《有机化学》课程教学资源（参考书籍）The Chemistry of Fungi, James R. Hanson, 2008

Copytighted Material James R Hanson The Chemistry of Fungi RSCPublishing Copyrighted Material

Preface The diverse structures. and bioloicl activities of fungal meta bolites have attracted chemists for many years.This book is an introduction to the chemistry of fungal metabolites.The aim is to illustrate,within the context of fungal metabolites,the historical progression from chemical to spectroscopic methods of structure elucidation,the development in biosynthetic studies from establishing sequences and mechanisms to chemical enzymology and genetics and the increa of the biologica o products Fur tosynth They use many of their secondary metabolites to secure a place in a competitive natural environment and to protect themselves from predation. Fungi are ubiquitous and their activities affect many aspects of our daily lives,whether it be as sources of pharmaceuticals and food or as spoilage or- ganisms and the causes of diseases in plants and man.The chemistry of the fungi involved in these activities has been the subject of considerable study. ars.Alt ough their ions can be large the spread of plant dise the qu metabo s that could be solate d precluded much chem work adven of spectroscopic methods.Whereas many natural products derived from plants were isolated before the 1960s on a scale that permitted extensive chemical degradation this was rarely the case for fungal metabolites.However,whenever it was possible, interesting chemistry was discovered. This book begins with an historical introduction followed by a description of the ge neral cher ical features that contribute to the growth of fungi.There are many thousands se stru ind it is n the purpose of the b k to list them all.There are databas The aim is to describe some of the more important metabolites classified ac cording to their biosynthetic origin.Biosynthesis provides a unifying feature underlying the diverse structures of fungal metabolites.Therefore,the next chapters begin with a general outline of the relevant biosynthetic pathway The Chemistry of Fungi By James R.Han C James R.Hanson.2008

Preface The diverse structures, biosyntheses and biological activities of fungal meta￾bolites have attracted chemists for many years. This book is an introduction to the chemistry of fungal metabolites. The aim is to illustrate, within the context of fungal metabolites, the historical progression from chemical to spectroscopic methods of structure elucidation, the development in biosynthetic studies from establishing sequences and mechanisms to chemical enzymology and genetics and the increasing understanding of the biological roles of natural products. Fungi occupy an important place in the natural world. As non-photosynthetic organisms they obtain their nutrients from the degradation of organic material. They use many of their secondary metabolites to secure a place in a competitive natural environment and to protect themselves from predation. Fungi are ubiquitous and their activities affect many aspects of our daily lives, whether it be as sources of pharmaceuticals and food or as spoilage or￾ganisms and the causes of diseases in plants and man. The chemistry of the fungi involved in these activities has been the subject of considerable study, particularly over the last 50 years. Although their ramifications can be large, as in the spread of plant diseases, the quantities of metabolites that could be isolated precluded much chemical work until the advent of spectroscopic methods. Whereas many natural products derived from plants were isolated before the 1960s on a scale that permitted extensive chemical degradation this was rarely the case for fungal metabolites. However, whenever it was possible, interesting chemistry was discovered. This book begins with an historical introduction followed by a description of the general chemical features that contribute to the growth of fungi. There are many thousands of fungal metabolites whose structures are known and it is not the purpose of the book to list them all. There are databases that fulfil this role. The aim is to describe some of the more important metabolites classified ac￾cording to their biosynthetic origin. Biosynthesis provides a unifying feature underlying the diverse structures of fungal metabolites. Therefore, the next chapters begin with a general outline of the relevant biosynthetic pathway The Chemistry of Fungi By James R. Hanson r James R. Hanson, 2008 v

Preface before pre senting a detailed des at ar many nd th that dis tinctive metabolites of the more c arately.Many fungal metabolites are involved in the interactions of fungi with plants and others are toxic to man.Some of these are described in the sub sequent chapters.Fungi can transform chemicals in ways that can complement actions.The use as reagents forms the of the at dea T which c r the liter nted to resent me of the chemistry and biological activity than was deseribed in those volumes.A great deal has been discovered since they were published.Reviews on various aspects of microbiological chemistry that have appeared in Natural Product Reports and else where are cited in the bibliography. Finally tha Dr Brian Cross and John Gre who firs e to mi d production of the book. James R.Hanson University of Sussex

before presenting a detailed description of particular metabolites. Investi￾gations into these biosyntheses have utilized many subtle isotopic labelling experiments. Compounds that are fungal pigments and those that are dis￾tinctive metabolites of the more conspicuous Basidiomycetes are treated sep￾arately. Many fungal metabolites are involved in the interactions of fungi with plants and others are toxic to man. Some of these are described in the sub￾sequent chapters. Fungi can transform chemicals in ways that can complement conventional reactions. The use of fungi as reagents forms the subject of the final chapter. This book owes a great deal to Brian Turner’s Fungal Metabolites, volumes which cover the literature to 1982, although I have attempted to present more of the chemistry and biological activity than was described in those volumes. A great deal has been discovered since they were published. Reviews on various aspects of microbiological chemistry that have appeared in Natural Product Reports and elsewhere are cited in the bibliography. Finally, I wish to thank Dr Brian Cross and Dr John Grove who first introduced me to microbiological chemistry at The Frythe, Professor Tom Simpson FRS who read the manuscript and Dr Merlin Fox of the Royal Society of Chemistry for his help in the production of the book. James R. Hanson University of Sussex vi Preface

Books include tetronic acids,the nonadrides,and zara- gozic acids. The Chemistry of Fungi J.R.Hanson's book The Chemistry of Fungi presents a can only offer a short insight into their structural good overview of important natura diversity.as exemplified by a discussion of anthra dea quinone pigme nts,pulvinic acids,metal complexes volatiles plant pathogens and my toxin There then follows a discussion of plant diseases Therefore.the book fills a gap.since no books caused by fungi.such as the gray mold fungus devoted to fungal natural products have been (Botrytis cinerea)that attacks more than 200 diffe p shed in the e last th ent pla including many crop plants an distributed from tree to tree by the elm-bark beetle.is also discussed. The penultimate chapter is devoted to the 09 an instrumental analytical methods such as mass include the trichothecenes s the aflatoxins,and the spectrometry and,first and foremost.NMR ergot alkaloids,as well as the amanitins and H last chapter d the application o funei..、 the influ of environmenta omplished only with great difficulty,such as the conditions and the age of the cultures on the stereoselective hydroxylation of the CH,group in ctionof con lites and describes dor the the steroid skeleton for the prepa- des a rich collect on af inform practical imp onanesinceanlibidilepi tion in densely packed form focuss ne on te on a large scale from fungal cultures The following four chapters deal ith constit Reports.As the number ol a cording their hetlprod important co perties the discussing particular compounds of these classes the structural elucidation,and the biosynthesisof many ning the compounds a e disc he from amino acids covers not only the commer helpful glosary explains the important B-lactam antibiotics,such as penicillin most important terms in fungal biology.However. sion of the book is y by s al fo and lcks transplantation medicine because of their immu mation on its absolute configuration. The suppressive activity.Outstanding representatives typical odor of mush oms is not caused by (S)-1 n the group of polyketides are griseofulvin,kr octen-3-ol bu by (R)-1-octen-3-ol.A severe shor the the cholesterol level.The chapte which cites only few selected par ers That would e penes and terpenoids is especially detailed for a textbook but this book nc luding topics such the chemistry of h ded for experence d natural produ nes f th berellins that and pap ergosterol.which is important for the cell wall on.Roy Despite these deficiencies,which may be easily construction of fungr a shor improved in a new editi I reco nmend the boc ng w bi natu sts 845 interScience 2008 Wiley-VCH Verlag GmbH Co.KGaA.Weinheim Angew.Chem Int.Ed 2008.48.846-848

The Chemistry of Fungi J. R. Hansons book The Chemistry of Fungi presents a good overview of important natural products from fungi, dealing with their roles as antibiotics, fungicides, pigments, volatiles, plant pathogens, and mycotoxins. Therefore, the book fills a gap, since no books devoted to fungal natural products have been published in the last few years. Hanson begins with a historical retrospective, highlighting the changes in research on the isolation and structure elucidation of natural products, including those of fungi, that occurred during the last few decades through advances in chromatographic separation techniques and in instrumental analytical methods such as mass spectrometry and, first and foremost, NMR spectroscopy. In the second chapter Hanson describes the methods used to establish mycelial cultures of fungi, discusses the influences of environmental conditions and the age of the cultures on the production of secondary metabolites, and describes methods for their isolation and for the elucidation of their biosynthesis, which is a topic of great practical importance, since antibiotics are isolated on a large scale from fungal cultures. The following four chapters deal with constit￾uents of fungi arranged according to their bioge￾netic origin, including amino acids, polyketides, terpenoids, and precursors of the citrate cycle. In discussing particular compounds of these classes, the author puts special emphasis on explaining the elucidation of the structures and of their biosyn￾thesis. The chapter on fungal constituents derived from amino acids covers not only the commercially important b-lactam antibiotics, such as penicillin and cephalosporin, but also the diketopiperazines, gliotoxin, cyclopenin, cochliodinol, agaritine, and the cyclosporins that are of eminent importance in transplantation medicine because of their immu￾nosuppressive activity. Outstanding representatives in the group of polyketides are griseofulvin, known for its ability to attack dermatophytic fungi, and the statins, highly valued for their function of depress￾ing the cholesterol level. The chapter on fungal terpenes and terpenoids is especially detailed, including topics such as the chemistry of the trichothecenes that inhibit the sporulation of the plant-pathogenic fungus Botrytis allii, of the gib￾berellins that influence plant growth, and of ergosterol, which is important for the cell wall construction of fungi. That is followed by a short chapter dealing with fungal compounds that orig￾inate at least partly from the citrate cycle. These include tetronic acids, the nonadrides, and zara￾gozic acids. The seventh chapter is devoted to fungal pig￾ments and volatiles. Pigments play a major role in fungi, and even a chapter devoted entirely to them can only offer a short insight into their structural diversity, as exemplified by a discussion of anthra￾quinone pigments, pulvinic acids, metal complexes, and carotenoids. There then follows a discussion of plant diseases caused by fungi, such as the gray mold fungus (Botrytis cinerea) that attacks more than 200 differ￾ent plant species, including many crop plants and their fruits. Dutch elm disease, in which the fungus Ceratocystis ulmi is distributed from tree to tree by the elm-bark beetle, is also discussed. The penultimate chapter is devoted to the most important mycotoxins and to toxins of fruiting bodies of mushrooms. Those described include the trichothecenes, the aflatoxins, and the ergot alkaloids, as well as the amanitins and psilocybin. The last chapter deals with the application of fungal enzymes in reactions that otherwise can be accomplished only with great difficulty, such as the stereoselective hydroxylation of the CH2 group in position 11 of the steroid skeleton for the prepa￾ration of corticoids. The book provides a rich collection of informa￾tion in densely packed form, focussing on terpe￾noids, which the author has reviewed several times in Natural Products Reports. As the number of natural products derived from fungi is so enormous, the book can only present a selection of the most important compounds. Although the properties, the structural elucidation, and the biosynthesis of many compounds are discussed, the book contains little information about chemical synthesis. The table of contents gives easy access to the natural products discussed, and a very helpful glossary explains the most important terms in fungal biology. However, this generally positive impression of the book is marred by some serious mistakes: Thus, the struc￾tural formula of amanitin is incorrect and lacks information on its absolute configuration. The typical odor of mushrooms is not caused by (S)-1- octen-3-ol but by (R)-1-octen-3-ol. A severe short￾coming is the incompleteness of the collection of references in the chapter “Further Reading”, which cites only few selected papers. That would be acceptable for a textbook, but this book is mainly intended for experienced natural products chemists, who are certainly interested in ob￾taining background information from original papers. Despite these deficiencies, which may be easily improved in a new edition, I recommend the book as an important source of information to all natural products chemists, as well as to biochemists, Acid Catalysis in Modern Organic Synthesis By James R. Hanson. Royal Society of Chemistry, Cam￾bridge 2008. 204 pp., hard￾cover £ 60.—ISBN 978- 0854041367 Books 846 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2009, 48, 846 – 848

bird's-eye vew ll the orm the tr Peter spiteller cially in recent years. Institut fur Organische Chemie und Biochemiell It is extremely satisfying to realize that genetic Technische Universitat Munchen(Germany) informatio at last DOl:10.1o02/anie.200804895 short time The ni no doubt in my mind that the genetic information that is emerging will contribute substantially to the earch in the area Although tissue for formation will not be fully elucidated on the basis This is the third and most ambi of genetics alone.By definition.biomineralization tious ort by Ed Ind Ba ein the interface between and bic sto pro st a hese,and mineralization in a comprehensive treatment. In the compendium presented here,the high- The first book,Biomineralization:From Biology to lights are,in my opinion,in the attempts to bridge on.appea the gaps be 0n, ially be volume series Handbook of Biomineralization structures and biological structures where all the assembles the various aspects of the subject under action occurs,is still poorly understood.The articles the titles Biol b d b Sch on magnet chc bac touch on these t oblems andar intere constitute an important source of information for In the area of carbonate mineralization.where this rapidly developing and n field. in general much more is known about mechanisms he edit t to cover dge d more suc ully.Th apter b of b an and for alization of the sea urchin larval skelet on fron the results that they have achieved.However,this is development to cell biology,from the gene regu- not really a handbook.A handbook is a compen- latory network to matrix proteins and their fun dium o ned to provid m ion and uch a d m of for tion.Marsh takes a similar approach to the different Take,for description of coccolith calcification.The chapters Proteins"relate the exi on fun of teeth is indeed covered systematically.from the tional matrix macromolecules within a framework formation and structure of teeth to biom chanical of structure function relationships design,to and tre th rege ded to ob f hi 1- n of the bon tior cesses only then can we t rly under tissue and its structure,of how bone is formed,and stand the properties of these fantastically complex what is known about it.That is clearly a significant and sophisticated materals It is fascinating to gap in a ser tha claims to be a s approacn erstan Riomineralization is concerned with evolution ical properties of the tissues is beginnin genetics,molecular biology,cell biology,biochem- (see e.e.g..Fratzl and Gupta.Chapter 23 of Vol 1 stry.biomechar cs.materials science.chemistry. Zaslansky and Weiner,Chapter 13 of Vol.3) mo ar rec conclude onceptual con h all these aspects It thus becomes possible.after alization?",encapsulates the views of Baucrlein ngew.Chem.Int.Ed.2009.48.846-848 2009 Wiley-VCH Verlag GmbH Co.KGaA,Weinheim www.angewandte.org 847

biologists, pharmaceutical chemists, and nutritional chemists dealing with fungi. Peter Spiteller Institut fr Organische Chemie und Biochemie II Technische Universitt Mnchen (Germany) DOI: 10.1002/anie.200804895 Handbook of Bio￾meralization This is the third and most ambi￾tious effort by Edmund Buerlein and his co-authors to produce a set of multi￾authored books encompassing the vast area of biomineralization in a comprehensive treatment. The first book, Biomineralization: From Biology to Biotechnology and Medical Application, appeared in 2000. A revised and enlarged version appeared in 2004 under a similar title. Now, this new three￾volume series Handbook of Biomineralization assembles the various aspects of the subject under the titles Biological Aspects and Structure Forma￾tion, Biomimetic and Bioinspired Chemistry, and Medical and Clinical Aspects. All these books now constitute an important source of information for this rapidly developing and exciting field. The editors have made a heroic effort to cover all the areas of this vast subject: I am full of admiration for their vast amount of work and for the results that they have achieved. However, this is not really a handbook. A handbook is a compen￾dium of information that is designed to provide comprehensive answers in a certain area. In my opinion it is impossible to achieve such a goal in biomineralization by assembling a collection of manuscripts from different authors. Take, for example, bones and teeth, the two mineralized tissues of medical/clinical importance, which are mainly addressed in the third volume. The subject of teeth is indeed covered systematically, from the formation and structure of teeth to biomechanical design, tooth diseases and treatment, tooth regen￾eration, and finally tissue engineering of teeth. In contrast, there is no general description of the bone tissue and its structure, of how bone is formed, and what is known about it. That is clearly a significant gap in a series of books that claims to be a handbook of biomineralization. Biomineralization is concerned with evolution, genetics, molecular biology, cell biology, biochem￾istry, biomechanics, materials science, chemistry, crystallography, thermodynamics, molecular recog￾nition, structural biology, physiology, and pathol￾ogy. The Handbook of Biomineralization addresses all these aspects. It thus becomes possible, after observing with a birds-eye view all the enormous amount of work reported here, to identify some of the trends that are developing in the area, espe￾cially in recent years. It is extremely satisfying to realize that genetic information is at last becoming available in an area where very little was known, at least in the field of invertebrates, until a very short time ago. There is no doubt in my mind that the genetic information that is emerging will contribute substantially to the advancement of research in the area. Although it is true that genetic factors govern all processes of tissue formation, it is also true that mechanisms of formation will not be fully elucidated on the basis of genetics alone. By definition, biomineralization involves the interface between minerals and biol￾ogy, and a good understanding of both of these, and of their interplay, is needed. In the compendium presented here, the high￾lights are, in my opinion, in the attempts to bridge the gaps between structure, function, morphology, and genetics—a very difficult enterprise indeed, especially because the interface between mineral structures and biological structures, where all the action occurs, is still poorly understood. The articles by Jogler and Schuler on magnetotactic bacteria and by Douglas and co-authors on protein cages touch on these problems and are very interesting. In the area of carbonate mineralization, where in general much more is known about mechanisms, the gap is bridged more successfully. The chapter by Wilt and Ettensohn covers all aspects of biominer￾alization of the sea urchin larval skeleton, from development to cell biology, from the gene regu￾latory network to matrix proteins and their func￾tion, from ion and macromolecule transport to skeletal morphogenesis, and from matrix–mineral interactions to structure and mechanism of forma￾tion. Marsh takes a similar approach to the description of coccolith calcification. The chapters by Arias on “Egg Shell Growth and Matrix Macro￾molecules” and by Marin on “Unusually Acidic Proteins” relate the existing information on func￾tional matrix macromolecules within a framework of structure–function relationships. These efforts represent what is needed to obtain a comprehensive understanding of biomineraliza￾tion processes. Only then can we properly under￾stand the properties of these fantastically complex and sophisticated materials. It is fascinating to observe how, from this approach, an understanding of the biological design that results in the mechan￾ical properties of the tissues is beginning to emerge (see, e.g., Fratzl and Gupta, Chapter 23 of Vol 1; Zaslansky and Weiner, Chapter 13 of Vol. 3). I want to conclude with a conceptual consid￾eration. The first article in the series, entitled “Growth and Form: What is the Aim of Biominer￾alization?”, encapsulates the views of Buerlein Handbook of Biomeraliza￾tion Edited by Edmund Buer￾lein, Peter Behrens, and Matthias Epple. Wiley-VCH, Weinheim 2007. 1269 pp., hardcover E 499.— ISBN 978-3527316410 Angewandte Chemie Angew. Chem. Int. Ed. 2009, 48, 846 – 848 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org 847

Contents Chapter 1 Fungi and the Development of Microbiological Chemistry 1.5 History of Fungal Metabolites 6 1.5.1 Fungal Metabolites in the Nineteenth Century 1.5. Fungal Metabolites 1900-1940 153 15.5 796 1.5.6 Fungal Metabolites 1965-2005 1.5.7 History of Biosynthetic Studies with Fungi 15 Chapter 2 The Chemistry of Growing Fungi The Culture Medium 3 ngal Met bolite 4 The Stages in a Fermentation 23 2.5 Utilization of the Constituents of the Medium 2.6 Fungi Growing in the Wild 2.7 Biosynthetic Experiments Chapter 3 Fungal Metabolites Derived from Amino Acids 3.1 Introduction 3.2 Penicillins

Contents Chapter 1 Fungi and the Development of Microbiological Chemistry 1.1 Introduction 1 1.2 Structure of Fungi 2 1.3 Classification of Fungi 4 1.4 The Fungal Cell Wall 5 1.5 History of Fungal Metabolites 6 1.5.1 Fungal Metabolites in the Nineteenth Century 7 1.5.2 Fungal Metabolites 1900–1940 8 1.5.3 Fungi in the Antibiotic Era, 1940–1960 10 1.5.4 Study of Fungal Plant Diseases 1940–1965 12 1.5.5 Impact of Spectroscopic Methods on Structure Elucidation 13 1.5.6 Fungal Metabolites 1965–2005 13 1.5.7 History of Biosynthetic Studies with Fungi 15 Chapter 2 The Chemistry of Growing Fungi 2.1 The Culture Medium 18 2.2 Laboratory Fermentation 20 2.3 Isolation of Fungal Metabolites 21 2.4 The Stages in a Fermentation 23 2.5 Utilization of the Constituents of the Medium 25 2.6 Fungi Growing in the Wild 28 2.7 Biosynthetic Experiments 29 Chapter 3 Fungal Metabolites Derived from Amino Acids 3.1 Introduction 32 3.2 Penicillins 33 The Chemistry of Fungi By James R. Hanson r James R. Hanson, 2008 vii

Contents 3.3 Cephalosporins 3 4 Biosynthesis of B-Lactams 3.5 Metabolites Containing a Diketopiperazine Ring 39 % 3.5.2 Gliotoxi 3.6 The Cyclopenin-Viridicatin Group of Metabolites 3.7 Tryptophan-derived Metabolites 3.8 Glutamic Acid Derivatives 3.9 Fungal Peptides 45 Chapter 4 Polyketides from Fungi 4.1 Introduction 47 4.2 Polvketide Biosynthesis 48 4.3 Triketides 4.4 Tetraketides 51 4.4.1 6-Methylsalicylic Acid 4.4.2 Patulin and Penicillic Acid 443 Gladiolic Acid and its Relatives 4.4.4 Tetrake tide T nes 4.4.5 Mycophenolic Acid 567 4.5 Pentaketides 4.5.1 Citrinin 4.5.2 Terrein 4.6 Hepta-and Octaketides 4.6.1 Griseofulvin 61 4.6.2 Cladosporin(Asperentin) 47 Polyketide Lactones Statin Cytochalas ins 568 4.10 Fatty Acids from Fung 8 4.11 Polyacetylenes from the Higher Fungi 70 Chapter 5 Terpenoid Fungal Metabolites 5.1 Introduction D 3 osynthesis of Fungal Terpenoids Mo 54 Sesquiterpenoids 5.4.1 Cyclonerodiol 5.4.2 Helicobasidin 5.4.3 Trichothecenes 5.4.4 PR-Toxin 5.4.5Botryanes 81

3.3 Cephalosporins 36 3.4 Biosynthesis of b-Lactams 37 3.5 Metabolites Containing a Diketopiperazine Ring 39 3.5.1 Mycelianamide 40 3.5.2 Gliotoxin 40 3.6 The Cyclopenin-Viridicatin Group of Metabolites 42 3.7 Tryptophan-derived Metabolites 42 3.8 Glutamic Acid Derivatives 44 3.9 Fungal Peptides 45 Chapter 4 Polyketides from Fungi 4.1 Introduction 47 4.2 Polyketide Biosynthesis 48 4.3 Triketides 50 4.4 Tetraketides 51 4.4.1 6-Methylsalicylic Acid 51 4.4.2 Patulin and Penicillic Acid 52 4.4.3 Gladiolic Acid and its Relatives 55 4.4.4 Tetraketide Tropolones 56 4.4.5 Mycophenolic Acid 57 4.5 Pentaketides 58 4.5.1 Citrinin 58 4.5.2 Terrein 60 4.6 Hepta- and Octaketides 61 4.6.1 Griseofulvin 61 4.6.2 Cladosporin (Asperentin) 64 4.7 Polyketide Lactones 65 4.8 Statins 66 4.9 Cytochalasins 68 4.10 Fatty Acids from Fungi 68 4.11 Polyacetylenes from the Higher Fungi 70 Chapter 5 Terpenoid Fungal Metabolites 5.1 Introduction 73 5.2 Biosynthesis of Fungal Terpenoids 73 5.3 Monoterpenoids 76 5.4 Sesquiterpenoids 76 5.4.1 Cyclonerodiol 77 5.4.2 Helicobasidin 78 5.4.3 Trichothecenes 78 5.4.4 PR-Toxin 81 5.4.5 Botryanes 81 viii Contents

Contents ix 5.4.6 Culmorin and Helminthosporal 5.4.7 Sesquiterpenoids of the Basidiomycetes 43 5.5 Diterpenoid fungal metabolites 93 5.51 Virescenosides 552 Rosanes 2 55.3 Gibberellins and Kaurenolides 554 55.5 Aphidicol 5.5.6 Fusico cins and Cotylenins Sesterterpenoids 5.7 Fungal Triterpenoids and Steroids 185 5.7.I Ergosterol 106 57.2 Fusidane Steroidal Antibiotics 107 5.7.3 Viridin,Wortmannin and their Relatives 111 5.7.4 Triterpe 113 5.8 Meroterpenoid 116 Chapter 6 Fungal Metabolites Derived from the Citric Acid Cycle 6.1 Introduction 120 6.2 Citric Acid and Related Acids 120 6.3 Fungal Tetronic Acids Canadensolide and Avenaciolide 65 Nonadrides 124 6.6 Squalestatin 126 Chapter 7 Pigments and Odours of Fungi 7.1 Introduction 127 7.2 Polyketide Fungal Pigments 128 7.2.1 Fumigatin 128 7)) Auroglaucin and Flavoglaucin 129 73 Hyd oxyanth he Pigme 74 apht opyrone Pigments 7.2.5 Extended and Dimeric Quinone 131 7.3 Fungal Pigments Derived from the Shikimate Pathway 1 7.3.1 Terphenyls 32 7.3.2 Pulvinic Acids 13 7.4 Some Pigments Containing Nitrogen 135 7.5 138 al Carotenoids 138 7.6 Lichen Subs 7.7 Od ours of Fungi 7.7.1 Organoleptic Components of Mushrooms 7.7.2 Volatile Fungal Metabolites Containing Sulfur

5.4.6 Culmorin and Helminthosporal 84 5.4.7 Sesquiterpenoids of the Basidiomycetes 85 5.5 Diterpenoid Fungal Metabolites 93 5.5.1 Virescenosides 94 5.5.2 Rosanes 94 5.5.3 Gibberellins and Kaurenolides 97 5.5.4 Aphidicolin 101 5.5.5 Pleuromutilin 102 5.5.6 Fusicoccins and Cotylenins 102 5.6 Sesterterpenoids 104 5.7 Fungal Triterpenoids and Steroids 105 5.7.1 Ergosterol 106 5.7.2 Fusidane Steroidal Antibiotics 107 5.7.3 Viridin, Wortmannin and their Relatives 111 5.7.4 Triterpenoids of the Basidiomycetes 113 5.8 Meroterpenoids 116 Chapter 6 Fungal Metabolites Derived from the Citric Acid Cycle 6.1 Introduction 120 6.2 Citric Acid and Related Acids 120 6.3 Fungal Tetronic Acids 122 6.4 Canadensolide and Avenaciolide 123 6.5 Nonadrides 124 6.6 Squalestatins 126 Chapter 7 Pigments and Odours of Fungi 7.1 Introduction 127 7.2 Polyketide Fungal Pigments 128 7.2.1 Fumigatin 128 7.2.2 Auroglaucin and Flavoglaucin 129 7.2.3 Hydroxyanthraquinone Pigments 129 7.2.4 Xanthone and Naphthopyrone Pigments 130 7.2.5 Extended and Dimeric Quinones 131 7.3 Fungal Pigments Derived from the Shikimate Pathway 132 7.3.1 Terphenyls 132 7.3.2 Pulvinic Acids 133 7.4 Some Pigments Containing Nitrogen 135 7.5 Terpenoid Pigments 138 7.5.1 Fungal Carotenoids 138 7.6 Lichen Substances 140 7.7 Odours of Fungi 142 7.7.1 Organoleptic Components of Mushrooms 142 7.7.2 Volatile Fungal Metabolites Containing Sulfur 144 Contents ix

Contents Chapter 8 The Chemistry of Some Fungal Diseases of Plants 8.1 Introduction 147 8.2 General Chemistry of Plant-Fungal Interactions 14 8.3 Chemistry of some Leaf-spot Diseases 8.3.1 Botrytis cinerea 14g 8.3.2 Alternaria Leaf-spot Diseases 151 8.3.3 Cercospora Leaf-spot Diseases 153 83.4 Diseases Caused by 8.4 ease of the Gramineae fecting Fungi 8.6 Some Fungal Diseases of Trees 4151599 8.6.1 Dutch Elm Disease 8.6.2 Eutypa Dieback 160 8.6.3 Armillaria mellea 161 8.6.4 Phytophthora cinnamomi 162 8.6.5 Silver-leaf Disease 866 ria lligena Canker 8.6.7 Canker Diseases of 8.7 Trichoderma Species as Anti-fungal Agents 6666 8.8 Fungal Diseases of Plants and Global Warming Chapter 9 Mycotoxins 9.1 Introduction 165 9.2 9.3 9.5 Aflatoxins 96 Mycotoxins of Penicillium Species 9.7 Poisonous Mushrooms 173 Chapter 10 Fungi as Reagents 10.1 Introduction 177 10.2 Xenobiotic Transformations 10.21 Microbial Hydrolysis 10.22 Microbial Redox Reactions 10.2. Microbiological Hydroxylation 103 Biosynthetically-patterned Biotransformations

Chapter 8 The Chemistry of Some Fungal Diseases of Plants 8.1 Introduction 147 8.2 General Chemistry of Plant–Fungal Interactions 148 8.3 Chemistry of some Leaf-spot Diseases 149 8.3.1 Botrytis cinerea 149 8.3.2 Alternaria Leaf-spot Diseases 151 8.3.3 Cercospora Leaf-spot Diseases 153 8.3.4 Diseases Caused by Colletotrichum Species 154 8.4 Fungal Diseases of the Gramineae 155 8.5 Root-infecting Fungi 157 8.6 Some Fungal Diseases of Trees 159 8.6.1 Dutch Elm Disease 159 8.6.2 Eutypa Dieback 160 8.6.3 Armillaria mellea 161 8.6.4 Phytophthora cinnamomi 162 8.6.5 Silver-leaf Disease 162 8.6.6 Nectria galligena Canker 162 8.6.7 Canker Diseases of Cypress 163 8.7 Trichoderma Species as Anti-fungal Agents 163 8.8 Fungal Diseases of Plants and Global Warming 164 Chapter 9 Mycotoxins 9.1 Introduction 165 9.2 Ergotism 165 9.3 Trichothecenes as Mycotoxins 166 9.4 Other Fusarium Toxins 168 9.5 Aflatoxins 169 9.6 Mycotoxins of Penicillium Species 171 9.7 Poisonous Mushrooms 173 Chapter 10 Fungi as Reagents 10.1 Introduction 177 10.2 Xenobiotic Transformations 177 10.2.1 Microbial Hydrolysis 178 10.2.2 Microbial Redox Reactions 179 10.2.3 Microbiological Hydroxylation 180 10.3 Biosynthetically-patterned Biotransformations 183 x Contents

Contents xi Epilogue 188 Further Reading and Bibliography 190 Glossary 204 Subject Index 209

Epilogue 188 Further Reading and Bibliography 190 Glossary 204 Subject Index 209 Contents xi