Synthesis of Marine Natural Products 2: Nonterpenoids

333 Pages·1992·7.6 MB·English

by  K. F. Albizati, V. A. Martin, M. R. Agharahimi, D. A. Stolze (auth.)

Bioorganic Marine
Chemistry Volume 6
Edited by Paul J. Scheuer
K.F. Albizati, V.A. Martin,
M.R. Agharahimi, D.A. Stolze
Synthesis of
Marine Natural Products 2
Nonterpenoids
With 161 Structures and 263 Schemes
Springer-Verlag
Berlin Heidelberg New York London
Paris Tokyo Hong Kong Barcelona Budapest
Professor Paul J. Scheuer
University of Hawaii at Manoa, Department of Chemistry
2545 The Mall, Honolulu, Hawaii 96822, USA
ISBN-13:978-3-642-76840-8 e-ISBN-13:978-3-642-76838-5
DOl: 10.1007/978-3-642-76838-5
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Library of Congress Catalog Card Number 89-649318
© Springer-Verlag-Berlin Heidelberg 1992
Softcover reprint of the hardcover 1s t edition 1992
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51/3020-5421O-Printed on acid-free paper
Preface
Volumes five and six of Bioorganic Marine Chemistry differ from their
predecessors in two respects - they deal exclusively with laboratory
synthesis of marine natural products and they represent the effort of a
single author and his associates.
The rationale for these departures is readily perceived. For
several decades organic synthesis has without doubt been the
most spectacular branch of organic chemistry. While the late R.B.
Woodward's dictum - organic compounds can undergo only four
basic reactions: they can gain electrons; they can lose electrons; they
can be transformed with acid or with base - is still true, the wealth
and variety of available reagents which will accomplish chemical
transformations has reached staggering proportions. Little wonder
then, that synthetic methodology has achieved a high degree of
predictability and total synthesis of natural products has been
successfully directed toward ever more challenging targets. As for the
second point, that of single authorship, multiple authorship would
invariably have led to gaps and overlaps, thus making it difficult to
assemble and assess recent research in a systematic and comprehens-
ive fashion.
These two volumes are significant not only as a testimonial to the
productivity and versatility of marine biota and to the virtuosity of
synthetic chemists. As the material is presented along biogenetic
principles, it is ideally suited to support research into the biosynthesis
of marine metabolites. The comprehensive nature of the work makes
it an easy matter to compare and evaluate different synthetic
approaches prior to any synthesis of labelled precursors.
The division into terpenoid (V 01. 5) and nonterpenoid (V 01. 6)
compounds is a natural one not only because of bulk. Nonterpenoid,
particularly amino acid-derived, metabolites have become the fastest
growing group of marine natural products. As recently as a decade
ago, this position was held by di-, and earlier by sesquiterpenoids.
This change parallels the current trend in research emphasis. Much
early work in marine natural products was the result of serendipitous
collections and separations. By contrast, most of today's research is
guided by biological activity, which in tum is skewed toward those
VI Preface
activities - e.g. antitumor, antiviral, which receive funding in in-
dustrialized societies.
While reading and editing the manuscript I was struck by the
large impact which marine natural product research has made on
organic synthesis and indeed on contemporary chemistry. It oc-
curred to me that these books could be valuable auxiliary texts for
graduate courses in Organic Synthesis.
I am indebted to Dr. Albizati and his associates for the monu-
mental task which this endeavor entailed. As before, I should like to
express my appreciation to Springer Verlag for their prompt and
expert cooperation. As always, I look forward to hearing from
members of the scientific community how we can improve future
volumes in the series.
August, 1991 Paul J. Scheuer
Table of Contents
3 Amino Acids and Peptides 1
3.1 Various Amino Acids 1
3.1.1 Camosadine . 1
3.1.2 Ovothiols A and C 1
3.1.3 (alpha)-Kainic Acid and allo-Kainic Acid. 3
3.1.4 Domoic Acid 9
3.1.5 Tetraacetylclionamide 13
3.1.6 Demethyldysidenin and Demethylisodysidenin 14
3.2 Brominated Tyrosine Derivatives . 17
3.2.1 Quinols 17
3.2.2 Aplysinadiene 19
3.2.3 Aerothionin, Homoaerothionin and
Aerophobin-1 20
3.2.4 Bastadins -1, -2, -3, and -6 . 20
3.3 Peptides. 25
3.3.1 Didemnins 26
3.3.2 Jaspamide. 30
3.3.3 Geodiamolides A and B. 39
3.3.4 Thiazole-containing Peptides . 43
3.3.4.1 Patellamides A, Band C 43
3.3.4.2 Ulicyclamide and Ulithiacyclamide. 51
3.3.4.3 Ascidiacyclamide and Dolastatin-3 . 54
3.3.5 Dolastatin-10 and Hexaacety1celenamide . 59
3.3.6 Teleocidin A-1 (Lyngbyatoxin A) and
Teleocidin A-2 . 63
4 Fatty Acid Derived Metabolites 69
4.1 Haloethers of Laurencia sp. . 69
4.1.1 Laurencenyne 69
4.1.2 Laurediol. 71
4.1.3 Laurediol Derivatives. 74
4.1.4 Laurencin. 74
4.1.5 Laurenyne 78
4.1.6 cis-Maneonenes A and B 79
VIII Table of Contents
4.1.7 trans-Maneonene B 79
4.1.8 Panacene. 84
4.2 Prostanoids 84
4.2.1 Clavulones 84
4.2.1.1 Clavulones I and II 87
4.2.1.2 Clavulone III 87
4.2.1.3 Desacetylclavulone II. 91
4.2.1.4 Chlorovulone II 92
4.2.1.5 Preclavulone A . 92
4.2.2 Punaglandins 96
4.2.2.1 Punaglandin 4 . 96
4.2.2.2 Punaglandin 3 and (7 E)-
Punaglandin-4 102
4.2.3 Hybridalactone . 106
4.3 C 8-C ll Algal Pheromones 107
4.3.1 Dictyoprolene 107
4.3.2 Dictyopterenes . 107
4.3.2.1 Dictyopterene A 110
4.3.2.2 Dictyopterene B (Hormosirene) 115
4.3.2.3 Dictyopterene C and
Dictyopterene C" . 117
4.3.2.4 Dictyopterene Df (Sirenin,
Ectocarpene) . 119
4.3.2.5 4-n-Butyl-2,6-Cycloheptadienone. 120
4.3.2.6 Multifidene 121
4.3.2.7 Desmarestene and Viridiene 125
4.3.2.8 Lamoxirene . 128
4.3.2.9 Aucantene 128
4.3.2.10 Fucoserratene 131
4.3.2.11 Giffordene 133
4.3.2.12 Clavularins A and B . 135
4.4 Miscellaneous Metabolites 139
4.4.1 Acarnidines 139
4.4.2 Pahutoxin. 139
4.4.3 D-erythro-l-Desoxydihydroceramide-l-
Sulfonic Acid 142
4.4.4 Phosponosphingoglycolipid from Turbo
cornutus 144
4.4.5 Metabolites of Plexaura fiava . 144
4.4.6 N otheia anomala Metabolite 146
4.4.7 Octacosadienoic Acids 147
4.4.8 Hexacosadienoic Acids 156
4.4.9 Diacetylenes from Reniera fulva 156
Table of Contents IX
5 Nitrogenous Metabolites. . . . . . 158
5.1 Indoles and Related Compounds. 158
5.1.1 Flustramine B . 158
5.1.2 Surugatoxins. . . 158
5.1.3 Various indoles. . 165
5.1.3.1 Trikentrins 165
5.1.3.2 Indoles Related to Aplysinopsin . 169
5.1.3.3 Dendrodoine. . . . . . .. 172
5.1.3.4 Tetrahalogenoindoles. . . .. 173
5.1.3.5 (E)-3-(6-Bromoindole-3-yl)Prop-2-
enoate. . . . . . . 173
5.2 Carbazoles. . . . . . . . . . . 175
5.2.1 Hyellazole and 6-Chlorohyellazole 175
5.2.2 Eudistomins. . . . . . 179
5.2.2.1 Eudistomin A . . 179
5.2.2.2 Eudistomins H, I, P 180
5.2.2.3 Other Eudistomins 181
5.2.3 Manzamine C 188
5.3 Pyridines . . . . 192
5.3.1 Navenone A . 192
5.3.2 Pulo'upone . 193
5.3.3 Ascididemin. 195
5.3.4 Aaptamine and Demethoxyaaptamine . 199
5.3.5 Amphimedine . . . . . . . .. 206
5.4 Guanidine-Containing and related Metabolites 210
5.4.1 Tetrodotoxin. 210
5.4.2 Saxitoxin. 211
5.4.3 Ptilocaulin . 217
5.4.4 Oroidin . . 220
5.4.5 Dibromophakellin . 223
5.4.6 Girolline. . . . 223
5.5 Nuc1eosides and Related Substances. 226
5.5.1 Mycalisin. . . . . . . . 226
5.5.2 Phidolopin . . . . . . . 227
5.5.3 6-Imino-1,9-dimethyl-8-oxopurine 228
5.5.4 1-Methylisoguanosine (Doridosine) . 229
5.6 Reniera Alkaloids . . 230
5.6.1 Mimosamycin . . . . . . . . 230
5.6.2 Reniera Isoindole. . . . . . . 231
5.6.3 7-Methoxy-1,6-dimethyl-5,8-Dihydroiso-
quinoline-5,8-dione and N-Formyl-1,2-
dihydrorenierone 234
5.6.4 Renierone. . . . . . . . . . . 237
X Table of Contents
5.7 Zoanthoxanthins. 241
5.8 Pyrrole-Containing Alkaloids 243
5.8.1 Oscarella lobularis Pyrrole Metabolite. 243
5.8.2 5-Nonylpyrrole-2-Carbaldehyde . 243
5.8.3 Pentabromopseudilin . 245
5.8.4 Bonellin, Methyl Ester 246
6 Miscellaneous Metabolites . 249
6.1 Metabolites Related to Citric Acid 249
6.1.1 Delesserine 249
6.1.2 Leptosphaerin 250
6.2 Brominated Phenolic Esters. 253
6.3 Others 256
6.3.1 Metabolites of Delisia jimbriata 256
6.3.2 Kjellmanianone. 259
6.3.3 Pukeleimide A 259
6.3.4 Latrunculin B 260
6.3.5 Bisucaberin 262
6.3.6 Hormothamnione . 262
6.3.7 Bissetone . 266
6.3.8 (8,8)-Palythazine 267
6.3.9 Dysidin 267
6.3.10 Grateloupia jilicina Metabolite and
Related Compounds . 271
6.3.11 Didemnenones A and B. 272
6.3.12 Tridacna maxima Metabolite 275
6.3.13 Nereistoxin 275
6.3.14 3-n-Hexyl-4,5-dithiacycloheptan-5-one . 277
6.3.15 3-Methylnavenone B 277
6.3.16 Malyngolide . 279
6.3.17 Okadaic Acid 294
6.3.18 Debromoaplysiatoxin. 299
7 Summary. 311
8 References . 312
Subject Index 32)
Abstract
The growth and extent of chemical synthesis of marine natural
products from the years 1960-1989 has been evaluated and reviewed
in a near-comprehensive fashion for the first time. The rapid growth
in the breadth and depth of this field in a comparatively short period
of time mirrors the growth and interests of the synthesis community
at large. Synthesis chemists are stimulated primarily by compounds
which possess potential biomedical importance and/or provocative
structures, of which there is an abundance among the metabolites
from marine sources. Continued growth in this area is projected. The
information in this review consists primarily of synthetic schemes
and pathways which, after analysis, have been set to words. The
metabolites synthesized have been organized according to broad
biogenetic lines, including terpenes, alkaloids, fat-derived com-
pounds, amino-acid-derived and miscellaneous.