A Specialist Periodical Report The Alkaloids Volume 4 A Review of the Literature Published between July 1972 and June 1973 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. B. 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. S. S. Salgar, Pennsylvania State University, U.S.A. M. Shamma, Pennsylvania State University, U.S.A. V. .A. Snieckus, University of Waterloo, Ontario, Canada 0 Copyright 1974 The Chemical Society Burlington House, London, WIV OBN ISBN:0 85186 287 X Library of Congress Catalog No. 70-616637 Set in Times on Monophoto Filmsetter and printed offset by J. W. Arrowsmith Ltd., Bristol, England Made in Great Britain Foreword This fourth volume in the series of Specialist Periodical Reports on Alkaloids follows the pattern established by its predecessor, and comprises summaries of progress in the whole field of alkaloid chemistry for the period July 1972-June 1973. In addition there is also included a more extended review of the aporphine alkaloids, in which are discussed developments in this sub-group of benzyliso- quinoline alkaloids since the last comprehensive survey was compiled. The length of this chapter reflects the continuing enormous activity in this area, and amply illustrates the versatility of biosynthetic processes in the construction of substituted aporphines. It is hoped that Dr. Shamma’s account, which includes a reference list of the 107 aporphines known up to the summer of 1973, will prove invaluable to all chemists interested in the structural and biosynthetic relation- ships in the aporphine group. My request last year for reprints of papers in the less accessible journals has met with some response, for which I hasten to acknowledge my appreciation. The Senior Reporter and all contributors hope that alkaloid chemists will continue to send us such reprints, which help substantially ig the prompt com- pilation of these Reports. Once again it is a pleasure to acknowledge the enthusiastic co-operation of my colleagues, in circumstances that in some respects become more difficult with each succeeding year. As always, we shall welcome suggestions concerning the presentation of future Reports. J. E. SAXTON Contents Chapter 1 Biosynthesis 1 By R. B. Herbert 1 Piperidine, Pyridine, and Pyrrolidine Alkaloids 1 Lycopodine 1 Dioscorine 3 Anabasine 4 Nicotine 7 Miscellaneous Pyridine Alkaloids 9 Coniine 10 Nigrifactin 11 R h izoct omi a leg um ini col a Bases 12 Quinolizidine Alkaloids 12 Cry ogenine 13 Tropane Alkaloids 13 2 Isoquinoline Alkaloids 15 Morphine Alkaloids 15 Magnoflorine 17 Alpinigenin 18 Colchicine 19 3 Amaryllidaceae Alkaloids 23 Lycorenine 23 Lycorine 24 Ismine 25 4 Alkaloids Derived from Tryptophan 26 Dimethyltryptamine Derivatives 26 Pyrrolni trin 28 Echinulin 29 Strychnine 30 Ergot 32 5 Terpenoid and Steroidal Alkaloids 35 Daphn iphy llum A1 kaloids 35 Steroidal Alkaloids 37 vi Contents 6 Miscellaneous Aliphatic Bases 38 Betalaines 38 Cephalosporin C 40 M it omy cins 40 M ycelianamide 42 7 Miscellaneous Aromatic Bases 42 Dolichotheline 42 Quinoline Alkaloids 43 Nybomycin 44 Benzoxazinones 44 Pyrimidines 45 Phenazines 46 Chapter 2 Pyrrolidine, Piperidine, and Pyridine Alkaloids 50 By V. A. Snieckus 1 Pyrrolidine Alkaloids 50 2 Piperidine Alkaloids 51 3 Pyridine Alkaloids 58 4 Mono- and Sesqui-terpenoid Alkaloids 67 Chapter 3 Tropane Alkaloids 78 By J. E. Saxton Chapter 4 The Pyrrolizidine Alkaloids 84 By J. E. Saxton 1 General 84 2 The Ester Alkaloids 85 3 Pharmacological Aspects 98 Chapter 5 The Indolizidine Group 100 By J. E. Saxton Contents vii Chapter 6 The Quinolizidine Alkaloids 104 By J. E. Saxton 1 The Cytisine-LupanineSparteine-Matrine Group 104 Occurrence, and Isolation of New Alkaloids 104 Structural, Spectroscopic, and Chemical Studies 107 2 Ormosia Alkaloids 113 3 Alkaloids of Coccinellidae 115 Chapter 7 Qu inoline, Quinatoline, Acridone, and Related 117 Alkaloids By V. A. Snieckus 1 Quinoline Alkaloids 117 2 Quinazoline Alkaloids 12 4 3 Acridone and Related Alkaloids 125 Chapter 8 P-Phenethylamines and the lsoquinoline Alkaloids 128 By V. A. Snieckus 1 General 128 2 fl-Phenethylamines 129 3 Simple Isoquinoline Alkaloids 133 4 Benzylisoquinoline Alkaloids 137 5 Pavine Alkaloids 142 6 Dibenzopyrrocolines 143 7 Proaporphine, Aporphine, and Phenanthrene Alkaloids 143 8 Morphine and Morphinandienone Alkaloids 154 9 Colchicine Alkaloids 162 10 Cularine 164 11 Protoberberine Alkaloids 164 12 Protopine Alkaloids 172 13 Benzophenanthridine Alkaloids 174 ... Cont ents Vlll 14 Phthalidekoquinoline Alkaloids 178 15 Rhoeadine and Papaverrubine Alkaloids 179 16 Spirobenzylisoquinoline Alkaloids 183 17 Alkaloids from Hypecoum erectum 185 18 Ipecacuanha Alkaloids 186 19 Dimeric Benzylisoquinoline Alkaloids 188 Chapter 9 The Aporphines 197 By M. Shamma and S. S. Salgar 197 1 Introduction 199 2 New Alkaloids 199 0-Methylbulbocapnine 199 Norcorydine 200 N-M e thy1h ernovine 200 10-0-Methylhernovine 20 1 N-Methy 1- 10-0-methylh ernovine 20 1 Lindcarpine 202 N-Methyl-lindcarpine 202 Norglaucine 203 Wilsonirine 204 Predicentrine 204 Norpredicentrine 205 Bracteoline ( - )-Dicentrine 205 206 Deh ydrodicentrine 206 ( & )-Isoboldine 206 Duguetine 207 Cataline 208 Dehydroglaucine 208 Nornantenine 209 Nordomesticine 210 Hernandine 21 1 Ocokryptine 21 1 Oconovine 212 Thalicsimidine (p urpureine) 212 Norpurpureine 212 0-Demet hylpurpureine 213 Dehydro-ocoteine 214 Didehydro-ocoteine