PROFILE OF QUINOLIZIDINE ALKALOIDS IN ULEX SPECIES

P. Máximo and A. Lourenço

Departamento de Química, Centro de Química Fina e Biotecnologia, Faculdade de Ciências e Tecnologia
Universidade Nova de Lisboa, Quinta da Torre, 2825-114 Caparica, Portugal.

INTRODUCTION
Ulex australis
Ulex Ulex jussiaiei Ulex densus Clemente subs. Welwitschianus
The Ulex genus (Leguminosae, subfamily Papilionoideae) grows in Portugal as different species Webb Webb (Planchon) Espírito Santo, Cubas, Lousã
species, through large extensions of the country. Some of these species are spread in restrict
areas and have distinct morphological characters while others, that grow on the central zone Taxa 1.1/94 1/95 2/97
designation 2.1/94 3/95
of the country, whose characterisation is ambiguous and that have been classified differently Ulex airensis
3.1/94 1/96 Ulex minor Ulex europaeus
by several authors under the designation of U. parviflorus. More recently a new work has 2/95 2/96 Espírito Santo, Roth. L.
appeared [1] that, after the analysis of a large number of specimens, makes the distinction 4/95 3/96 Cubas, Lousã
between the taxa on the basis of morphological, chromosomic, ecological and geographic 4/96 1/97
2/98
5/96 1.2/94 1.3/94
factors. Considering this latter botanical classification and with the intention to add chemical 5/98
1/98
information to it, here we present the quinolizidine alkaloids (QA) profiles of the 19 Ulex taxa
and the chemotaxonomic considerations deduced from them.

RESULTS AND DISCUSSION

R2
In 19 taxa from 6 different species of Portuguese Ulex (Table 1), a dipiperidine H3CO N NCH3 H3CO N N
alkaloid (ammodendrine), 16 known quinolizidine alkaloids (sparteine, -isosparteine, N-
methylcytisine, cytisine, hydroxysparteine, 5,6-dehydrolupanine, rhombifoline, lupanine, R1
hydroxy-N-methylcytisine, N-formylcytisine, N-acetylcytisine, anagyrine, pohakuline, CH2OH
CH2OH
dehydrobaptifoline, baptifoline and epibaptifoline) and 4 new quinolizidine alkaloids
(jussieiines A-D) [2] were identified by GC and GC-MS analysis. These alkaloids were jussiaeiine A jussiaeiine B R1 = R2 = H
detected in almost each species and are, apparently, a typical QA profile of Portuguese
Ulex. jussiaeiine C R1 = OH; R2 = H
NCH3
jussiaeiine D R1 = H; R2 = OH
The different characteristics
N
between species seems to be the
relative amount of the 7 more
abundant alkaloids present
1.3/94
O
(cytisine, N-methylcytisine,
1.2/94

N
(-)-N-methylcytisine
anagyrine and jussiaeiines A-D). The
quantitative GC analysis of these N
QA was performed for all taxa and NH H
by principal component analysis O
(PCA) the amount of each alkaloid in N (-)-anagyrine
each taxa provided the grouping of
the several species (Graph 1). Ulex O
europaeus and Ulex minor are (-)-cytisine
Graph 1
isolated from the other species and Factor analysis by principal component extraction of 19 taxa of
form Group 1. Portuguese Ulex.

PCA was performed for the remaining species (Graph 2) providing the identification of 3 more major groups:
Group 2 (2/97, 4/95, 4/96 and 5/96), Group 3 (3/95 and 2/96) and Group 4 (1/95, 1/96, 3/96, 1/97, 1/98, 2/98
and 5/98). Species 1.1/94, 2.1/94, 3.1/94 and 2/95 are in-between taxa.
From this study the well characterised species U. airensis, U. australis, U. densus, U. europaeus, and U. minor
1/98

5/98

form individual groups with characteristic quinolizidine alkaloid profiles. Some of the taxa known as U. jussiaei are
2/98

3/96
1/97

still undefined and others are distribute over the former groups.
1/96

2.1/94 2/97
1/95

4/95
5/96
Confronting both statistical and botanical classification we can make the following comments: U. europaeus
2/95
4/96

and U. minor, U. australis and U. airensis can be considered as different species, representing Groups 1, 2 and 4,
respectively. The taxa classified as U. densus can be separated in two chemodemes, D1 and D2; one we can
3.1/94

1.1/94

consider as the ‘true densus’ represented by chemodeme D1 (we now rename Group 3), clearly isolated from the
remaining Groups, and chemodeme D2 we include in Group 4. Interestingly, the previous species classified as U.
3/95
2/96

jussiaiei, the most controversial botanical species, is wide spread. Some of it’s taxa are included in Groups 2 and 4
(4/95, 4/96 and 5/96, 1/98, respectively) and some (1.1/94, 2.1/94, 3.1/94 and 2/95) are still undefined. From
biosynthetic considerations probably these later taxa are in an intermediate stage of development towards any of
Graph 2
the other species or represent hybrid forms.
Factor analysis by principal component extraction of 17 taxa of
Portuguese Ulex.

In order to establish the

Complete Linkage
resemblance between species,
Squared Euclidean distances
specimens classified on the basis of
morphological characters as U. CONCLUSIONS
europaeus (1.3/94), U. minor (1.2/94),
1.2/94

1.3/94

3/95
U. densus (3/95, 2/96), U. australis Portuguese Ulex is rich in -pyridone type QA. The most
2/96
(2/97) and Ulex airensis (2/98, 5/98) abundant alkaloids in each specimen are cytisine, N-
2/97
were submitted to cluster analysis. methylcytisine, anagyrine and jussiaeiines A-D. Statistic
2/98
The results obtained are depicted in treatment of the amount of each of these alkaloids allowed us to
5/98
Graph 3. Analysis of this graph classify the several taxa in 5 different species which are in
confirms the results previously good agreement with botanical classification. Jussiaeiines A-D
obtained by principal component
0 2000 4000 6000 8000 10000 12000 14000 16000
Linkage Distance apparently play a relevant role in differentiating Portuguese U.
analysis and once more, U. europaeus and the occurrence of these alkaloids in each species may be
Graph 3 and U. minor, are clearly isolated from related to the phylogeny of the genus.
Cluster analysis based on chemical characters of U. europaeus the remaining species. Closest to
(1.3/94), U. minor (1.2/94), U. densus (3/95, 2/96), U.
australis (2/97) and Ulex airensis (2/98, 5/98).
these we find U. densus that reveals
close proximity to U. australis and U. ACKNOWLEDGMENTS
airensis.
We wish to thank the staff of the Herbário, Museu,Jardim Botânico, Faculdade de Ciências, Universidade
de Lisboa, Portugal, for collecting and classifying the plant material.
REFERENCES We wish to thank Prof. Michael Wink and Andreas Tei, from the Institut für Pharmazeutische Biologie,
Universitat Heidelberg, Germany, for the mass spectra.
[1] Espírito-Santo, M. D., Cubas, P., Lousã, M. F., Pardo, C. and Costa, J. C. (1997) Anal. Jar. Bot. de One of us (P. M.) wishes to thank FCT (Portugal) for a PRAXIS XXI fellowship.
Madrid 55, 49.
[2] Máximo, P. and Lourenço, A. (2000) J. Nat. Prod. 63 (2), 201.