The Alkaloids Vol.03

352 Pages·1973·22.47 MB·English

A Specialist Periodical Report
The Alkaloids
Volume 3
A Review of the Literature Published between
July 1971 and June 1972
Senior Reporter
J. E. Saxton, Department of Organic Chemistry, University of Leeds
Reporters
R. Goutarel, Centre Nationale de la Recherche Scientifique, Gif-sur-
Yvette, France
R. 6. Herbert, University of Leeds
J. A. Joule, University of Manchester
Mme. F. Khuong-Huu, Centre Nationale de la Recherche Scientifique,
Gif - sur- Yvette, France
S. W. Page, University of Georgia, U.S.A.
S. W. Pelletier, University of Georgia, U.S.A.
M. Shamma, Pennsylvania State University, U.S.A.
V. A. Snieckus, University of Waterloo, Ontario, Canada
0 Copyright 1973
The Chemical Society
Burlington House, London, W1 V OBN
ISBN: 0 85186 277 2
Library of Congress Catalog No. 70-6 16637
Set in Times on Monophoto Filmsetter and printed offset by
J. W. Arrowsmith Ltd., Bristol, England
Made in Great Britain
Foreword
This third volume in the series of Specialist Periodical Reports on Alkaloids
comprises reviews of progress in the whole field of alkaloid chemistry for the
period July 1971 to June 1972. For the first time we include a summary of recent
developments in the chemistry of the Steroidal Alkaloids of the Solanum and
Veratrum Groups. In thischapter, contributed by R. B. Herbert, the emphasis has
properly been given to the period of review adopted for the volume as a whole,
but in order to fill in the gap between existin2 reviews and July 1971 the salient
literature references in this area from the beginning of 1970 have also been
included.
Once again it is a pleasure to acknowledge the enthusiastic co-operation of
my colleagues in the preparation of this Report, and to record my sincere ap-
preciation of the efforts they have made to produce their respective reviews by
the agreed date. That there was a short delay before the final manuscript arrived
was solely due to factors that could neither have been anticipatednorc ircumvented
-the inevitable hazard of attempting to compile a comprehensive, critical
summary of the literature within three months of the end of the period under
review. In this connection it is obvious that the accessibility of material in the
major international journals presents no problem; but all contributors to these
volumes would greatly appreciate reprints of papers published in minor and/or
regional journals that are not found in every library. In case of a change of author
it would be most convenient if such reprints were mailed to the Senior Reporter,
who will then forward them to the appropriate contributor.
Suggestions concerning the presentation of subsequent Reports in this series
will, as always, be welcomed.
J. E. Saxton

Cont ents
Chapter 1 Biosynthesis
By R. B. Herbert
Terpenoid Indole Alkaloids 1
Ergot 6
Betalaines 8
Gramine 10
Indolmycin 10
Gliotoxin 12
Pyrro lni trin 13
/I-Carboline, Simple Isoquinoline, and Phenylethylamine
A1 kaloid s 14
Dolichotheline 17
Benzylisoquinoline Alkaloids 17
Amaryllidaceae Alkaloids 21
Lunarine 24
Piperidine Alkaloids 25
Pyrrolidine Alkaloids 32
Quinoline Alkaloids 34
Quinazoline A1 kalo ids 35
Phenazines 36
Pyrrolizidine Alkaloids 40
Steroidal Alkaloids 40
Chapter 2 Pyrroiidine, Piperidine, and Pyridine Alkaloids
By V. A. Snieckus
1 Pyrrolidine Alkaloids 43
2 Piperidine Alkaloids 46
3 Pyridine Alkaloids 51
4 Mono- and Sesqui-terpenoid Alkaloids 55
vi The A lka lo ids
Chapter 3 Tropane Alkaloids 67
By J. E. Saxton
Chapter 4 The Pyrrolizidine Alkaloids
By J. E. Saxton
1 General 76
2 The Necine Bases and Simple Related Alkaloids 79
3 The Ester Alkaloids 82
4 Pharmacological Aspects 89
Chapter 5 The lndolizidine Group
By J. E. Saxton
1 Efueocurpus Alkaloids 91
2 The Tylophorine Group 94
Chapter 6 The Quinolizidine Alkaloids
By J. E. Saxton
1 Occurrence, and Isolation of New Alkaloids 95
2 Tetracyclic Alkaloids 99
Lupanine-Sparteine Group 99
Matrine Group 102
3 Alkaloids of Coccinellidae 105
Chapter 7 Quinoline, Quinazoline, Acridone, and Related
Alkaloids
By V. A. Snieckus
1 Quinoline Alkaloids 104
2 Quinazoline Alkaloids 112
3 Acridone Alkaloids 114
Chapter 8 The lsoquinoline Alkaloids
By M. Shamma
P-Phenethylamines and Simple Isoquinolines 116
Benzylisoquinolines 119
Isoquinolones 122
Contents vi i
Pavines and Isopavines 122
Bisbenzylisoquinolines 123
Cularines 128
Cularine-Morphine Dimers 129
Dibenzopyrrocolines 129
Proaporphines 129
Aporphines 130
Proaporphine-Benzylisoquinoline Dimers 139
Aporphine-Benzylisoquinoline Dimers 139
Oxoaporphines 142
Phenanthrenes 143
Taspine 143
Protoberberines 144
Benzoph enan th ridines 149
Protopines 150
Phthalideisoquinolines 151
Spirobenzylisoquinolines 152
Rhoeadines and Papaverrubines 155
Morphines and Morphinandienones 157
Emetine and Related Alkaloids 163
Simple Phenethylisoquinolines 163
Androcymbine Analogues and the Homomorphines 163
Homoaporphines and Homoproaporphines 164
Colchicine and Related Alkaloids 166
Phen yltetrah ydroisoquinolines 166
N-Benzyltetrah ydroisoquinolines 166
Cherylline 167
Naphthalenoisoquinolines 167
Azafluoran thenes 168
Chapter 9 Amaryllidaceae and Related Alkaloids 169
By V. A. Snieckus
Chapter 10 Erythrina and Related Alkaloids 180
By V. A. Snieckus
Chapter 11 lndole Alkaloids
By J. A. Joule
1 Simple Alkaloids 187
Non-tryptamines 187
Non-isoprenoid Tryptamines 188
...
Vlll The A lkalo ids
2 Isoprenoid Tryptamine and Tryptophan Alkaloids 192
Non-terpenoid Alkaloids 192
Monot erpeno id A1 kalo id s 194
Yohimbine-Corynantheine-Heteroyohimbine (and
Related Oxindoles) Group 194
Sarpagine-Ajmaline-Picraline Group 204
Strychnine-Akuammicine-Uleine Group 207
Eburnamine-Aspidospermine Group 208
Ibogamine-Cleavamine Group 214
Skeletal Rearrangements and Interconversions 214
3 Biogenetically Related Quinoline Alkaloids 214
4 Bisindole Alkaloids 22 1
Chapter 12 Lycopodium Alkaloids 227
By V. A. Snieckus
Chapter 13 Chemistry of the Diterpene Alkaloids
By S. W. Pelletier and S. W. Page
1 Introduction 232
2 Structural and Chemical Investigations 232
Aconitum and Delphinium Alkaloids : C ,-Skeleton 232
Oxonitine 232
Aconosine 234
Lapaconidine 234
Mass Spectral Studies of the C ,-Diterpene Alkaloids 235
Aconitum and Delphinium Alkaloids : C,,-Skeleton 240
Staphisine 240
Atisine-Isoatisine Rearrangement 24 1
Rearrangement of ent-Kaurane-158, 168-epoxide to
en?-(1 6 R)-Atisane-15 -one 242
Mass Spectral Studies of Ajaconine 243
Duphniphyllum Alkaloids 244
Secodaphniphylline and Methyl Homosecodaphni-
phyllate 244
Daphnilactone-A 245
Daphnilactone-B 245
3 Synthetic Studies 246
Aconitine-type Alkaloids : Syntheses Directed
toward Delphinine 246
Veatchine- and Atisine-type Alkaloids 248
Novel Syntheses of the Diterpenoid BCD Ring System 248