SUB Hamburg
Jean-Michel Kornprobst B/103659
Encyclopedia of Marine Natural Products
Volume 1: General Aspects, Microorganisms, Algae, and Fungi
Translated from French by
T. B. Tarn Ha
WILEY-BLACKWELL
Contents
Foreword XXI
Preface and Acknowledgements XXIII
List of Figures XXV
List of Tables XXXV
Abbreviations, Acronyms, and Cell Lines XXXIX
Volume 1
PartiGeneral Aspects and DocumentaryResources
lSystems of Classification of Living Organisms:Great Steps in Chemical and BiologicalEvolution 3
Whittaker's five kingdoms system 3
Discovery of Archaea(Archaebacteria):ternary model of living organisms 4
Characteristics of cell membranes 5
Some recent data on terpenes 7
Main stages of evolution 8
Exceptional resources of marine biodiversity 9
Selection of documentary resourcess 10References 10Websites 12
General Information on the MarineEnvironment 13
Physicochemical aspects 13Chemical composition of seawater 13
Optical properties of seawater 15Rapid absorption of light in relation to depth 15Selective absorption of the wavelengths 15
Biological and ecological aspects 16Primary and secondary metabolites 16Ecomones: vectors of chemical communication 16Phenomena of dependence 16
Dependence on light 16Dependence on temperature 17Dependence on salinity 17
Main types of interspecific relations 17Commensalism 17Symbiosis 17Parasitism 17
The hierarchy of ecological levels and spacedistribution of marine organisms 18Plant biodiversity: phylogeny of the algae 18Animal biodiversity 21Biochemical characteristics of sessile animals 23Estimation of biomass 23
Selection of documentary resources 24References 24Websites 25
Chemistry of Marine Natural Substances:Originality, Diversity, Distribution 27
General introduction 27
Distribution of nitrogenous and non-nitrogenoussecondary metabolites 27
Distribution of secondary metabolites by chemicalclass 28
Characteristics of the secondary metabolitesof marine organisms 29Incorporation of halogens 30Incorporation of sulfur 31Incorporation of silicon 32
Encyclopedia of Marine Natural Products. Jean-Michel KornprobstCopyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, WeinheimISBN: 978-3-527-327O3-4
VI11 Contents
Rare chemical elements encountered in marinesubstances: As, B, Ni, V, Zn 32
Arsenic 32Boron 32Nickel 33Vanadium 33Zinc 33
Selection of documentary resources 34References 34Websites 36
Basic Marine Pharmacology 37
The hopes of the past 37
The realities of the present 391. Ethnopharmacology 392. The triptych: biodiversity-chemodiversity-pharmacodiversity 403. Methods 44
Future directions 46
Selection of documentary resources 53References 53Websites 56
Documentary Resources 59
Short historical background 59
Printed documentation 60Chemical Abstracts, Biological Abstracts,Current Contents 60Basic works 60Reference works 61Articles published in volumes not entirelydedicated to marine organisms 61Scientific journals and the impact factor 62Scientific journals specializing in developmentsin natural marine products 62Articles about development publishedin scientific journals 65Proceedings of the major international symposia 66General articles on the synthesis of marine naturalproducts 66
Electronic documentation 67"Static" databases 68"Dynamic" databases 68Searching for information on the Internet 68
Part 2Archaea (Archebacteria) and Eubacteria
6
Archaea (Archaebacteria) 73
General introduction 73
Membrane lipids 74
Pranylquinones 79
Cyclic polysulfides 80
Bacteriorhodopsin of halophiles 81
Extremozymes 82
Appendix i: Stereospecific numbering (sri) 83
Selection of documentary resources 83References 83Experimental documentation 85Websites 85Synthesis 86
Eubacteria - 1 87
Cell walls and Gram reaction 87Anaerobic and aerobic photosynthesis:bacteriochlorophylls 88
Brief overview of marine bacteria 90
Piezophile (barophile) and psychrophile bacteriafrom extreme environments 91
Examples of metabolites isolatedfrom non-photosynthetic bacteria 91
Lipopolysaccharides and other characteristicsof some Gram-negative bacteria 106
Anaerobic photosynthetic bacteria 107
Aerobic photosynthetic bacteria 107
Anammox bacteria and "ladderane lipids" 108
Appendix 2 110
Selection of documentary resources 111References 111Websites 116Synthesis 116
Contents IX
8
Eubacteria - 2 121
Prochlorophyta 121
Taxonomy of Prochlorophyta 121
Unique characteristics of photosynthesisin Prochlorococcus 122
Biochemical data on Prochloron didemni 123
Biochemical data on Prochlorothrix hollandica 123
Cyanobacteria 124
Traditional classification of cyanobacteria 124
Photosynthetic pigments 125
Membrane lipids 128
General characteristics of the secondarymetabolites 129
Malyngamides and other chlorinated derivatives 130
Semiplenamides A-G and besarhanamides A-B 133
Aplysiatoxin, oscillatoxin-A
and other brominated derivatives 134
Other non-peptidic nitrogenous derivatives 135
Lipopeptides, peptides and depsipeptides 137
Other toxins 147
Sulfated compounds 148Polymethoxyalkenes and poly-/?-hydroxybutyricacids (PHBAs) 150
Other molecules 151
Appendix 3 153
Appendix 4 154
Selection of documentary resources 155References 155Websites 162Synthesis 163
Part 3Photosynthetic Eukaryotes
Bacillariophyceae (Diatoms) 173
Frustules: fundamental characteristics of diatoms 173
Bases of classification of diatoms 174
Primary metabolites 174
Photosynthetic pigments 174
Membrane lipids 175
Terpenic hydrocarbons 177
Other terpenic derivatives: descriptionof the two biosynthetic pathways 179
Genera Nitzschia and Pseudo-nitzschia: domoicacid 180
Other molecules 181
Appendix 5 183
Appendix 6 184
Selection of documentary resources 185References 185Websites 187Synthesis 188
10Chrysophyceae, Raphidophyceae,Haptophyceae 191
Chrysophyceae 191General presentation: simplified classification 191Photosynthetic pigmentsand storage polysaccharides 191Fatty acids 191Sterols 191Other derivatives 192
Raphidophyceae 193
Haptophyceae 193General presentation: simplified classification 193Photosynthetic pigments 194Sterols 194Fatty acids and other linear derivatives 195Prymnesins 196Particular characteristics of Pavlova pinguisand Pkurochrysis carterae 197
Contents
Appendix 7 198
Selection of documentary resources 199References 199Websites 200Synthesis 200
11
Dinophyceae (Dinoflagellates) 201
General aspects 201
Classification of dinoflagellates 202
Photosynthetic pigments 202
Sulfated exopolysaccharides 203
Sterols 204
Fatty acids 204
Glycolipids 207
Amphidinols and other polyhydroxylated polyenicderivatives 207
Toxic proliferations: endo- and exotoxins 211
Main types of dihoflagellate toxins 212
Cyclic polyethers 212
Okadaic acid and derivatives 220
Toxic macrolides: amphidinolides, caribenolide, gonio-domin A, hoffmanniolide 222
Complexity of the biosynthesis of polyketides 225
Saxitoxin and its derivatives 225
Nitrogenous toxins with imine function 228
Zooxanthellatoxins (ZTs) and other nitrogenoustoxins 229
Pfiesteria piscicida: a particularly toxicdinoflagellate 232
Sulfur-containing derivatives 232
Phosphorus derivatives 233
Selection of documentary resources 233References 233Websites 241Synthesis 242
12Chlorophyceae (Green Algae)and Marine Spermatophyta 251
General aspects 251
Elements of classification of marine macroalgae 251
Classification of Chlorophyceae 252
Chlorophylls, carotenes and xanthophylls 252
Storage polysaccharides: starches 254
Cell-wall polysaccharides 255
Matrix polysaccharides 255
Membrane lipids: fatty acids and sterols 255
Oxylipins 258
Background on the secondary metabolitesof Chlorophyceae 259
Terpenes 259
Meroterpenes of Dasycladales 262
Aromatic derivatives 263
Amino acids, amines, betaines 264
Peptides and depsipeptides: kahalalides 264
Other nitrogen-containing derivatives 265
Sulfur-containing derivatives 267
Marine Spermatophyta (phanerogams) 267
Selection of documentary resources 268References 268Websites 272Synthesis 273
13
Rhodophyceae (Red Algae) 275
Special features of red algae 275
Classification of Rhodophyceae 275
Photosynthetic pigments 277
Storage monosaccharides and polysaccharides 278
Skeleton polysaccharides 278
Matrix polysaccharides: carrageenans and agars 278
Carrageenophytes and agarophytes 281
Gelling agents and thickeners 281
Contents X I
Other types of matrix polysaccharides 282
Phospholipids and fatty acids 282
Oxylipins and prostaglandins 284
Sterols and ecdysteroids 285
General comments on the secondary metabolites 286
Secondary metabolites of Cryptonemiales 287
Secondary metabolites of Gelidiales 290
Secondary metabolites of Rhodymeniales 290
Polyhalogenated monoterpenes of Gigartinales 291
Diterpenes of Sphaerococcus coronopifolius(Gigartinales, Sphaerococcaceae) 293
Macrocydic pyrones of Phacelocarpus labillardieri(Gigartinales, Sphaerococcaceae) 297
Polycavernosides of Polycavernosa tsudai(Gigartinales, Gracilariaceae) 297
Brominated meroditerpenes of Calhphycus serratus(Gigartinales, Solieriaceae) 298
Halogenated phloroglucinols of Rhabdonia verticillata(Gigartinales, Solieriaceae) 299
Sulfated aromatic derivatives of Tichocarpus crinitus(Gigartinales, Tichocarpaceae) 299
Nitrogen-containing derivatives of Gigartinales 299
Halogenated compounds of Ceramiales:general comments 300
Polyhalogenated monoterpenes of Pantoneuraplocamioides (Ceramiales, Delesseriaceae) 301
Sesquiterpenes of Laurenda(Ceramiales, Rhodomelaceae) 301
Halogenated diterpenes of Laurenda 310
Non-halogenated hydroperoxyditerpenesof Laurenda 319
Squalenoids of Laurenda speciesand Chondria armata 319
Cyclic halogenated C,5 ethers and polyethersof Laurenda and Chondria 322
Bromo- and polybromophenols of Ceramiales 325
Nitrogen-containing bromophenolsof Rhodomela confervoides 328
Other nitrogen-containing derivativesof Ceramiales 329
Cyclic polysulfides of Chondria californica 332
Arsenic-containing derivativeof Chondria crassicaulis 332
Some atypical derivatives of Laurenda spedes 333
Halogenated derivatives of Nemaliales 333
Acetylenic acids of Liagora farinosa 335
Sulfated triterpene alcohols of Trideocarpa fragilis 336
Cyclic peptide from Galaxaura filamentosa 337
Appendix 8 337
Appendix 9 338
Selection of documentary resources 338References 338Websites 352Synthesis 353
14
Phaeophyceae (Brown Algae) 361
General introduction; 361
Classification of Phaeophyceae 361
Photosynthetic pigments 363
Laminarans and other storage osides 363
Matrix polysaccharides: alginic acids and alginates 364
Fucoidans (sulfated fucans) 365
Lipids and fatty acids 367
Oxylipins of Laminariales 367
Epoxy lipids of Notheia anomala (Chordariales) 370
Sterols 371
Volatile hydrocarbons and sexual chemotaxy 372
Background on the secondary metabolites 376
Sesquiterpenes of Dictyotales 376
Cyclic diterpenes of Dictyotales 377
Linear diterpenes of Fucales and other derivatives 382
Phenols and phlorotannins 385
Other aromatic derivatives 388
Meroterpenes: general comments 389
Prenylated quinones and hydroquinones 389
Meromonoterpenes of Sporodinus bolleanus 390
X I I Contents
Merosesquiterpenes of Dictyopteris species 391
Meroditerpenes of the genera Taoniaand Stypopodium 392
Meroditerpenes of Cystoseira species: chemotaxonomyof Cystoseiraceae 396
Nahocols and isonahocols: rearranged linearmeroditerpenes of Sargassum autumnale 401
Derivatives of nitrogen, phosphorus and arsenic 402
Sulfur-containing derivatives 404
Iodinated derivatives 405
Appendix io 406
Appendix n 407
Selection of documentary resources 407References 407Websites 417Synthesis 418
15
Major Uses of Macroalgae 423
Overview 423
Estimate of resources 423
Edible seaweeds 425
Dietary properties of marine algae 425
Physicochemical aspects of phycocolloids 426
Economic aspects of phycocolloids 428
Major producing countries of phycocolloids 428
Main applications of agars 428
Main applications of carrageenans and furcellar-ans 430
Main applications of alginic acid and alginates 430
Summary of research in the field of healthcare 431
Antiviral and immunostimulant sulfatedpolysaccharides of red, brown and green algae 431
Anticoagulant and antithrombotic propertiesof fucoidans 432
Antitumoural, immunomodulatory and antiviralproperties of fucoidans 433
Other examples of biological activitiesof macroalgae 434
Uses of algae in cosmetics 434
Uses of algae in agriculture and livestockproduction 435
Selection of documentary resources 435References 435Proceedings of the latest International SeaweedSymposia 440Websites 440
Part 4Fungi and Other Eukaryotic UnicellularNon-photosynthetic Organisms
16Fungi 445
The Fungal Kingdom: the conceptof marine fungi 445
Mastigomycetes and Eumycetes (true fungi) 446
Elements of classification of Eumycetes 446
Background information on the structureof chitin 446
Fatty acids 446
Sterols 446
Membrane peptides of fungi: peptaibols 448
General comments on secondary metabolitesof marine fungi 449
Substances isolated from fungi collectedfrom the surface of the sea 449
Substances isolated from fungi from sedimentsand other inert substrates 450
Substances isolated from fungi associatedwith cyanobacteria 454
Algicolous fungi: general remarks 454
Substances isolated from fungi associatedwith green algae and marine Spermatophyta 454
Substances isolated from fungi associatedwith red algae 458
Substances isolated from fungi associatedwith brown algae 459
Substances isolated from lignicolous fungi 461
Substances isolated from fungi associatedwith sponges 465
Contents X I I I
Substances isolated from fungi associatedwith cnidarians 473
Substances isolated from fungi associatedwith molluscs 474
Substances isolated from fungi associatedwith bryozoans 476
Substances isolated from fungi associatedwith echinoderms 476
Substances isolated from fungi associatedwith crustaceans 478
Substances isolated from fungi associatedwith tunicates (ascidians) 478
Substances isolated from fungi associatedwith fish 480
Selection of documentary resources 481References 481Websites 488Synthesis 489
17Thraustochytrids and Ciliates 493
Taxonomic position of thraustochytridsand overview of the group 493
Carotenoids of thraustochytrids 493
Long-chain (n-3) polyunsaturated fatty acidsof thraustochytrids 493
Long-chain fatty acid composition and phylogenyof thraustochytrids 495
o-Glucosylceramides of thraustochytrids 495
Introduction to the chemistry of ciliates 496
Terpenes of Euplotes 497
Keronopsins of Pseudokeronopsis rubra 498
Selection of documentary resources 499References 499Websites 501Synthesis 501
18Introduction to Marine Biotechnology 503
Introduction 503
Recent developments in the cultureof invertebrates 503
Lipids and pigments: examplesof nutritional applications 504
New substances and biomaterials: examplesof biomedical applications 506
Bioremediation and biofouling: examplesof environmental applications 507
Dialkylphthalates in marine organisms 508
Another type of application: bioadhesives 508
Some examples of biotechnology in Prokaryotes 509
Selection of documentary resources 510General references 510References 510Websites 516
Volume 2
Part5Porifera, Cnidaria, and Ctenophora
19
Porifera (Sponges) 521
Overview of the universe of sponges 521
Metabolites of Calcarea (calcareous sponges) 524General characteristics of Calcarea 524Fatty acids 524Sterols 524Non-nitrogenous derivatives of speciesof the genus Leucetta 525Imidazole alkaloids and zinc complexes isolated fromthe genera Leucetta, Leucosolenia and Clathrina 526a,co-Bis long-chain aminoalcohols 528Nitrogen-containing macrolides and cyclicpeptides 529Other nitrogen-containing compounds of Calcarea 529
Metabolites of Hexactinellida 530
Classification and membrane constituentsof Demospongiae 531Classification 531
X I V Contents
Some physical observations on demosponges 532Shape and size 532Consistency 532Colour and odour 532
Diversity of membrane constituents:some examples 536Phospholipids and demospongic acids 538Fatty acids with 5,9 dienic structure 541Other mono- and polyunsaturated fatty acids 543Branched fatty acids 544Isoprenic acids 547Cyclopropanic acids 548Brominated acids 5502-O substituted acids 551Sulfur derivatives of demospongic acids 553Intracellular localization and biological activityof demospongic acids 555Brief reminder about conventional sterols 555Unconventional sterols produced by changesin the tetracyclic system 556Unconventional sterols produced by polymethylationof the side chain 561Sterols with degraded side chains 564Sterols and stanols with cyclopropanicand cyclopropenic side chains 564Secosterols 566Polyhydroxylated steroids and derivatives,peroxysterols 569Sulfated sterols 571Chlorinated sterols and sterones 574Nitrogen-containing sterols 576Glycolipids 577
Secondary metabolites of Homoscleromorpha 582Fatty acids, polyketides and oxylipinsof Plakinastrella and Plakortis 582Cyclic peroxides and peroxylactonesof Plakinastrella and Plakortis 584Glycosides 587Polyhydroxylated sterols of Oscarella lobularis 587Alkaloids and other original nitrogen derivativesof Plakortis and Cortidum 587
Secondary metabolites of Astrophorida 590Acetylenic fatty acids of Stelletta 591Glycolipids: caminosides and pachymosides 591Triterpenes of malabaricane and isomalabaricane:sesterterpenes 591Triterpenic glycosides and steroidal glycosides 593Substituted tetramic acids and derived glycosides 596Erylusamines, erylusine and erylusidine 598Cyclic depsipeptides, peptolidesand macrolactones 598Nitrogen-containing terpenes 602
Bengazoles and bengamides 603Atypical nitrogenous derivatives 605Phosphorus-containing derivatives similarto calyculin A 607Aromatic sulfated derivatives 608Isotactic polymethoxydienes of Myriastra davosa 608
Secondary metabolites of Hadromeridaand Chondrosida 609Perforating power of Clionaidae 609lyso-Phospholipids and sulfated sphingosinesof Spirastrella abata 610Brominated acetylenic derivatives of Diplastrella 611Cyclic peroxides 612Terpenes 613Unconventional sterols 614Macrolactones: latrunculins and spongistatins 615Atypical glycosides of Latrunculia corticata 617Other nitrogen-free toxins 617Peptides and depsipeptides 618Pyrrole derivatives and other nitrogen-containingheterocycles 619Atypical nucleosides 621
Secondary metabolites of Lithistida 622Particular characteristics of lithistid sponges 622Nitrogen-containing sesquiterpenes of Theonella 623Specific glycolipids of Theonella swinhoei,Discodermia calyx and D. dissoluta 623Long-chain polyacetylenic derivatives of Theonellasp. 6243/9-Methoxysterols of Jereicopsis graphidiophora 6244-Methylenesterols and sterones of Theonella 624Macrolides 626Examples of acetogenins: discodermolide,calyculins and onnamides 629Linear peptides 630Mono- and bicyclic peptides 632Symbiotic origin of some polypeptides 635Cyclic and linear depsipeptides 635Atypical nitrogenous derivatives 639
Secondary metabolites of Spirophorida 640Atypical sterols of Cinachyra, Microscleroderma,and Scleritoderma 640Cinachyrolide A 640Microsclerodermins and aciculitins 641Examples of atypical derivatives of some spongesof the Tetillidae 641
Secondary metabolites of Agelasida 642Sterols 642Diterpenes and carotenoids 642Merosesquiterpenes and nitrogen-containingmeroditerpenes 643
Contents XV
Galactosylceramides and glycolipids 644Oroidin and related CnN5 bromopyrrole alkaloids 646
Agelastatin A series 649Other series 650
Pyrrole-2-carboxylic acid derivatives 650Other examples of nitrogen-containingheterocycles 650Betaines 651
Secondary metabolites of Halichondrida 652A-nor-steroids and other non-conventional sterols 652Conventional terpenes 654Nitrogen-containing terpenes: isonitrilesand related derivatives 659Other terpenes 666Long-chain linear polyaminesand a,co-bis-isothiocyanates 668Polyethers: halichondrins, okadaicand glycookadaic acids 668Various lipids 670Linear peptides of the genera Aulettaand Cymbastela 672Depsipeptides and cyclic peptides 672Pyrrole, imidazole, pyridine, isoquinolineand indole derivatives 678
Pyrrole derivatives 678Imidazole derivatives 678Pyridine and isoquinoline derivatives 679Indole derivatives 679
Heterocycles related to the oroidin family 681Atypical halogenated and sulfur-containingderivatives 682
Secondary metabolites of Haplosclerida 683Acetylenic derivatives 685Atypical fatty acids 691Terpenes and meroterpenes 693Triterpenic glycosides 699Hopanoids, steroids and sterosides 701Macrolides, depsipeptides and cyclic peptides 704Amino alcohols and glycosphingolipids(cerebrosides) 705Manzamines and related derivatives 707Quinolizidine and 1-oxaquinolizidine derivatives 707Pyridine derivatives and 3-alkylpyridinium salts 714Pyridoacridine alkaloids 716Pyrroloquinones and other examplesof nitrogen-containing heterocycles 717Quinones and sulfated hydroquinones 721Very long-chain linear sulfated derivatives 722Thiocyanatins: a,«-dithiocyanatesof Oceanapia sp. 722Some information on freshwater haplosderidsponges 723
Secondary metabolites of Poecilosderida 724Sterols, steroids and sterosides 725Terpenes and triterpenic glycosides 727Polybrominated acetogenins and oxylipins 732Long-chain acetynenic derivatives: raspailynes 732Glycolipids 733Brominated aromatic derivativesof Hamigera tarangaensis 733Macrolides 734Chondropsins: cyclic depsipeptidesof Chondropsis sp. 736Eurypamides (Microdona eurypa), microcionamides(Clathria abietina) and other cyclic peptides 737Linear amides 738Examples of some atypical sulfur-containingderivatives 739Pyrrole and indole derivatives 741Pyridines, quinolizines and pyridoacridines 742Guanidine derivatives 743Pyrroloiminoquinones and pyrroloquinones 747Azasugars 748Other examples of polycyclic alkaloids 748Phosphorus and arsenic-containing derivatives,betaines 750
General information on the metabolitesof sponges lacking mineral spicules 751
Secondary metabolites of Dendroceratida 753Terpenes and meroterpenes 754Sterols 760Polybromophenols and polybromodiphenyl ethersof Dysidea 761Nitrogen compounds 763
Secondary metabolites of Dictyoceratida 768Terpenes and meroterpenes 768Sterols 788Glycolipids 789Polybromodiphenyl ethers and other halogenatedaromatic derivatives 789Macrolides: laulimalide, altohyrtins, chondropsinsand haterumalides 790Linear and cyclic peptides, depsipeptides 791Alkaloids and other nitrogen-containingcompounds 793Phosphorus derivatives 795Atypical sulfur derivatives 796
Secondary metabolites of Verongida 7963,5-Dibromotyrosine derivatives 797Other nitrogen-containing compounds 805Glycerol ethers and glycosphingolipids 807Sulfated aromatic compounds 807Metabolites specific to the family Ianthellidae 808
X V I Contents
Selection of documentary resources 811References 811Some Proceedings of the International SpongeConferences 875Websites 875Synthesis 875
20
Cnidaria and Ctenophora 925
General introduction 925
Simplified classification of Cnidaria 925
Hermatypic and ahermatypic corals:coral bleaching 928
General information on metabolites of Cnidaria 929
Membrane constituents and secondary metabolitesof Octocorallia (Anthozoa) 930Prostaglandins and prostanoids 930Phospholipid fatty acids, glycolipidsand other lipidic derivatives 935General remarks on the sterols of Octocorallia 939Gorgosterol and other cyclopropane-containingsterols 940Polyoxygenated steroids 944Sterones and chlorinated sterones 948Sulfur-containing steroids 951Cyclized side-chain sterols 951Secosterols 952Sterosides, pregnane and nor-pregnane derivatives 955Sesquiterpenic hydrocarbons 958Halogenated and nitrogen-containingsesquiterpenes 959Sesquiterpenes with original carbon skeletons 962Examples of sesquiterpeneswith a classical carbon skeleton 968General account of diterpenes 974Linear and monocyclic diterpenes 975General information on bicyclic diterpenes 991Chlorinated diterpenes 995Other examples of briarane derivatives 996Nitrogen-containing diterpenes of dadiellane/eunicellane: eleutherobin and analogues,labiatamides 999Other examples of cladiellane/eunicellanediterpenes 1004Diterpenes of serrulatane and other bicyclic carbonskeletons 1005Bicyclic C s /Cn diterpenes 1005Bicyclic diterpenes containing a cyclopropane 1006Some other examples of bicyclic diterpenes 1011
General account of tricydic diterpenes 1014Pseudopterosins, other amphilectane derivativesand analogues 1014Other examples of tricyclic and tetracydicditerpenes 1019Comments on the origin of terpenes 1023Non-terpenic nitrogenous derivativesof Octocorallia 1023
Membrane constituents and secondary metabolitesof Hexacorallia (Anthozoa) 1027Fatty acids, oxylipins and acetylenic derivatives 1027Sterols and ecdysteroids 1029Terpenes 1031Carotenoids of sea anemones 1033Aromatic derivatives 1033Ceramides 1033Examples of nitrogenous pigments:zoanthoxanthins and calliactin 1034Palytoxins 1034Mycosporines 1036Betaines, phosphobetaines, purinesand other nitrogen-containing derivatives 1037Zoanthamine alkaloids 1039Cytolysins, neuropeptides and other venomsof sea anemones 1042
Venoms and other metabolites of Medusozoa 1042Some data on the Cubozoa and other jellyfish 1043Bioluminescence of jellyfish and other Cnidaria 1044Some results on the secondary metabolitesof other Hydrozoa 1045
Ctenophora 1049
Selection of documentary resources 1049References 1049Websites 1082Synthesis 1083
Volume 3
Part 6Protostomes
21Worm-like Organisms: 1 1097
Platyhelminthes 1097Macrolides and other compounds from symbiosiswith Amphidinium sp. 1097Staurosporine derivatives and other metabolitesfrom Platyhelminthes 1100
Contents X V I I
Nemertea 1101
Background on Annelida and Echiura 1102Lipids and sexual pheromones of polychaetes 1103Pigments of polychaetes and echiurans 1104Bromophenols of polychaetesand of the phoronid Phoronopsis viridis 1105Examples of nitrogen- and sulfur-containing derivativesfrom polychaetes 1105
Selection of documentary resources 1107References 1107Websites 1112Synthesis 1113
22Bryozoa, Phoronida and Brachiopoda 1115
Bryozoans (Bryozoa, Ectoprocta) 1115Background and classification 1115Lipids and aromatic compounds 1116Bryostatins 1118Pyrrole and pyrrolidine alkaloids 1121Indole and physostigmine alkaloids 1123Quinoline, isoquinoline and /?-carbolinederivatives 1124Original heterocydic systems 1126Nitro compounds 1126Sulfoxonium salts and "Dogger Bank itch" 1126
Phoronida and Brachiopoda 1127
Selection of documentary resources 1127References 1127Websites 1131Synthesis 1131
23Molluscs 1135
General characteristics and classification 1135
General information on lipids: hydrocarbons,fatty acids, oxylipins and sterols 1136
Metabolites of prosobranch gastropods 1140Some chemical data on Archaeogastropoda 1140Keyhole limpet haemocyanin 1143Chemical data on Mesogastropoda 1143Secondary metabolites of Neogastropoda 1145A brief history of Tyrian Purple 1146Indirubins 1147Conopeptides and conotoxins 1148
Toxic salivary secretions: tetrodotoxin, surugatoxinand neosurugatoxin 1151
Metabolites of opisthobranch gastropods 1152General characteristics of the order Anaspidea 1153Examples of food chains between sea haresand algae 1153Aplysioviolin and carotenoid pigments 1159Nitrogen-containing meroterpenes 1159Macrolactones: aplyolides, aplysiatoxins, aurisides,dolabelides, aplyronines and syphonoside 1160Peptides and depsipeptides: dolastatinsand aurilides 1162Other examples of nitrogenous derivativesof Anaspidea 1166Antimicrobial and anti-tumour glycoproteinsof the genera Aplysia and Dolabella 1168Polypropionates of Dolabella auriculariaand Dolabrifera dolabrifera 1168General information on the secondary metabolitesof Cephalaspidea 1169Alkylbenzenes and 2- and 3-alkylpyridinesof Cephalaspidea 1170Peptides and depsipeptides of Philinopsis speciosa 1171Polyketides of Clione antarctica 1172Secondary metabolites of Notaspidea 1173Background on the chemistry of nudibranchs 1175Terpenes, terpenoids and steroidsof nudibranchs 1175Prostaglandin lactones of Tethys fimbria 1187Cytotoxic macrolides of nudibranchs 1188Chlorinated polyacetylenic derivativesof Diaulula sandiegensis 1189Relations between nudibranchs and calcareoussponges: amino-2-imidazole derivatives 1190Relations between nudibranchsand bryozoans: pyrrole derivatives 1190Guanidine derivatives and other alkaloidsof nudibranchs 1191Nucleosides and peptides of nudibranchs 1192Simplified assessment of nudibranch chemistry 1193General remarks on metabolites of sacoglossans 1193Terpenes of sacoglossans 1194Polypropionate derivatives of sacoglossans 1194Kahalalides: cytotoxic depsipeptidesof the coupled Elysia/Bryopsis sp. 1196
Metabolites of pulmonate gastropods 1197Sesquiterpenes and diterpenes of the generaOnchidella and Trimusculus 1197Polypropionate derivatives of pulmonates 1198Cytotoxic depsipeptides of Onchidium sp. 1199
XVI11 Contents
Metabolites of Bivalvia (Lamellibranchiata) 1200Degradation products of chlorophyll aof Ruditapes phillipiharum 1201Carotenoids 1203Some data on polar lipids (plasmalogensand cardiolipids) 1203Polar sterols of Patinopecten yessoensisand 20-isosterols of Macoma balthica 1204Fatty acids and other lipid derivatives 1206Azaspiracids and other toxins 1206Polyamines, alkaloidsand various nitrogen-containing derivatives 1211Arsenic-containing derivativesof Tridacna maxima 1213Examples of biopolymers 1213
Metabolites of cephalopods 1213
Selection of documentary resources 1215References 1215Websites 1237Synthesis 1238
24
Arthropoda 1249
Chitin and chitosans 1249
Carotenoid pigments 1251
Lipid derivatives 1253
Hormones controlling crustacean moultingand other steroids 1253
Some examples of sulfur-, nitrogen- and arsenic-containing metabolites of crustaceans 1256
Some data on marine cheliceriforms 1257
Selection of documentary resources 1258References 1258Websites 1261Synthesis 1261
25Introduction to chemical ecology 1263
Examples of intraspecific relations 1264Sexual pheromones: sperm-activating peptidesof urchins and molluscs 1264Examples of alarm pheromones 1265
Examples of interspecific relationships 1265Predator-prey relationships: defence allomonesof algae and invertebrates 1266
Defence allomones in associationsbetween microorganisms and invertebrates 1267Elicitors and defence allomones of algae 1271Substances inducing metamorphosis of larvae 1272Formation of epibiosis (biofouling)and antifouling substances 1273Food attractants and stimulants 1274
Selection of documentary resources 1274References 1274Websites 1280Synthesis 1280
Part 7Deuterostomes
26Echinoderms 1283
General remarks and classification 1283
General comments on the chemistryof echinoderms 1284
Metabolites of crinoids(feather stars and sea lilies) 1287Quinonic pigments 1287Sterols, glycolipids and phosphoceramides 12883,5-Dibromotyrosine derivatives 1289
Metabolites of echinids (sea urchins) 1290Echinochrome A, spinochromes and carotenoids 1290Fatty acids, prostaglandins, glycosphingolipidsand other lipids 1292Nitrogen- and sulfur-containing metabolites 1296Sulfated fucans and galactans 1297
Metabolites of ophiuroids(brittle stars and basket stars) 1297Lipids 1298Sulfated carotenoids 1299Sterols and sulfated sterols 1300Alkaloids 1301
Metabolites of asteroids (sea stars and starfish)Sterols and sulfated sterols 1304Free and sulfated polyhydroxysterols 1309Nitrogen- and phosphorus-containingpolyhydroxysterols 1313Steroidal glycosides and asterosaponins 1313Carotenoids 1328Fatty acids and oxylipins 1328Glycolipids, ceramides, cerebrosidesand gangliosides 1329Nitrogen-containing derivatives 1329
1304
Contents X I X
Metabolites of holothuroids (sea cucumbers) 1335Fatty acids 1336Sterols, 4<z-methylsterols and triterpenes 1336Holothurins 1336Carotenoids 1347Trepang 1348Cerebrosides and gangliosides 1348Atypical nitrogen-containing derivativesof Cucumaria frondosa 1351Oligosaccharides and sulfated polysaccharides 1352
Selection of documentary resources 1352References 1353Websites 1366Synthesis 1367
27Worm-like Organisms: 2. Chaetognathaand Hemichordata (Enteropneustaand Pterobranchia) 1369
Short description of Chaetognatha 1369
Short description of Hemichordata 1369
Aromatic and heteroaromatic derivativesof enteropneusts 1370
Cephalostatins of Cephahdiscus gikhristi(Pterobranchia) 1372
Selection of documentary resources 1373References 1373Websites 1374Synthesis 1374
28Ascidians (Tunicates) 1377
Reminder about the concept of the chordate 1377
Description of tunicates and classificationof the Ascidiacea 1377
General information on the chemistryof ascidians 1379
Lipids: fatty acids, acyltunichlorins, polyketidesand oxylipins 1380
Amino alcohols, sphinganines, serinolipids,ceramides and cerebrosides 1382
Sterols and steroids 1384
Carotenoids 1386
Sulfated polysaccharides of ascidian tunics 1386
Nitrogenous biopolymers and lectins 1387
Metabolites of Didemnidae 1388Didemnaketals and chlorinated diterpenesof Lissoclinum species 1388Aromatic polysulfanes and other atypicalsulfur derivatives 1390Lamellarins and other pyrrole alkaloids 1392Derivatives of quinoline, pyridoacridineand pyrroloacridine 1394Derivatives of tyramine, tryptophan, indoleand yS-carboline 1396Cytotoxic linear amides: bistratene Aand bistramides 1400Linear peptides and 1,4-diketopiperazines 1401Cyclic peptides 1402Macrolides: patellazoles 1408Cyclic depsipeptides: didemnins, Aplidin® (plitidepsin)and other derivatives 1409Purines, nucleosides and analogues 1413
Metabolites of Polycitoridae 1414Terpenes of Cystodytes sp.and Polycitor adriaticus 1414Aromatic polysulfanes of Polydtor adriaticus 1414Nitrogenous macrolides: iejimalides 1415Simple pyrrole and indole alkaloids 1415/?-Carboline alkaloids: eudistominsand related derivatives 1416Decahydroquinoline alkaloids: lepadins 1418Quinolizidine and indolizine alkaloids 1420Perhydropyrrolo[2,l-j] and perhydropyrido[2,l-j]quinoline alkaloids: cylindricines 1420Pyridoacridine alkaloids and related derivatives 1421Other types of alkaloids 1424Cyclic peptides 1426
Metabolites of Polydinidae 1426Long-chain sulfated alkanes and terpenesof Sidnyum turbinatutn 1427Terpenes and meroterpenes 1427Para- and metacyclophanes: longithoronesand related derivatives 1427Simple aromatic derivatives 1430Nitrogenous and non-nitrogenous macrolides 1430Long-chain amines and amino alcohols,sphingosines 1432Piperidine alkaloids: pseudodistomins 1433Indole and yS-carboline alkaloids 1434Quinoline and pyridoacridine alkaloids 1436Bis-steroidal alkaloids of Ritterella tokioka:ritterazines 1436Purines and nucleosides 1437
XX Contents
Miscellaneous nitrogenous derivatives 1439
Metabolites of Ascidiidae 1441Vanadium, intracellular acidity of blood cellsand peptide ligands 1441
Metabolites of Cionidae 1445
Metabolites of Diazonidae 1446
Metabolites of Perophoridae 1447Metabolites isolated from speciesof the genus Perophora 1447Tetrahydroisoquinoline alkaloids: ecteinascidins
Metabolites of Molgulidae and Pyuridae 1449Lipids and non-nitrogenous derivatives 1449Nitrogenous derivatives, antimicrobial peptidesand proteins 1450
Metabolites of Styelidae 1453Non-nitrogenous derivatives 1453Phenylethylamine derivatives, various alkaloidsAntibacterial purines and peptides 1456
Selection of documentary resources 1456References 1456Websites 1477Synthesis 1477
1447
1453
29Vertebrates: Fish, Reptilesand Mammals 1489
Fish 1489Squalene and other lipid derivativesof Chondrichthyes and Agnatha 1489Bile steroids of sharks and hagfish:scymnol, myxinol and derivatives 1490Squalamine and other aminosterols of sharksMigratory pheromones and sex hormonesof lampreys 1493Inhibition of angiogenesis by shark cartilage:Neovastat® 1494General account of lipid derivatives ofOsteichthyes 1494Venoms and toxins: defence substances offishAntifreeze proteins of polar fish 1501Sulfated glycosaminoglycans of the extracellularmatrix 1502
Reptiles 1502
Mammals 1503Lipid composition and residues of chlorinatedpesticides 1503Ambergris, ambrein and ambrox 1504
1491
1497
Selection of documentary resourcesReferences 1504Websites 1511Synthesis 1511
1504
Index 1515