suggested an

exomethylene double bond, which was conﬁrmed by

al., 1994). Therefore 24 should be an epimer of the

product obtained by Morais et al. (1988) by acetyla-

tion of (+)-gymnomitr-8(12)-en-9a-ol.

2.2. Marsupella aquatica

1

two signals in the H NMR spectrum at ꢀ 4.84 (1H, t,

J=2.2 Hz) and 5.01 (1H, t, J =2.2 Hz). The signal at

ꢀ 6.04 (1H, ddt, J₁=10.1, J₂=4.7, J₃=2.2 Hz) was

assigned to the oxygenated methine proton. The 2D

¹H–¹H COSY, HMQC, and HMBC spectra conﬁrmed

the structure of 24. The spatial interactions of protons

derived from the NOESY spectrum furnished the relative

This liverwort was collected near Gaschurn/Mon-

tafon, Austria, in July 2001 at an elevation of 1900 m.

Hydrodistillation of the fresh plant material yielded a

complex mixture of volatiles from which the following

constituents were identiﬁed by comparison witha spec-

tral library (Joulain and Konig, 1998): b-elemene

(0.4%), a-barbatene (0.4%), isobazzanene (0.5%),

b-barbatene (3.2%), b-acoradiene (1.3%), (+)-amor-

pha-4,11-diene (8) (9.6%), and (À)-amorpha-4,7(11)-

diene (9) (25.2%). The enantiomer of 8 has been descri-

bed as an intermediate of the artemisinin biosynthesis

by Bouwmeester et al. (1999), while the enantiomer of 9

is a constituent of Ageratina adenophora (Weyerstahl et

al., 1997). Three unknown compounds 7, 10 and 11

were isolated by preparative GC and investigated by

mass spectrometry, NMR and chemical correlation in

combination withenantioselective GC.

4

conﬁguration of 24. A well-resolved longrange J-cou-

pling was observed for methylene protons H-5 and H-3,

indicating that the ﬁve-membered ring structure exhibits

a ﬁxed W-orientation of the four bonds. Spatial inter-

actions were also observed between H-9 and H-5b, H-

3b, H-7/10 and, to a minor extent, withthe H-12 pro-

tons, suggesting that they are located on one side and

between H-13/14, while H-15 and H-3a are located at

the other side of the molecule plane, thus indicating

a-orientation of H-9 (Table 3).

The absolute conﬁguration of 24 was conﬁrmed by

chemical correlation with (À)-gymnomitr-8(12)-en-

9b-ol (6) (Nagashima et al., 1994). The hydrolysis pro-

duct of 24 gave the same GC–MS characteristics and

retention times on achiral polysiloxane and chiral

cyclodextrin derived GC phases as 6. Moreover, ¹H

NMR data of 6 recorded in C₆D₆were totally in

2.2.1. (À)-Myltayl-8(12)-ene (7)

7, a sesquiterpene hydrocarbon with a rare skeleton,

eluted just after b-barbatene from an non-polar dime-

thylpolysiloxane column and was isolated for the ﬁrst

time from a natural source. The mass spectrum exhibits

a molecular ion signal at m/z 204 and an elemental

composition C₁₅H₂₄. Th e¹H NMR spectrum of 7 was

accordance withthose reported for

6 (Nagashima et

recorded in bothC D₆and CDCl₃for better resolution

6

Table 4

Important ¹H–¹³C long-range HMBC coupling correlations of (À)-

of the various multiplet signals. The ¹H NMR spectrum

in C₆D₆showed three methyl singlets at ꢀ 0.77, 0.91 and

0.92. The oleﬁnic carbon signals at ꢀ 102.0 (t) and 154.5

(s) suggested an exocyclic double bond, which was con-

ﬁrmed by two signals in the ¹H NMR spectrum at ꢀ 4.69

(1H, d, J =1.6 Hz) and 4.90 (1H, d, J =1.5 Hz). A

system of methylene protons coupling with each other

at ꢀ 1.77 (1H, br.d, J =16.4 Hz) and 2.47 (1H, d,

myltayl-8(12)-ene (7)

Carbon

Protons

C-1

C-2

C-6

C-8

H-7, H-10a, H-10b, H-13, H-14, H-15

H-3b / H-4a / H-11a, H-14, H-15

H-5a, H-9a, H-10a, H-13

H-9a, H-9b, H-11a, H-11b

Table 5

NMR coupling correlations of selina-4,11-dien-9a-ol (10) recorded in CDCl₃

Proton

¹H–¹H COSY correlations

NOESY correlations

H-1a

H-1b, H-2a / 8a, H-2b, H-14

H-1a, H-6b

H-1b / 6a

H-1a, H-6b, H-14

H-1b / 6a

H-2a / 8a

H-2b

H-1a, H-3a / H-3b / 7, H-1b /6a / 8b, H-9

H-1a, H-3a, H-3b

H-8b, H-14

H-3a, H-3b

H-3a / H-3b / 7

H-6b

H-8b

H-1b / 8b, H-2b, H-6b, H-12a, H-12b

H-1b / 6a / 8b H-15

H-2a / 8a, H-9

H-6b, H-9, H-13, H-15

H-1b / 6a, H-3a /3b /7

H-2a / 8a, H-6b

H-9

H-1b /6a / 8b, 2a /8a

H-3a / H-3b / 7

H-12a, H-12b

H-1a, H-2a / 8a, H-3a /3b/7

H-13

H-12a, H-12b

H-13

H-14

H-3a /3b /7, H-12a, H-12b

H-1a, H-2a / 8a, H-2b /6a / 13

H-6b

H-1a

H-3a / 3b / 7, H-6a / 13

H-15

84

A. Martins Adio et al. / Phytochemistry 61 (2002) 79–91

1

J=16.4 Hz) was also observed. The 2D H–¹H COSY,

HMQC and HMBC spectra conﬁrmed the structure of

7. Important ¹H–¹³C long-range couplings of (À)-myltayl-

8(12)-ene (7) are given in Table 4.

the protons from the NOESY spectrum (Table 5) furn-

ished the relative conﬁguration.

To determine the absolute conﬁguration we have car-

ried out a chemical correlation of the fully hydro-

genated products of 10 with the hydrogenation products

of (+)-a-selinene, which was found to be a major con-

stituent of M. alpina (see below). The results derived

from GC withan achiral polysiloxane column showed

that two out of the four hydrogenation products of 10

gave identical retention times withthe two hydrogenation

products of (+)-a-selinene, but diﬀerent retention times

were observed when enantioselective GC was applied.

This indirectly conﬁrmed that the actual conﬁguration

of 10 at the stereogenic centers C-7 and C-10 might have

the opposite conﬁguration as (+)-a-selinene from

M. alpina. This is an interesting observation which

indicates that biosynthetic pathways may diﬀer even in

the closely related plant species of M. aquatica and

M. alpina.

The relative conﬁguration of 7 was deduced from the

NOESY spectrum, which showed spatial interaction

between H-13 and H-5a, H-7, H-11b and also between

1

H-15 and H-3a, H-4a, H-9a. The H NMR, recorded in

CDCl₃, was totally in agreement with that of synthetic

(Æ)-7 (Srikrishna et al., 1994), but we suggest to use a

diﬀerent numbering system, which is consistent with

that of (À)-myltaylenol, a sesquiterpene alcohol pre-

viously identiﬁed as a constituent of the liverwort Mylia

taylori by Takaoka et al. (1985). A structurally related

sesquiterpene hydrocarbon, cyclomyltaylane, has been

reported by Wu and Chang (1992). Takaoka et al.

(1988) and Asakawa et al. (1991) have also reported the

isolation of the oxygenated derivatives (À)-myltaylenol

and cyclomyltaylenol. Takaoka et al. (1985) suggested

that the myltaylane framework may be derived from cis-

farnesyl diphosphate through C-3–C-7 cyclization of

b-chamigrene followed by migration of the C-3 methyl

group to the vicinal position.

2.2.3. (À)-2-Acetoxyamorpha-4,7(11)-diene (11)

The mass spectrum of 11 exhibits a molecular ion at

m/z 262 and an elemental composition C₁₇H₂₆O₂. Th e

¹H NMR and ¹³C NMR spectral patterns were similar

to those of amorpha-4,7(11)-diene (9) withadditional

signals due to the presence of an acetate group. The

proton signal at ꢀ 5.28 (1H, dt, J₁=2.8, J₂=8.5 Hz)

was assigned to the oxygenated methine group and ꢀ

1.72 (3H, s) to the methyl of the acetyl group. By ana-

2.2.2. (+)-Selina-4,11-dien-9ꢂ-ol (10)

The mass spectrum of 10 exhibits a molecular ion

signal at m/z 220 and an elemental composition

C₁₅H₂₄O. The H NMR spectrum in C₆D₆was not well

resolved in the range of ꢀ 1.65–1.90 but the overlapping

1

signals integrated to 6 H. In the H NMR in CDCl₃

lysis of the H–¹H COSY, HMQC and HMBC spectra

with less overlapping signals in this range, three methyl

singlets were detected at ꢀ 1.10, 1.63 and 1.76. The

deshielded signal at ꢀ 3.37 (1H, dd, J₁=3.8, J₂=11.7

Hz) was assigned to a proton adjacent to a hydroxy

group. The exomethylene proton signals showed a mul-

tiplet at ꢀ 4.72–4.75 in CDCl₃and well resolved signals

in C₆D₆at ꢀ 4.80 (1H, s) and 4.83 (1H, s). The 2D

¹H–¹H COSY (Table 5), HMBC and HMQC spectra

conﬁrmed the structure of 10. The spatial interactions of

the structure was identiﬁed as 11. The relative conﬁgur-

ation of 11 was derived from the NOESY spectrum

(Table 6). 11 was then converted to the corresponding

alcohol by alkaline hydrolysis. Rigorous hydrogenation

of this alcohol resulted under simultaneous dehydration

in four fully saturated diastereoisomeric amophane/

cadinane/muurolanes (molecular mass 208), which were

compared with the corresponding fully hydrogenated

products of 9. GC investigations on a column witha

Table 6

NMR coupling correlations of (À)-acetoxyamorpha-4,7(11)-diene (11)

Proton

¹H–¹H COSY correlations

NOESY correlations

H-1 /8a

H-2

H-2, H-6, H-8b

H-1 /8a, H-3a, H-3b, H-10

H-2, H-5, H-6, H-15

H-3a, H-3b, H-15

H-1 / 8a, H-3a, H-3b, H-15

H-1 /8a, H-9b

H-2, H-3a, H-3b, H-6, H-8b, H-14

H-1 /8a, H-3a, H-3b, H-5, H-6

H-1/8a, H-2, H-14, H-15, ^aH-17

H-2, H-6, H-15

H-3a, H-3b

H-5

H-6

H-1/ 8a, H-2, H-5, H-12

H-1 /8a, H-13

H-8b, H-9b

H-8b

H-9a

H-9b

H-9b, H-10

H-1/8a/10, H-8b, H-9a

H-9a, H-14

H-6

H-1/8a, H-9a, H-14

H-3a, H-3b, H-14

H-6

H-10/17

H-12

H-13

H-8a, H-8b

H-10

H-3a, H-3b, H-5, H-6

H-8b

H-1 /8a, H-9b

H-3a, H-3b

H-14

H-15

a

H-17-acetyl protons.

A. Martins Adio et al. / Phytochemistry 61 (2002) 79–91

85

Table 7

Important NMR coupling correlations of (À)-trans-selina-4(15),11-dien-5-ol (12)

Protons

¹H–¹H COSY correlations

NOESY correlations

H-3b

H-6a

H-7

H-1b / 3a, H-2a /(8a,8b), H-15a, H-15b

H-6b, H-7

H-1a, H-1b / 3a, H-15a, H-15b, -OH

H-6b, H-7, H-15a, -OH

H-6a, H-9b, H-12a, H-12b

H-1a, H-2a / (8a, 8b), H-9b

H-6a, H-7

H-2a / (8a ,8b), H-6a, H-6b, H-12a, H-12b

H-9b, H-2a / (8a, 8b)

H-2a / (8a, 8b), H-9a, H-14

H-7, H-12a, H-12b

H-9a

H-9b

H-13

H-14

-OH

H-6a, H-7, H-12a, H-12b

H-1a, H-1b / 3a, H-2a / (8a, 8b), H-2b, H-9a, H-15a, H-15b

H-3b, H-6a, H-7

H-1b / 3a, H-9b

–

Table 8

Important ¹H–¹³C long-range HMBC coupling correlations of (À)-

2.3. Marsupella alpina

trans-selina-4(15),11-dien-5-ol (12)

M. alpina was collected in July 2001 near Gaschurn

(Austria) at an elevation of 2000 m. a-Pinene (4.2%)

was the only major monoterpene in the hydrodistilla-

tion product. In addition 1-octen-3-ol (1.1%) and its

acetate (1.2%) were detected. In the sesquiterpene

region anastreptene (0.8%), cis-a-bergamotene (0.8%),

b-santalene (1.2%), (À)-selina-4,11-diene (8.4%),

eudesma-3,5,11-triene (3%; Mekem Sonwa et al., 1997),

(+)-a-selinene (3.7%) and the sesquiterpene lactones

(À)-dihydrodiplophyllin (2.5%; Asakawa et al., 1979)

and diplophyllolide [=(À)-4,11(13)-eudesmadien-12,8-

olide, 24.3%; Benesova et al., 1975] were identiﬁed by

comparison witha spectral library (Joulain and Ko nig,

1998) and withreference compounds of known con-

ﬁguration by enantioselective GC (Konig et al., 1999).

Three unknown compounds 12 (10.7%), 13 (7.8%) and

14 (7.2%) were isolated by preparative GC and investi-

gated by mass spectrometry, NMR, chemical corre-

lation reactions and enantioselective GC.

Carbon

Protons

C-4

C-5

H-1b /3a, H-2b, H-3b, H-15a, H-15b, -OH

H-1b / 3a, H-6a, H-6b, H-14, H-15a, H-15b, -OH

H-1b /3a, H-2a / (8a, 8b), H-6a, H-9a, H-9b, H-14, -OH

H-2a / (8a, 8b), H-6b, H-7, H-13

C-10

C-11

2.3.1. (À)-trans-Selina-4(15),11-dien-5-ol (12)

12 is a sesquiterpene alcohol with the eudesmane ske-

leton. The mass spectrum showed a molecular ion at m/

z 220 and an elemental composition of C₁₅H₂₄O. The

¹H NMR spectrum of 12 recorded in C₆D₆showed two

singlets at ꢀ 0.85 and 1.65 corresponding to methyl

groups. The presence of two exomethylene double

bonds was conﬁrmed by carbon signals at ꢀ 107.3 (t),

152.9 (s) and 108.9 (t), 150.8 (s), respectively. This

assignment was conﬁrmed by three signals in the ¹H

NMR spectrum at d 4.59 (1H, s), 4.73 (1H, s) and 4.85

(2H, d, J =11.4 Hz), respectively. The tertiary hydroxyl

group was assigned to carbon-5. The 2D ¹H–¹H COSY,

HMBC, and HMQC spectra conﬁrmed the structure of

12. The spatial interactions of protons from the NOESY

spectrum furnished the relative conﬁguration. (Tables 7

and 8). Rigorous catalytic hydrogenation of 12 resulted

in a simultaneous dehydration to two fully saturated dia-

stereoisomeric eudesmanes (molecular mass 208), which

were compared with the fully hydrogenated products of

authentic (+)-a-selinene (Fig. 2). The comparison by

Fig. 2. Chemical correlation of (À)-trans-selina-4(15),11-dien-5-ol (12)

and (+)-8,9-epoxyselina-4,11-diene (13) with( +)-a-selinene.

cyclodextrin derived chiral stationary phase showed that

the two compounds gave the same retention times for

all the fully hydrogenated products. Thus, the absolute

conﬁguration at stereogenic centers C-1, C-6 and C-10

of 9 and 11 are identical. The a-hydroxyl orientation

was deduced from the spatial interaction of H-2 with H-

1/8a, and H-6 in the NOESY spectrum (Table 6).

86

A. Martins Adio et al. / Phytochemistry 61 (2002) 79–91

Table 9

Important NMR coupling correlations of (+)-8,9-epoxy-selina-4,11-

diene (13)

suggested structure 13. Its relative conﬁguration resul-

ted from the NOESY spectrum (Tables 9 and 10). The

absolute conﬁguration of 13 was again determined by

chemical correlation with (+)-a-selinene in conjunction

withenantioselective gas chromatography (Fig. 2).

Proton

¹H–¹H COSY correlations

NOESY correlations

H-7

H-8

H-8, H-12b

H-6b, H-9, H-14

H-8, H-14

H-8, H-12b, H-13

H-7, H-9, H-12b, H-13

H-1a, H-1b, H-8, H-14

H-7, H-8, H-12a

H-6a, H-9

2.3.3. (+)-cis-Selina-4(15),11-dien-5-ol (14)

H-9

H-12b

H-14

In the gas chromatogram 14 eluted just after 13. Th e

mass spectrum showed a molecular ion at m/z 220 indi-

cating an elemental composition of C₁₅H₂₄O. The

¹H NMR spectrum of 14, recorded in C₆D₆, showed

two singlets corresponding to methyl groups at ꢀ 1.07 and

1.66. The presence of the two exomethylene double bonds

was conﬁrmed by carbon signals at ꢀ 109.0 (t), 110.2 (t)

and 2Â 149.6 (s). The signal at ꢀ 75.1 (s) was assigned to

the tertiary carbon with the hydroxy group. Interestingly,

H-7, H-12a, H-13

H-8, H-9

Table 10

Important ¹H–¹³C long-range HMBC couplings of (+)-8,9-epoxy-

selina-4,11-diene (13)

Carbon

Protons

C-4

C-5

H-3a, H-3b, H-6a, H-6b, H-9, H-15

H-1a, H-1b, H-3a, H-3b, H-6a, H-6b, H-9, 14, H-15

H-1a, H-1b, H-6b, H-9, H-14

H-7, H-13

1

the H NMR, ¹³C NMR, HMBC, HMQC and GC–MS

C-10

C-11

data of 14 were almost identical to those of 12 except that

1

the signals in the H NMR spectrum of 14 were con-

siderably broadened at room temperature which is typical

for cis-decalin derivatives (Jakupovic et al., 1988; Brown,

1994), thus, indicating that 14 should be an epimeric form

of 12. The sense of optical rotation of 14 is positive. This

suggests that 14 should be enantiomeric to (À)-5b-

hydroxy-b-selinene reported by Jakupovic et al. (1988).

Although the investigated Marsupella species are all

members of the same family of the gymnomitriaceae their

spectrum of metabolites is very diﬀerent. M. emarginata

produces mainly sesquiterpenoids withb-longipinane

skeleton, while amorphane and eudesmane type com-

pounds are prevailing in M. aquatica and M. alpina. This is

again an example that morphological similarity of mem-

bers of the same plant family does not necessarily result in

the generation of a similar pattern of metabolites.

enantioselective GC showed that all the fully hydro-

genated products generated from (+)-a-selinene and

from 12 gave the same retention times. In addition,

identical mass spectra of the hydrogenated samples were

recorded. Thus, the absolute conﬁguration of 12 at the

stereogenic centers C-7 and C-10 was conﬁrmed. The

b-orientation of the hydroxyl group was derived from

the NOESY spectrum (Table 7). Compound 12 exhibits

opposite conﬁguration to the reported (+)-5a-hydroxy-

b-selinene which was isolated from the aerial parts of

Cassinia subtrapica F. Mell. by Jakupovic et al. (1988)

and synthesized by Xiong et al. (1998) and Zhou et al.

1

(2000). The H NMR spectra, recorded in CDCl₃, were

consistent with the three earlier reports. This result also

correlates withthe presence of ent-(À)-selina-4,11-diene

and ent-(+)-a-selinene in the hydrocarbon fraction of

the same liverwort sample.

3. Experimental

3.1. General experimental procedures

2.3.2. (+)-8,9-Epoxyselina-4–11-diene (13)

This new sesquiterpene with the eudesmane skeleton

was also isolated from M. alpina. The mass spectrum

exhibits a molecular ion at m/z 218 and an elemental

composition of C₁₅H₂₂O. The ¹H NMR spectrum

showed signals of three singlets for the methyl groups at

ꢀ=1.27, 1.46 and 1.82. The downﬁeld shifted methyl

signals at ꢀ 1.46 and 1.82 suggested that both are sepa-

rately attached to double bonds. The oleﬁnic carbon

signals at ꢀ 148.0 (s), and 111.4 (t), suggested an exo-

methylene double bond, which was conﬁrmed by two

signals in the ¹H-NMR spectrum at ꢀ 4.89 (1H, t, J=1.6

Hz) and 5.07 (1H, s). The oxygenated methine proton at

ꢀ 2.59 (1H, d, J =3.8 Hz) couples withthe adjacent

oxygenated methine proton at ꢀ 3.06 (1H, d, J =3.8

3.1.1. Gas chromatography

Orion Micromat 412 double column instrument with

25 m fused silica capillaries withpolysiloxane CPSil-5

and polysiloxane CPSil-19 (Chrompack); Carlo Erba

Fractovap 2150 or 4160 gas chromatographs with 25 m

fused silica capillaries withoctakis(2,6-di- O-methyl-3-

O-pentyl)-g-cyclodextrin, heptakis(2,6-di-O-methyl-3-

O-pentyl)-b-cyclodextrin or heptakis(6-O-tert-butyldi-

methylsilyl-2,3-di-O-methyl)-b-cyclodextrin in OV 1701

(50%, w/w), split injection; split ratio approx. 1:30;

FID; carrier gas 0.5 bar H₂; injector and detector tem-

ꢀ

peratures were 200 and 250 C, respectively.

3.1.2. Preparative GC

Modiﬁed Varian 1400 and 2800 instruments, equip-

ped withstainless steel columns (1.85 m Â 4.3 mm) with

1

Hz). Information from 2D H–¹H COSY, HMQC and

HMBC spectra in addition to the ¹³C NMR and DEPT

A. Martins Adio et al. / Phytochemistry 61 (2002) 79–91

87

10% polydimethylsiloxane SE-30 on Chromosorb

W-HP or with2.5% octakis(2,6-di- O-methyl-3-O-pen-

3.2. Plant material and essential oils

tyl)-g-cyclodextrin in OV-170 (50%, w/w) on Chromo-

The collection sites for the 3 Marsupella species are

indicated above. The essential oils were prepared by

hydrodistillation (2 h) of aqueous homogenates of fresh

and green or air-dried plants using n-hexane as collec-

tion solvent. Because of the greatly diﬀering weight the

freshmaterial was not weighed.

sorb

G-HP

or

with6% ephtakis(6-

O-tert-

in

butyldimethylsilyl-2,3-di-O-methyl)-b-cyclodextrin

SE-52 (50%, w/w) on Chromosorb W-HP; FID; helium

as carrier gas at a ﬂow rate of 240 ml/min.; injector and

detector temperatures were 200 and 250 ^ꢀC, respectively

(Hardt and Konig, 1994).

3.3. Isolation of single constituents of the essential oils

3.1.3. GC–MS

Electron impact (70 eV) and chemical ionization

(NH3 or isobutane) GC–MS were carried out on a

Hewlett Packard HP 5890 gas chromatograph coupled

witha VG Analytical 70–250S mass spectrometer.

All isolations were carried out using SE-30- and/or

SE-52-columns followed by at least one cyclodextrin

phase column.

3.4. (À)-ꢁ-Longipinene

3.1.4. NMR-spectroscopy

NMR measurements were carried out witha Bruker

WM 400 or a Bruker WM 500 instrument in C₆D₆and/

or CDCl₃using TMS as internal standard.

Colourless oil; sense of optical rotation (benzene):

(À); ¹³C NMR (125.7 MHz, C₆D₆): ꢀ=22.0 (t, C-9),

24.1 (t, C-4), 24.4 (q, C-14), 26.2 (t, C-5), 28.0 (q, C-12),

28.5 (q, C-13), 32.9 (s, C-11), 39.5 (d, C-6), 39.8 (t,

C-10), 41.7 (t, C-8), 42.5 (s, C-7), 51.4 (d, C-2), 53.1(d,

C-1), 105.6 (t, C-15), 153.7 (s, C-3).

3.1.5. Polarimetry

Measurements were performed witha polarimeter

341 (Perkin-Elmer) at 589 nm at 20 ^ꢀC. Due to

the very small amounts of isolated compounds only

the sense of optical rotation is given to avoid

inaccurracies.

3.5. (À)-7-epi-Eremophila-1(10),8,11-triene (1)

Colourless oil; RI_CPSil5=1507; sense of optical rota-

tion (benzene): (À); ¹H NMR (500 MHz, C₆D₆):

ꢀ=0.80 (d, 3H, CH₃-15, J=6.6 Hz), 0.94 (s, 3H, CH₃-

14), 1.20–1.29 (m, 1H, H-6a), 1.31–1.40 (m, 2H, H-3a,

H-4),1.45–1.53 (m, 1H, H-3b), 1.68 (s, 3H, CH₃-13),

1.90 (dd, 1H, H-6b, J=4.4, 11.3 Hz), 2.01 (br. d, 2H,

H-2, J=4.0 Hz), 2.99 (br. d, 1H, H-7, J =11.7 Hz), 4.84

(t, 1H, H-12a, J=1.6 Hz), 4.92 (s, 1H, H-12b), 5.41 (t,

1H, H-1, J=3.5 Hz), 5.56 (d, 1H, H-8, J=9.8 Hz), 6.08

(dd, 1H, H-9, J₁=2.5, J₂=9.8 Hz); ¹³C NMR (125.7

MHz, C₆D₆): ꢀ=15.7 (q,C-15),17.9 (q, C-14), 20.4 (q,

C-13), 26.0 (t, C-2), 27.1 (t, C-3), 36.2 (s, C-5), 38.9 (d,

C-4), 40.7 (t, C-6), 42.2 (d, C-7), 110.7 (t, C-12), 124.6

(d, C-1), 128.1 (d, C-8), 130.0 (d, C-9), 141.4 (s, C-10),

149.4 (s, C-11); MS (EI, 70 eV), m/z (rel. int.): 202

[M⁺] (100), 187 (59), 173 (15), 159 (38), 145 (97), 131

(91), 117 (55), 105 (71), 91 (90), 77 (47), 65 (24), 55

(29), 41 (78).

3.1.6. Thin layer chromatography

Thin layer chromatography was eﬀected using glass

and aluminum plates of silica 60 F₂₅₄(Merck). An

ethanolic solution of sulfuric acid (10%) and anisalde-

hyde was used as spray reagent. The solvent system used

was n-hexane:ethyl acetate (3:1).

3.1.7. Chemical transformations

Hydrogenation was performed by bubbling hydrogen

gas through a stirred solution of ca. 1 mg of sample in 1

ml n-hexane and 0.5 mg Pd/C at room temp. for 1 h.

The reaction mixture was ﬁltered and the reaction pro-

ducts were analyzed by GC–MS and by GC on several

capillary columns withcyclodextrin derivatives.

Saponiﬁcation was executed by addition of a few

drops of 0.5% NaOH to a stirred solution of ca. 1 mg of

sample in 1 ml methanol. The mixture was stirred at

room temp. for 5 days. The reaction mixture was

extracted with hexane and the organic phase was ana-

lyzed by GC–MS and by GC on several capillary col-

umns withcyclodextrin derivatives.

Dehydration was carried out withca. 1 mg of sample

in 0.5 ml pyridine and 1 drop of phosphoryl chloride

under ice cooling. After 1 hof stirring at room temp. the

reaction was quenched by adding a few drops of water

and the mixture was extracted 3 times with hexane. The

organic phase was washed several times with water and

dried over Na₂SO₄.

3.6. (À)-4-epi-Marsupellol (2)

Colourless oil; RI_CPSil5=1614; sense of optical rota-

tion (benzene): (À); ¹H NMR (500 MHz, C₆D₆):

ꢀ=0.78 (s, 3H), 0.82 (s, 3H), 0.85 (s, 3H), 1.15 (br.d, 1H,

J=6.0 Hz), 1.28–1.33 (m, 2H), 1.43–1.47 (m, 4H), 1.71

(ddd, 1H, J₁=1.9, J₂=6.3, J₃=11.7 Hz), 1.88–1.91 (m,

1H), 2.24–2.29 (m,1 H), 2.60 (br.d, 1H, J=6.0 Hz),

4.44–4.47 (m, 1H), 4.82 (br.s, 1H), 5.10 (t, 1H, J=1.9

Hz); MS (EI, 70 eV), m/z (rel. int.): 220 [M⁺] (2), 202

(14), 187 (17), 175 (8), 159 (24), 145 (20), 135 (26), 119

88

A. Martins Adio et al. / Phytochemistry 61 (2002) 79–91

(25), 105 (39), 95 (41), 91 (63), 81 (54), 77 (46), 67 (48),

55 (62), 41 (100).

C₆D₆): ꢀ=0.79 (s, 3H, CH₃-12), 0.83 (s, 3H, CH₃-13),

1.10 (s, 3H, CH₃-14),1.22 (br.s, 1H, H-1), 1.27 (br.t, 2H,

H-10, J =5.0 Hz),1.40–1.49 (m, 3H, H-9, H-8a), 1.56–

1.61 (m, 1H, H-8b), 1.62 (s, 3H, CH₃CO-), 2.45 (br.t,

1H, H-6, J=4.1 Hz), 2.57 (d, 1H, H-2, J=5.7 Hz), 3.99

(s, 1H, H-5), 4.93 (s, 1H, H-15a), 4.97 (t, 1H, H-15b,

J=1.3 Hz), 5.44 (d, 1H, H-4, J=1.9 Hz); ¹³C NMR

(125.7 MHz, C₆D₆): ꢀ =19.3 (q, CH₃CO-), 20.5 (t, C-9),

24.6 (q, C-14), 26.3 (q, C-12), 26.6 (q, C-13), 31.1 (s,

C-11), 38.1 (t, C-10), 39.9 (s, C-7), 40.6 (t, C-8), 44.3 (d,

C-6), 49.9 (d, C-2), 52.2 (d, C-1), 79.6 (d, C-4), 80.1 (d,

C-5), 109.5 (t, C-15), 149.0 (s, C-3), 173.1 (s, CH₃CO-);

MS (EI, 70 eV), m/z (rel. int.): 236 (7), 218 (11), 203 (7),

189 (15), 175 (8), 161 (7), 147 (10), 133 (12), 125 (20),

119 (14), 105 (21), 91 (27), 77 (22), 69 (17), 55 (27), 43

(100); MS (CI, isobutane), m/z (rel. int.): 278 [M⁺] (1),

261 (16), 236 (11), 219 (100), 201 (99), 189 (15), 175 (11),

161(12), 145 (23), 135 (20), 119 (18), 109 (26), 95 (31), 81

(19), 69 (32), 61 (22).

3.7. (À)-Marsupellol acetate (18)

Colourless oil; RI_CPSil5=1673; R_f=0.93; sense of

1

optical rotation (benzene): (À); H NMR (500 MHz,

C₆D₆): ꢀ=0.60 (s, 3H, CH₃-14), 0.89 (s, 3H, CH₃-12),

0.92 (s, 3H, CH₃-13), 1.29–1.32 (m, 2H, H-10), 1.40

(br.t, 2H, H-8, J=5.7 Hz), 1.44–1.48 (m, 2H, H-9), 1.70

(s, 3H, CH₃CO-), 1.77–1.81 (m, 2H, H-5a, H-1), 1.82–

1.85 (m, 1H, H-6), 2.41 (ddd, 1H, H-5b, J =2.2, 8.8,

14.8 Hz), 2.54 (d, 1H, H-2, J=5.7 Hz), 4.86 (s, 1H,

H-15a), 5.17 (s, 1H, H-15b), 5.90 (dd, 1H, H-4, J=1.3, 8.8

Hz); ¹³C NMR (127.5 MHz, C₆D₆): ꢀ=21.2 (q, CH₃CO-),

22.0 (t, C-9), 24.3 (q, C-14), 27.9 (q, C-12), 28.3 (q, C-13),

32.9 (s, C-11), 36.8 (t, C-5), 38.9 (d, C-6), 39.7 (t, C-10),

41.3 (t, C-8), 42.1 (s, C-7), 50.5 (d, C-2), 54.1 (d, C-1), 68.7

(d, C-4),112.3 (t, C-15), 153.2 (s, C-3), 170.0 (s, CH₃CO-);

MS (EI, 70 eV), m/z (rel. int.): 262 [M⁺] (1), 247 (2), 220

(6), 202 (10), 187 (13), 177 (10), 159 (21), 145 (19), 132 (27),

118 (35), 105 (34), 91 (36), 79 (19), 69 (27), 55 (34), 43

(100); MS (CI, NH₃), m/z (rel. int.): 280 [M+NH4] (1),

263 [M+1] (3), 249 (2), 233 (2), 229 (2), 220 (27), 203 (100),

187 (10), 177 (7), 159 (15), 143 (19), 133 (27), 119 (54), 105

(30), 95 (24), 91 (25), 78 (27), 69 (7), 65 (7), 60 (6).

3.10. (À)-9-Acetoxygymnomitr-8(12)-ene (24)

Colourless oil; RI_CPSil5=1723; sense of optical rota-

tion (benzene): (À); ¹H NMR (500 MHz, C₆D₆):

ꢀ=0.75 (s, 6H, CH₃-13, CH₃-14), 0.90 (s, 3H, CH₃-15),

1.08 (dd, 1H, H-3a, J₁=6.9, J₂=12.9 Hz), 1.20 (dd, 1H,

H-5a, J₁=6.9, J₂=13.2 Hz), 1.35 (dd, 1H, H-10a,

J₁=10.4, J₂=12.9 Hz), 1.40 (d, 1H, H-11a, J=11.7 Hz),

1.64–1.73 (m, 1H, H-4a), 1.75 (s, 3H, CH₃-CO), 1.81–

1.87 (m, 1H, H-4b), 1.92 (ddd, 1H, H-11b, J₁=1.8,

J₂=4.7, J₃=11.7 Hz), 1.99 (dt, 1H, H-5b, J₁=6.9, J₂

=13.2 Hz), 2.11 (dt, 1H, H-3b, J₁=6.9, J₂=13.2 Hz ),

2.26–2.31 (m, 1H, H-10b), 2.30 (d, 1H, H-7, J=4.7 Hz),

4.84 (t, 1H, H-12a, J=2.2 Hz), 5.01 (t, 1H, H-12b,

J=2.2 Hz), 6.04 (ddt, 1H, H-9, J₁=2.2, J₂=4.7,

J₃=10.1 Hz); ¹³C NMR (125.7 MHz, C₆D₆): ꢀ=20.6 (q,

CH₃CO), 23.3 (q, C-14), 24.1 (q, C-13), 27.7 (q, C-15),

27.7 (t, C-4), 36.3 (t, C-3), 37.7 (t, C-5), 45.2 (s, C-1),

45.4 (t, C-10), 47.0 (t, C-11), 54.8 (s, C-6), 55.8 (s, C-2),

56.9 (d, C-7), 70.4 (d, C-9), 107.6 (t, C-12), 149.2 (s, C-

8), 170.1 (s, CH₃CO); MS (EI, 70 eV), m/z (rel. int.): 262

[M⁺] (2), 247 (1), 220 (16), 202 (19), 187 (10), 159 (7),

145 (6),123 (35), 106 (100), 96 (39), 95 (34), 91 (57), 81

(26), 55 (11), 43 (28).

3.8. (À)-4-epi-Marsupellol acetate (4)

Colourless oil; RI_CPSil5=1731; R_f=0.94 ; sense of

1

optical rotation (benzene): (À); H NMR (500 MHz,

C₆D₆): ꢀ=0.78 (s, 3H, CH₃-13), 0.83 (s, 3H, CH₃-12),

0.87 (s, 3H, CH₃-14), 1.27–1.31 (m, 2H, H-10), 1.42–

1.45 (m, 4H, H-9, H-8), 1.48 (br.s, 1H, H-1), 1.75 (s, 3H,

CH₃CO-), 1.78 (ddd, 1H, H-5a, J₁=1.9, J₂=6.0,

J₃=13.6 Hz), 1.86 (br.t, 1H, H-6, J =5.0 Hz), 2.56–2.59

(m, 1H, H-5b), 2.61 (d, 1H, H-2, J=6.3 Hz), 4.85 (d,

1H, H-15a, J=1.3 Hz), 5.02 (dd, 1H, H-15b, J₁=0.6, J₂

=1.9 Hz), 5.99–6.03 (m, 1H, H-4); ¹³C NMR (125.7

MHz, C₆D₆): ꢀ=21.0 (q, CH₃CO-), 21.8 (t, C-9), 23.4

(q, C-14), 27.9 (q, C-13), 28.4 (q, C-12), 32.9 (s, C-11),

34.9 (t, C-5), 39.4 (d, C-6), 39.7 (t, C-10), 41.9 (t,

C-8), 43.6 (s, C-7), 50.5 (d, C-2), 52.5 (d, C-1), 68.0

(d, C-4), 107.5 (t, C-15), 152.0 (s, C-3), 170.1 (s,

CH₃CO-); MS (EI, 70 eV), m/z (rel. int.): 262 [M⁺]

(2), 247 (2), 220 (3), 202 (9), 187 (11), 177 (5), 159

(16), 145 (13), 131 (22), 118 (24), 105 (25), 91 (35), 77

(18), 69 (19), 55 (27), 43 (100); MS (CI, NH3), m/z (rel.

int.): 280 [M+NH4] (1), 263 [M+1] (5), 233 (1), 220 (14),

203 (100), 187 (7), 177 (4), 159 (10), 147 (13), 133 (19), 119

(37),105 (19), 95 (17), 91 (16), 78 (11), 65 (4), 60 (6).

3.11. (À)-Myltayl-8(12)-ene (7)

Colourless oil; RI_CPSil5=1455; sense of optical rota-

tion (chloroform): (À); ¹H NMR (500 MHz, C₆D₆):

ꢀ=0.77 (s, 3H, CH₃-14), 0.91 (s, 3H, CH₃-13), 0.92 (s,

3H, CH₃-15), 1.06–1.22 (m, 3H, H-3a, H-5a, H-10a),

1.33–1.52 (m, 4H, H-3b, H-4a, H-5b, H-11a), 1.53–1.69

(m, 2H, H-4b, H-10b), 1.77 (br.d, 1H, H-9a, J=16.4

Hz), 1.83–1.90 (m, 1H, H-11b), 2.05 (d, 1H, H-7, J=4.4

Hz), 2.47 (d, 1H, H-9b, J=16.4 Hz), 4.69 (d, 1H, H-12a,

3.9. (+)-5-Hydroxymarsupellol acetate (5)

Colourless oil; RI_CPSil5=1856; R_f=0.55; sense of

1

optical rotation (benzene): (+); H NMR (500 MHz,

J=1.6 Hz ), 4.90 (d, 1H, H-12b, J=1.5 Hz); H NMR

A. Martins Adio et al. / Phytochemistry 61 (2002) 79–91

89

(500 MHz, CDCl₃): ꢀ=0.80 (s, 3H), 0.96 (s, 3H), 1.01 (s,

3.14. (+)-9-Hydroxyselina-4,11-diene (10)

3H), 1.13–1.34 (m, 3H), 1.37–1.69 (m, 4H), 1.72–2.20

(m, 5 H), 2.54 (d, 1H, J=16.3 Hz), 4.53 (s, 1H), 4.71 (s,

1H); ¹³C NMR (125.7 MHz, C₆D₆): ꢀ=19.4 (q, C-13),

19.5 (t, C-4), 23.4 (q, C-14), 27.8 (t, C-11), 28.1 (t, C-10),

28.9 (q, C-15), 30.4 (t, C-5), 33.7 (s, C-2), 36.6 (t, C-3),

40.6 (t, C-9), 47.2 (s, C-6), 53.1 (s, C-1), 58.0 (d, C-7),

102.0 (t, C-12), 154.5 (s, C-8); MS (EI, 70 eV), m/z (rel.

int.): 204 [M⁺] (25), 189 (20), 176 (4), 175 (3), 161 (19),

148 (12), 147 (10), 133 (22), 119 (42), 108 (100), 93 (60),

79 (37), 69 (32), 55 (31), 41 (56).

White, viscous oil; RI_CPSil5=1690; R_f=0.51; sense of

optical rotation (chloroform): (+); ¹H NMR (500

MHz, CDCl₃): ꢀ=1.10 (s, 3H, CH₃-14), 1.41 (dt, 1H,

H-1a , J₁=3.2, J₂=12.3 Hz), 1.51–1.58 (m, 2H, H-2a,

H-8a), 1.59–1.65 (m, 1H, H-2b), 1.63 (s, 3H, CH₃-15),

1.71–1.85 (m, 3H, H-1b, H-6a, H-8b), 1.76 (s, 3H,

CH₃-13), 1.89–2.1 (m, 3H, H-3, H-7), 2.52 (ddd, 1H, H-

6, J₁=1.7, J₂=3.2, J₃=13.6 Hz), 3.37 (br.dd, 1H, H-9,

J₁=3.8, J₂=11.7 Hz), 4.72–4.75 (m, 2H, H-12); ¹H

NMR (500 MHz C₆D₆): ꢀ=1.05 (s, 3H), 1.37–1.43 (m,

1H), 1.49–1.57 (m, 3H), 1.54 (s, 3H), 1.65–1.72 (m, 1H),

1.66 (s, 3H), 1.77–1.90 (m, 5H), 2.56 (d, 1H, J=12 Hz),

3.21 (dd, 1H, J₁=4.1, J₂=11.7 Hz), 4.80 (s, 1H), 4.83 (s,

1H); ¹³C NMR (125.7 MHz, CDCI₃): ꢀ=17.7 (q, C-14),

18.7 (t, C-2), 19.8 (q, C-15), 20.8 (q, C-13), 30.0 (t, C-6),

33.0 (t, C-3), 35.6 (t, C-8), 36.2 (t, C-1), 40.1 (s, C-10),

43.2 (d, C-7), 79.1 (d, C-9), 108.8 (t, C-12), 127.5 (s, C-

4), 133.1 (s, C-5), 149.2 (s, C-11); MS (EI, 70 eV), m/z

(rel. int.): 220 [M⁺] (35), 202 (17), 187 (17), 176 (25),

161 (23), 159 (21)145 (17), 133 (16), 123 (100), 105 (44),

97 (73), 91 (44), 81 (57), 77 (30), 67 (27), 55 (33), 41 (69).

3.12. ent-(+)-Amorpha-4,11-diene (8)

Colourless oil; RI_CPSil5=1480; sense of optical rota-

tion (benzene): (+); ¹H NMR (500 MHz, C₆D₆):

ꢀ=0.88 (d, 3H, CH₃-14, J=6.6 Hz), 0.88–0.98 (m, 1H,

H-9a), 1.61–1.21 (m, 1H, H-1), 1.30–1.47 (m, 2H, H-8a,

H-10), 1.48–1.60 (m, 2H, H-2a, H-3a), 1.61 (s, 3H, CH₃-

15), 1.62–1.67 (m, 1H, H-9b), 1.68–1.73 (m, 1H, H-8b),

1.72 (s, 3H, CH₃-12), 1.78–1.97 (m, 3H, H-3b, H-2b,

H-7), 2.57 (br. s, 1H, H-6), 4.81 (s, 1H, H-13a), 5.00 (dd,

1H, H-13b, J₁=1.3, J₂=3.3 Hz), 5.34 (d, 1H, H-5,

J=1.3 Hz); ¹³C NMR (125.7 MHz, C₆D₆): ꢀ=20.1 (q,

C-14), 22.7 (q, C-12), 23.8 (q, C-15), 26.2 (t, C-2), 26.5

(t, C-8), 26.7 (t, C-3), 28.2 (d, C-10), 35.8 (t, C-9), 38.0

(d, C-6), 42.1 (d, C-1), 48.0 (d, C-7), 110.4 (t, C-13),

121.4 (d, C-5), 134.8 (s, C-4), 148.2 (s, C-11); MS

(EI, 70 eV), m/z (rel. int.) 204 [M⁺] (70), 189 (58),

175 (11), 162 (30),147 (25), 133 (23), 121(100), 119

(97), 105 (41), 93 (68), 79 (53), 67 (26), 55 (33), 41

(45).

3.15. (À)-2-Acetoxyamorpha-4,7(11)-diene (11)

Colourless oil; RI_CPSil5=1800; sense of optical rota-

tion (benzene): (À); ¹H NMR (500 MHz, C₆D₆):

ꢀ=0.96–1.01 (m, 1H, H-9a), 1.08 (d, 3H, CH₃-14,

J=6.3 Hz), 1.51 (s, 3H, CH₃-15), 1.52–1.57 (m, 1H, H-

9b), 1.59 (d, 3H, CH₃-12, J=1.9 Hz), 1.63 (s, 3H, CH₃-

13), 1.68–1.71 (m, 1H, H-10), 1.72 (s, 3H, CH₃CO),

1.73–1.79 (m, 2H, H-8a, H-1), 2.10 (br.d, 2H, H-3,

J=8.5 Hz), 2.46–2.50 (m, 1H, H-8b), 3.57 (br.s, 1H, H-

6), 4.96 (s, 1H, H-5) 5.28 (dt, 1H, H-2, J₁=2.8, J₂=8.5

Hz); ¹³C NMR (125.7 MHz, C₆D₆): ꢀ=19.9 (q, C-12),

20.3 (q, C-13), 21.1 (q, CH₃CO), 21.7 (q, C-14), 22.8 (q,

C-15), 26.6 (t, C-8), 28.1 (d, C-10), 32.5 (t, C-3), 36.7 (t,

C-9), 40.9 (d, C-6), 45.0 (d, C-1), 75.1 (d, C-2), 122.0 (s,

C-11), 126.2 (d, C-5), 132.2 (s, C- 4), 133.5 (s, C-7),

169.9 (s, CH₃CO); MS (EI, 70 eV), m/z (rel. int.): 262

[M⁺] (1), 219 (1), 202 (42), 187 (27), 173(4), 160 (88),

159 (93), 145 (100), 131 (22), 119 (21), 105 (30), 91 (26),

77 (17), 67 (13), 55 (22), 43 (73).

3.13. (À)-Amorpha-4,7(11)-diene (9)

Colourless oil; RI_CPSil5=1484; sense of optical rota-

tion (chloroform): (À); ¹H NMR (500 MHz, C₆D₆):

ꢀ=0.89 (d, 3H, CH₃-14, J=6.3 Hz), 0.95–1.04 (m, 1H,

H-9a), 1.28–1.33 (m, 1H, H-1), 1.50–1.60 (m, 2H, H-2a,

H-10), 1.61–1.70 (m, 2H, H-9b, H-3a), 1.62 (s, 3H, CH₃-

15), 1.69 (s, 3H, CH₃-12), 1.72 (d, 3H, CH₃-13, J=2.2

Hz), 1.81–1.93 (m, 3H, H-8a, H-2b, H-3b), 2.56 (ddt,

1H, H-8b, J₁=3.2, J₂=6.3, J₃=13.6 Hz), 3.51 (br.s, 1H,

1

H-6), 5.12 (s, 1H, H-5); H NMR (500 MHz, CDCl₃):

ꢀ=0.88 (d, 3H, J=6.6 Hz), 0.90–0.93 (m, 1H), 1.24–1.27

(m, 1H), 1.55–1.59 (m, 2H), 1.62 (br.s, 3H), 1.63–1.66

(m, 1H), 1.67 (s, 3H), 1.68 (s, 3H), 1.61–1.79 (m, 2H),

1.88–1.97 (m, 2H), 2.48 (br.d, 1H, J=13.2 Hz), 3.36

(br.s 1H), 4.97 (s, 1 H,); ¹³C NMR (125.7 MHz, C₆D₆):

ꢀ=20.0 (2x q, C-12, C-14), 20.4 (q, C-13), 23.7 (q, C-15),

25.9 (t, C-3), 26.0 (t, C-2), 27.1 (t, C-8), 28.7 (d, C-10),

36.3 (t, C-9), 40.4 (d, C-6), 41.6 (d, C-1), 121.0 (s, C-11),

126.1 (d, C-5), 133.7 (s, C-4), 135.7 (s, C-7); MS (EI, 70

eV), m/z (rel. int.) 204 [M⁺] (67), 189 (41), 175 (5), 161

(100), 147 (18), 133 (26), 119 (45), 105 (56), 91 (45), 81

(67), 77 (31), 67 (17), 55 (33), 41 (59).

3.16. (À)-trans-Selina-4(15),11-dien-5-ol (12)

Colourless oil; RI_CPSil5=1629; R_f=0.87; sense of

optical rotation (chloroform): (À); ¹H NMR (500 MHz,

C₆D₆): ꢀ=0.85 (s, 3H, CH₃-14), 0.95–1.00 (m, 1H,

H-a),1.09–1.14 (m, 1H, H-9a), 1.39–1.44 (m, 1H, H-6a),

1.47–1.65 (m, 4H, H-2a, H-8, H-2b), 1.65 (s, 3H, CH₃-

13), 1.73–1.76 (m, 1H, H-6b), 1.92–2.05 (m, 3H, H-9b,

H-1b, H-3a), 2.52–2.65 (m, 2H, H-7, H-3b), 4.59 (s, 1H,

H-15a), 4.73 (s, 1H, H-15b), 4.85 (d, 2H, H-12, J=11.4

Hz); ¹H NMR (500 MHz, CDCl₃): ꢀ=0.88 (s, 3H), 1.06

90

A. Martins Adio et al. / Phytochemistry 61 (2002) 79–91

(br.d, 1H, J=13.2 Hz), 1.20 (dt, 1H, J₁=3.8, J₂=12.9

Hz), 1.51–1.62 (m, 5H), 1.67 (dt, 1H, J₁=4.7, J₂=13.2

Hz), 1.76 (s, 3H), 1.79–1.88 (m, 2H), 2.13 (dd, 1H,

J₁=4.7, J₂=3.2 Hz), 2.52 (m, 1H, J=4.1 Hz), 2.62 (dt,

1H, J₁=6.3, J₂=13.2 Hz), 4.96 (br.s, 1H), 4.73 (br.s,

1H), 4.75 (br.s, 1H,), 4.82 (t, 1H, J =1.6 Hz); ¹³C NMR

(125.7 MHz, C₆D₆): ꢀ=20.0 (q, C-14), 21.2 (q, C-13),

22.8 (t, C-2), 26.5 (t, C-8), 32.1(t, C-3), 34.6 (t, C-9),

35.3 (t, C-1), 35.8 (t, C-6), 38.4 (s, C-10), 40.3 (d, C-7),

75.5 (s, C-5), 107.3 (t, C-15), 108.9 (t, C-12), 150.8 (s,

C-11), 152.9 (s, C-4); MS (EI, 70 eV): m/z (rel. int.) 220

[M⁺] (7), 205 (24), 202 (25), 187 (57), 177 (15), 159 (13),

149 (13), 137 (32), 121 (22), 109 (33), 95 (65), 81 (52), 67

(50), 55 (54), 41 (100).

Chemischen Industrie. We thank Dr. V. Sinnwell for his

support in recording NMR spectra and Mrs. A. Mei-

ners and Mr. M. Preusse for GC–MS measurements.

References

Asakawa, Y., Toyota, M., Takemoto, T., Suire, C., 1979. Pungent

sesquiterpene lactones of the European liverworts Chiloscyphus

polyanthus and Diplophyllum albicans. Phytochemistry 18, 1007–

1009.

Asakaw, Y., Toyota, M., Ueda, A., Tori, M., Fukazawa, Y., 1991.

Sesquiterpenoids from the liverwort Bazzania japonica. Phytochem-

istry 30, 3037–3040.

Asakawa, Y., 1995. Chemical constituents of the bryophytes. In: Herz,

W., Kirby, G.W., Moore, R.E., Steglich, W., Tamm, C. (Eds.),

Progress in the Chemistry of Organic Natural Compounds, Vol. 65.

Springer, Vienna, New York.

3.17. (+)-8, 9-Epoxyselina-4,11-diene (13)

Benesova, V., Samek, Z., Vasickova, S., 1975. Structure of the sesqui-

terpenic lactone diplophyllolide and other components from the

liverwort Diplophyllum albicans (L.) Dum. Collection of Czechoslo-

vak Chemical Communications 40, 1966–1970.

Colourless oil; RI_CPSil5=1596; R_f=0.94; sense of

1

optical rotation (benzene): (+); H NMR (500 MHz,

C₆D₆): ꢀ =1.27 (s, 3H, CH₃-14), 1.31–1.36 (m, 2H, H-

1),1.46 (s, 3H, CH₃-15), 1.47–1.53 (m, 1H, H-2a), 1.62–

1.71 (m, 1H, H-2b), 1.72–1.81 (m, 2H, H-3), 1.82 (s, 3H,

CH₃-13), 2.10 (t, 1H, H-6a, J=11.7 Hz), 2.15–2.19 (m,

1H, H-7), 2.23 (dd, 1H, H-6b, J₁=2.8, J₂=11.4 Hz),

2.59 (d, 1H, H-9, J=3.8 Hz), 3.06 (d, 1H, H-8, J=3.8

Hz), 4.89 (t, 1H, H-12a, J=1.6 Hz), 5.07 (s, 1H, H-12b);

¹³C NMR (125.7 MHz, C₆D₆): ꢀ=18.4 (q, C-15), 19.0

(t,C-2), 21.2 (q, C-13), 22.5 (q, C-14), 25.4 (t, C-6), 32.1

(t, C-3), 33.5 (s, C-10), 35.8 (t, C-1), 46.4 (d, C-7), 56.8

(d, C-8), 60.6 (d,C-9), 111.4 (t, C-12), 124.5 (s, C-4),

133.4 (s, C-5), 148.0 (s, C-11); MS (EI, 70 eV), m/z (rel.

int.): 218 [M⁺] (26), 203 (27), 189 (20), 175 (22), 159

(17), 147 (32), 133 (31), 119 (39), 107 (67), 91(64), 79

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Article Doi

Volatile components from European liverworts Marsupella emarginata, M. aquatica and M. alpina

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