The Alkaloids, Volume 54

395 Pages·2000·14.14 MB·English

by  Geoffrey A. Cordell (Editor)

CONTRIBUTORS
Numbers in parentheses indicate the pages on which the authors’ contributions begin.
Josti MARIA BARBOSA-FILHO (l), Laboratorio de Tecnologia Farmaceu-
tica, Universidade Federal da paraiba, 58051-970 Joao Pessoa, PB, Brazil
EMIDIO VASCONCELOSL EITAO DA-CUNHA (l), Laboratorio de Tecnologia
Farmaceutica, Universidade Federal da paraiba, 58051-970 Joao Pessoa, PB,
Brazil
ALEXANDER IRVINE GRAY (l), Phytochemistry Research Laboratories, De-
partment of Pharmaceutical Sciences, University of Strathclyde, Glasgow,
Scotland
TOSHIKO KIGUCHI (19 l), Kobe Pharmaceutical University, Higashinada,
Kobe 658-8558, Japan
SOFIA MITAKU (259), Department of Pharmacy, Division of Pharmacog-
nosy, University of Athens, Panepistimopolis, Zografou, GR- 1577 1 Athens,
Greece
YASUOKI MURAKAMI (191) Toho University, School of Pharmaceutical
Sciences, Funabashi, Chiba 274-85 10, Japan
TAKEAKI NAITO (191), Kobe Pharmaceutical University, Higashinada,
Kobe 658-8558, Japan
ICHIYA NINOMIYA (191), Kobe Pharmaceutical University, Higashinada,
Kobe 658-8558, Japan
ALEXIOS LEANDROS SKALTSOUNIS (259), Department of Pharmacy, Divi-
sion of Pharmacognosy, University of Athens, Panepistimopolis, Zografou,
GR- 1577 1 Athens, Greece
MASANORI SOMEI (19 l), Kanazawa University, Faculty of Pharmaceutical
Sciences, Takara-machi, Kanazawa 920-8640, Japan
FRAN~OIS TILLEQUIN (259), Laboratoire de Pharmacognosie de
1’Universite RenC Descartes UMR/CNRS 8638, FacultC de Pharmacie, F-
75006 Paris, France
YUUSAKU YOKOYAMA (191), Toho University, School of Pharmaceutical
Sciences, Funabashi, Chiba 274-85 10, Japan
vii
PREFACE
Recent progress on three quite different alkaloid groups are discussed in
this volume of The Alkaloids: Chemistry and Biology.
The first chapter, by Barbosa-Filho, da-Cunha, and Gray, describes in great
detail the tremendous volume of research that has been conducted in recent
years on the alkaloids of the Menispermaceae, a family which produces a
wide structural range of benzylisoquinoline alkaloids. The second chapter is
a very special collaborative effort by three Japanese chemistry groups led by
Somei, Murakami, and Ninomiya discussing the recent developments on the
synthesis of the ergot alkaloids. Finally, Skaltsounis, Mitaku, and Tillequin
discuss the diverse acridone alkaloids from the perspectives of their isolation,
distribution, synthesis, and biological properties.
Geoffrey A. Cordell
University of Illinois at Chicago
ix
- CHAPTER l-
ALKALOIDS OF THE MENISPERMACEAE
Jo& U BARBOSA-FILHO, Em10 VASCONC~LOSL EITAO DA-CUNM
Laboratorio de Tecnologia Farma&utica
Universidade Federal da Paraiia
5805 l-970 - Jo&o Pessoa- PB, Brazil
AND
ALEXANDERI RVINE GRAY
Phytochemistry Research Laboratories
Department of Pharmaceutical Sciences
University of Strathclyde
Glasgow, Scotland
I. Introduction
A. Historical Aspects of the Family Menispermaceae
B. Botanical Studies
C. Brief Description of the Alkaloids
II. Survey of the Alkaloids of the Menispermaceae
A. Alkaloids of the Menispermaceae
B. The Possible Common Origin of the Alkaloids Isolated from Plants of the
Menispermaceae
C. Biosynthetic Map of the Menispermaceae
D. Classification of the Alkaloids of the Menispermaceae
E. Chemical Profile of the Menispermaceae
III. summary
IV. Conclusions
Acknowledgements
References
I. Introduction
The plant family Menispermaceae is widely known for the production of a
great variety of alkaloids. This was first noticed even before the family was created,
when, after the first visits of European colonists, they came back talking about
soldiers being wounded by arrows tipped with poison. Further details of this poison
came later when it was observed that it was composed of extracts from poisonous
herbs. There were many diierent herbs used to produce the poison, including one
known by the natives as “ourari”. It is believed that the term curare, which describes
THE ALKALOIDS, VOL. 54 Copyright D 2ooO by Academic Press.
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2 BARBOSA-FILHO, DA-CUNHA, AND GRAY
South American arrow poisons that kill by paralysis, is derived from this Indian
name (I). Curare is used principally for hunting and fishing purposes by the Indian
tribes of the Amazon region. In 1935 it was discovered that the alkaloid
tubocurarine was the main active ingredient of curare. At that time, the structure
given to this alkaloid was incorrect, and only in 1970 was the correct structure
elucidated, showing that only one of the isoquinoline nitrogens was quatemary. The
neuromuscular blocking activity of tubocurarine, very useful in anesthesia, led
scientists all over the world to try to synthesise compounds with stronger activity
and less toxicity. One of the compounds discovered in this way was the anaesthetic
“atracurium” developed by researchers at the University of Strathclyde and the
Wellcome Laboratories.
A. HISTORICAL ASPECTS OF THE FAMILY MENISPERMACEAE
The Menispermaceae (Moonseed family) was named by A. L. de Jussieu in
1789 and he included the generaMenispermum L., Cissampelos L., Leaeba Forsk.,
Epibaterium Forsk. and Abuta Aubl. (2). It was renamed later as Menispermoidees
by Ventenant and Menispermees by Jeaume. In 1824, it was finally designated
Menispermaceae by A.P. de Candolle, who divided the family into three tribes:
Menispermeae, Lardizabaleae and Schizandreae. The tribes Lardizabaleae and
Schizandreae were later included in the families Berberidaceae and Magnoliaceae,
respectively.
In 1851, Miers (3) described six tribes based on embryo structure:
Heterocinaceae, Anomospermeae, Tiliacoreae, Leptogoneae, Platygoneae and
Pachygoneae.
In 1867, Bentham and Hooker (4) subdivided the family into four tribes,
containing a total of 31 genera according to the morphology of the carpels, fruits
and seeds: Tinosporeae, Cocculeae, Cissampelideae and Pachygoneae.
In 1872, Baillon kept the same divisons as Bentham and Hooker, and
substituted the tribe Tinosporeae with Chasmanthereae( 2).
Finally, Diels (5) in 1910, based on Mier’s work, published a new division of
the family with 8 tribes: Anamirteae, Anomospermeae, Cocculeae, Fibraureae,
Hyperbaeneae, Peniantheae, Tinosporeae and Tricliseae; three sub-tribes of the
Cocculeae were delineated: Cocculineae, Stephaniineae and Cissampelineae
containing a total of 72 genera.
Diel’s idea, based on the morphological aspects of the albumen and
cotyledons was kept by Troupin when in 1962 he published a botanical study of the
African Menispermaceae (6). This is the division that is still used today (see Table I).
1. ALKALOIDS OF THE MENISPERMACEAE 3
B. BOTANICAL STUDIES
The family Menispermaceae is part of the order Ranunculales and is divided
into eight tribes and three sub-tribes. It is composed of some 72 genera and
approximately 400 species (5). Its species are distributed in all continents, with
predominance in the tropical regions. The largest genus in the family is Stephania
with 43 species, followed by Tinospora with 35, Abuta with 30, Tiliacora with 22,
and Cissampelos and Cyclea, both with 19 species.
The name Menispermaceae is derived from the half-moon shape of the
seeds( 2). According to Dahlgren’sc lassification (7), the position of the family is:
KINGDOM: Plantae
CLASS: Magnoliopsidae (= Angiospermae)
SUB-CLASS: Magnoliidae (= Dicotyledoneae)
SUPER ORDER: Ranunculiflorae
ORDER: Ranunculales
FAMILY: Menispermaceae
The plants are perennial. They are woody, being predominantly climbing shrubs
with anomalous stem structure. The leaves are alternate, the flowers are unisex and
the seedsm ay or may not have an endosperm.
Table I shows all of the 72 genera of the family in their respective tribes and
sub tribes, the approximate number of species,a nd their geographical distribution.
C. BRIEF DESCRPTION OF THE ALKALOIDS
The family is well known for the production of alkaloids of various kinds,
among which those derived from a I-benzyltetrahydroisoquinoline (cf. Scheme 2)
precursor are the most common. It is also notable that alkaloids of the
bisbenzylisoquinoline type are the most commonly found in plants of this family.
This group of compounds is an integral part in the preparation of many of the dart
poisons known as “curare”, used by the South American Indians to immobilise
(anesthetise?)a nimals and birds, and that served as models for the potent drugs used
in anesthesia such as “atracurium”. In reviewing the alkaloids from the family
Menispermaceae, covering the period from 1970 to 1997, it was found that 22
different classeso f alkaloids have been isolated from this family. Among these, the
bisbenzylisoquinoline types were the most abundant, with 604 citations from many
different plant species. In second place came the aporphine type with 303 citations,
and third, protoberberines with 275 citations. In contrast, it is interesting to note the
paucity of the citations for the other 19 types of compounds isolated from plants of
this family.
4 BARBOSA-FILHO, DA-CUNHA, AND GRAY
TABLE I
Subdivisions of the family Menispermaceae after Brummitt, 1992 (5,s).
TRJBES T GEOGRAF’HICAL DISTRlBUTION 1
Genera
ASIA OCEAN
Sub-tribe
TRICLISIEAE
17 Albertisia Beck
6 Anisocycla Baill.
1 Beinaertia Louis ex Troupiu *
3 Carronia F. Muell.
l
5 ChondodendronR uiz et Pavon
4 Curarea Bameby & Kmkoff
12 Epinehwm Hiem
2 HaematocarpusM iers *
1 Macrococculus Becc. *
1 Pleogvne Miers *
17 Pycnarrhena Miers
18 Sciadotenia Miers
1 Mclisia Bed.
3 S’heonema Miers *
22 Tiliacora Co&r.
10 Triclisia Bedh.
PENIANTBEAE
2 PenianthusM iers
1 SphenocentrumP ierre
ANAMIRTEAE
4namirta Colebr.
4rcangelisia Becc.
Coscinium Cokbr.
FIBRAUREAE
BuraFoiaT houafs
Fibraurea Lour.
Tinomiscium Miers
1. ALKALOIDS OF THE MENISPERMACEAE 5
TABLE I (Continued)
NlUUbU TRIBES T GEOGIUU’HICAL DISTRIBUTION
of Genera
species Sub-tribe AFRICA ASIA OCEAN
TINOSPOREAE
1 Aspidocatya Hook. F. & Thomson *
1 Calycocarpum NW. ex Spach *
2 Chasmanthera Ho&t.
1 Chlaenandra Miq. *
1 Dialyfheca Exell. & Mendonp *
3 Dioscoreophyllum Engl.
8 Disciphania Eichl. *
1 Fawceftia F. Muell. l J
2 Jateorhiza Miers
4 Kolobopetalum Engl.
1 Leptotherantha Louis ex Troupin *
4 Odontocatya Miers *
1 Orthogynium Baill. *
10 Parabaena Miers
1 Plafyfinospora (Engl.) Diels *
2 Pridania Gagnep.
l
2 Rhigiocatya h4iers
1 Sarcolophium Troupin *
1 SomphoxyIum Eichl. *
1 S’andropus A. C. Smith *
1 Sjmtriandrium Engl. *
35 Tinospora Miers
ANOMOSPERMEAE
30 4buta Aubl.
5 4nomospermum Miers *
4 Caryomene Bameby & Krukoff
1 Flissawhena h4iers
l
6 Telitoxicum Moldenke
continues)
6 BARBOSA-FILHO, DA-CUNHA, AND GRAY
TABLE I (Contimed)
alnlbfz TRIBES GEOGRAPHICAL DISTFUBUTION.
of Genera
species Sub-tribe AFRICA ASIA
HYPERBAENBAE
1 Hyperbaena
COCCULEAE
Cocculinae
11 Cocculus DC.
3 Diploclisia Miers
17 Hypserpa Miers *
2 Legnephora Miets
5 Litnacia Lour.
1 Limaciopsis Engl.
8 Menispermum L.
12 Pachygone Miers
6 Pericampylus Miers *
6 RhaptonemaM iers *
1 Sarcopetalum F. Muell.
2 VinomeniumD iels
1 SpirospermumT houars
1 StrychnopsisB ail].
1 Ungulipetalum Moldenke *
Stephaniinae
43 StephaniaL our.
Cissampelinae
4 llntizoma Miers
19 CissampelosL .
19 Cyclea Am. ex Wight
2 Paracyclea Kudo & Yatnamoto
* Genera with no phytochemical citation for any of their species.
1. ALKALOIDS OF THE MENISPERMACEAE 7
II. Survey of the Alkaloids of the Menispermaceae
A. ALKALOIDS OF THE MENISPERMACEAE
As stated above, the family Menispermaceae is very rich in diverse types of
alkaloids. Emphasis is given to the significant majority of alkaloids derived from
the benzyltetrahydroisoquinoline nucleus. One of the most important members of
this group of alkaloids is tubocurarine, which is part of curare, described for the
first time in 1805 by Humboldt, who observed its utilization by South American
Indians as a dart poison for hunting and fishing purposes. Its structure was
elucidated by King in 1935 (9), although he incorrectly assigned it as being a
bisquatemary salt of the bisbenzyltetrahydroisoquinoline nucleus. Only in 1970 was
it discovered that it was a monoquatemary salt. The synthesis of tubocurarine in
1958 by Veronin, opened the way for the use of other quatemary ammonium salts
as neuromuscular blocking agents which are more active and less toxic.
There are two previous reviews of the literature on alkaloids from the
Menispermaceae. The first was published by Tomita in 1952 (IO) and the second
was by Thomber in 1970 (II). The fact that the last review was published some 27
years ago presented an obvious challenge, given the large volume of publications
on alkaloids of the Menispermaceae that have appeared in the ensuing years. The
number of papers discussed by each of the previous reviews and the number of
papers reviewed in this work are seen in Table II. A limited review of alkaloids
from the South American Menispermaceae was published in 1996 (12).
As seen in Table II, in the 18 years between Tomita’s review and Thomber’s
review, the number of plant studies almost doubled and the number of alkaloids
isolated almost trebled. However, only one new class of alkaloid appeared. If we
compare Thomber’s review with the present review, we can see a huge and
significant increase in the number of plants studied (from 52 to 159) and in the
number of alkaloids isolated (from 241 to 1525).
TABLE II. Plants of the family Menispermaceae studied, number of alkaloids
described and number of bibliographic citations.
DATA OBATAINED FROM PLANTS ALKALOIDS NUMBER OF
STUDIED DESCRIBED CITATIONS
TOMITA’S REVIEW
1952 33 92 158
THORNBER’S REVIEW
1970 52 241 124
THIS WORK
(VP TO NOVEMBER 1996) 159 1525 531