The Alkaloids Vol.05

318 Pages·1975·22.34 MB·English

A Specialist Periodical Report
The Alkaloids
Volume 5
A Review of the Literature Published between
July 1973 and June 1974
Senior Reporter
J. E. Saxton, Department of Organic Chemistry,
University of Leeds
Reporters
H. 0. Bernhard, Siegfried AG, Zofingen, Switzerland
R. Goutarel, Centre Nationale de la Recherche Scientifique, Gif-sur-
Yvette, France
R. B. Herbert, University of Leeds
J. A. Joule, University of Manchester
Mme. F. Khuong- Huu, Centre Nationale de la Recherche Scientifique,
Gif-sur-Y vette, France
S. W. Page, University of Georgia, U.S.A.
S. W. Pelletier, University of Georgia, U.S.A.
V. A. Snieckus, University of Waterloo, Ontario, Canada
@ Copyright 1975
The Chemical Society
Burlington House, London, W1 V OBN
ISBN: 0 85186 297 7
ISSN : 0305-9707
Library of Congress Catalog No. 70-61 6637
Set in Times on Monophoto Filmsetter and printed offset by
J. W. Arrowsmith Ltd., Bristol, England
Made in Great Britain
Foreword
This fifth volume in the series of Speciulisr Periodical Reports on Alkaloids
reviews the literature from July 1973 to June 1974. Since the whole field of
alkaloid chemistry and biosynthesis has been covered, and since no additional,
extended reviews are included, this volume will, it is hoped, give a clear indication
of progress during the year under review, and the vigour and enthusiasm with
which this fascinating subject is currently being studied. In common with
previous years, the indole and benzylisoquinoline groups dominate the scene
with, of course, an ever increasing level of activity and sophistication in the realm
of biosynthesis. The smaller groups of alkaloids, although not so intensively
studied, continue, however, to provide examples of truly outstanding work ;
witness, for example, the ingenuity with which the immensely complicated di-
terpene alkaloids are being constructed.
Alkaloid chemistry is thus in a very healthj state, and it is on this optimistic
note that we present this volume, the last with which I shall be involved as Senior
Reporter. Volume 6 will be prepared under the direction of Professor M. F.
Grundon. It remains for me to acknowledge, as always, the enthusiastic co-
operation of my co-authors, but on this occasion I should also like to thank all
those distinguished alkaloid chemists who have contributed to the first five
volumes.
As this volume was being prepared for publication the sad news of the death
of Sir Robert Robinson was announced. Sir Robert it was who introduced me,
as an undergraduate, to alkaloid chemistry, and who later inspired me with
enthusiasm for the subject as a postgraduate student and subsequently as post-
doctoral Research Fellow. Numerous other organic chemists have shared the
inestimable privilege of working with him, but such has been Sir Robert’s con-
tribution to the subject and his influence on its development that all organic
chemists can be said to be his beneficiaries, and not simply those who have
worked directly with him. Many eloquent tributes will, I hope, be paid to his
achievements and to his memory, but a brief note of appreciation is particularly
apt in a volume on alkaloid chemistry for he, more than any other single chemist,
helped to raise the subject to the exciting discipline it is today by his own unique
gifts, a combination of a rare chemical insight and originality, a complete
mastery of organic chemistry, and quite remarkable intuitive powers.
Murch 1975 J. E. SAXTON

Contents
Chapter 1 Biosynthesis 1
By R. B. Herbert
1 Introduction 1
2 Piperidine, Pyridine, and Pyrrolidine Alkaloids 5
Piperidine Alkaloids 5
Lobinaline 8
Slaframine 9
Quinolizidine Alkaloids 10
Securinine 10
Proferrorosamine A 11
Tenellin 11
Tropane Alkaloids 12
Nicotine 14
3 Isoquinoline Alkaloids 15
Aporph i ne A1 kal oids 15
Alkaloids of Croton Species 17
Homoaporphine Alkaloids 18
Colchicine 18
4 Amaryllidaceae Alkaloids 19
5 Mesembrine Alkaloids 22
6 Evyrhrina Alkaloids 24
7 Alkaloids Derived from Tryptophan 25
Terpenoid Indole Alkaloids 25
Brevianamide 26
Cyclopiazonic Acid 26
Ergot Alkaloids 27
8 Miscellaneous Bases of Aromatic Origin 35
Furoquinoline Alkaloids 35
Pe ga n in e 37
Graveoline 38
Chrysogine 39
Benzodiazepine Bases 39
Anthramycin 40
Shihunine 42
vi The A Iku 1o id s
Phenazines 44
Ephedrine 45
Betalains 46
Prodigiosin 47
Phenet by lamines 48
Dolichotheline 48
9 Miscellaneous Bases of Aliphatic Origin 49
Tenuazonic Acid 49
Azetidine-2-carboxylic Acid 50
p-Lactam Antibiotics 51
Mitomycins, Geldanomycin, Rifamycin S, and
Streptovaricin D 52
Monoterpenoid Alkaloids 54
Chapter 2 Pyrrolidine, Piperidine, and Pyridine Alkaloids 56
By V. A. Snieckus
1 Pyrrolidine Alkaloids 56
2 Piperidine Alkaloids 57
3 Pyridine Alkaloids 6t
4 Monoterpenoid Alkaloids 63
5 Sesquiterpenoid Alkaloids 64
Nuphur Alkaloids 64
Dendvohiurn Alkaloids 67
Celustrus and Euonymus Alkaloids 67
Chapter 3 Tropane Alkaloids 69
By J. E. Saxton
Chapter 4 The Pyrrolizidine Alkaloids 77
By J. E. Saxton
1 The Necine Bases and Simple Alkaloids 77
2 The Ester Alkaloids 80
3 Pharmacological Aspects 86
Chapter 5 Indolizidine Alkaloids 57
By J. E. Saxton
1 Indolizidine Alkaloids of Dendrobium Species 87
2 Slaframine 88
3 Alkaloids of Tylophova Species 89
Conferits vii
Chapter 6 The Quinolizidine Alkaloids 93
By J. E. Saxton
1 The Cytisine-Lupanine-Sparteine-Matrine Group 93
Occurrence, and Isolation of New Alkaloids 93
Chemical, Spectroscopic, and Synthetic Studies 95
2 The Ormosiu Alkaloids 99
3 Alkaloids of the Coccinellidae 101
Chapter 7 Quinoline, Quinazoline, Acridone, and Related
Al ka Io ids 103
By V. A. Snieckus
1 Quinoline Alkaloids 103
2 Quinazoline Alkaloids 108
3 Acridone Alkaloids 109
Chapter 8 p-Phenethylamines and the lsoquinoline Alkaloids 111
By H. 0. Bernhard and V. A. Snleckus
I General 111
2 p-Phenethylamines 112
3 Simple Isoquinoline Alkaloids 118
4 Benzylisuquinoline Alkaloids 125
5 Pavine Alkaloids 131
6 Dibenzopyrrocoline Alkaloids 133
7 Proaporphine, Aporphine, and Phenanthrene Alkaloids 134
8 Morphine and Morphinandienone Alkaloids 141
9 Colchicine Alkaloids 147
10 Cularine Alkaloids 149
I1 Protoberberine Alkaloids 149
12 Protopine Alkaloids 155
13 Benzophenanthridine Alkaloids 155
14 Phthalideisoquinoline Alkaloids 158
15 Rhoeadine and Papaverrubine Alkaloids 159
The A I kal o ids
16 Spirobenzylisoquinoline Alkaloids 163
17 lpecacuanha Alkaloids 164
18 Dimeric Benzylisoquinoline Alkaloids 164
Chapter 9 Amaryllidaceae and Related Alkaloids 170
By V. A. Snieckus
Chapter 10 Erythrina and Related Alkaloids 176
By V. A. Snieckus
1 Erythrinu and Homoerythrina Alkaloids 176
2 Cephlotuxus Alkaloids 179
Chapter 1 1 I ndole Alkaloids 183
By J. A. Joule
1 Introduction 183
2 Simple Alkaloids 191
Non-tryptamines 191
Non-isoprenoid Tryptamines 194
3 Isoprenoid Tryptamine and Tryptophan Alkaloids 197
Non-terpenoid Alkaloids 197
Monot erpenoid A1 kal oids 200
Yohimbine-CorynantheineHeteroyohimbine (and
Related Oxindoles) Group 200
Sarpagine- Ajmaline-Picraline Group 207
S trychnine-Akuammicine-Condylocarpine-
Ellipticine Group 209
Eburnamine-Aspidospermine Group 213
I bogamine-Cleavamine Group 218
4 Biogenetically Related Quinoline Alkaloids 219
5 Bisindole Alkaloids 222
Chapter 12 Lycopodium Alkaloids 228
By V. A. Snieckus