Funayama / Cordell Alkaloids

A Treasury of Poisons and Medicines
1. Auflage 2014
ISBN: 978-0-12-417314-9
Verlag: Elsevier Science & Techn.
Format: EPUB
Kopierschutz: 6 - ePub Watermark

E-Book, Englisch, 294 Seiten

Alkaloids are a large group of structurally complex natural products displaying a wide range of biological activities. The purpose of Alkaloids: A Treasury of Poisons and Medicines is to classify, for the first time, the alkaloids isolated from the natural sources until now. The book classifies all of the alkaloids by their biosynthetic origins. Of interest to the organic chemistry and medicinal chemistry communities involved in drug discovery and development, this book describes many alkaloids isolated from the medicinal plants, including those used in Japanese Kampo medicine. - Classifies and lists alkaloids from natural sources - Occurrence and biosynthetic pathways of alkaloids - Indicates key uses and bioactivity of alkaloids

Professor Shinji Funayama obtained his Ph.D. in natural product chemistry at Tohoku University (Sendai, Japan) in 1980. After three years as a postdoctoral fellow at the Department of Pharmacognosy and Pharmacology, College of Pharmacy, University of Illinois at Chicago (UIC) under the supervision of Professor Geoffrey A. Cordell, he joined the Kitasato Institute (Tokyo, Japan) as a senior researcher. After seven years, he joined as a Lecturer and was promoted to Assistant Professor at the Pharmaceutical Institute, Tohoku University. After six years in this position, he joined as an Associate Professor at Aomori University (Aomori, Japan). He was promoted to Professor there, and also served as a Guest Professor at Hirosaki University. After eight years, he became a Professor at Nihon Pharmaceutical University (Saitama, Japan) in 2003 and served as a Department Head for 10 years. He is the author of about 150 research publications, book chapters, comprehensive reviews, and professional publications; is the author of 11 books, with five more in progress; and is the Associate Editor-in-Chief of the Pharmaceutical Biology (USA). He is a Councilor of the Japanese Society for History of Pharmacy. His interests include the chemistry and biosynthesis of alkaloids, the relationship of poisons and human beings, the Japanese ancient history of Poisons and Medicines, and also the use of vegetables as chemical reagents.

Autoren/Hrsg.

Funayama, Shinji

Cordell, Geoffrey A.

Inhaltsverzeichnis

1;Front Cover;1
2;Alkaloids;4
3;Copyright;5
4;CONTENTS;6
5;FOREWORD;10
6;Introduction;12
6.1;1. THE DEFINITION OF AN ALKALOID;13
6.2;LITERATURE CITED;17
6.3;2. CLASSIFICATION OF ALKALOIDS;17
6.4;LITERATURE CITED;20
6.5;3. HUMANS AND ALKALOIDS;21
6.6;LITERATURE CITED;23
6.7;4. DEVELOPMENT OF PHARMACOGNOSY AND NATURAL PRODUCT CHEMISTRY, AND ALKALOIDS;23
6.8;LITERATURE CITED;27
6.9;5. BRIEF HISTORY OF JAPANESE PHARMACEUTICAL SCIENCES AND ALKALOIDS;27
6.10;LITERATURE CITED;29
6.11;6. CNS STIMULATION AND ALKALOIDS;29
6.12;LITERATURE CITED;31
7;Chapter 1 - Alkaloids Derived from Phenylalanine and Tyrosine;32
7.1;1.1 PHENYLETHYLAMINES (PHENETHYLAMINES);33
7.2;LITERATURE CITED;36
7.3;1.2 L-DOPA AND DOPAMINE;36
7.4;LITERATURE CITED;38
7.5;1.3 THYROID GLAND AND THYROXINE;38
7.6;LITERATURE CITED;39
7.7;1.4 COCLAURINE AND COCLAURINE-TYPE ALKALOIDS;40
7.8;LITERATURE CITED;42
7.9;1.5 TUBOCURARE AND D-TUBOCURARINE;43
7.10;LITERATURE CITED;45
7.11;1.6 APORPHINE-TYPE ALKALOIDS;45
7.12;LITERATURE CITED;48
7.13;1.7 ARISTOLOCHIA SPP. AND ARISTOLOCHIC ACID;48
7.14;LITERATURE CITED;51
7.15;1.8 PHELLODENDRON AMURENSE AND BERBERINE;51
7.16;LITERATURE CITED;54
7.17;1.9 CHELIDONIUM MAJUS AND CHELIDONINE;54
7.18;LITERATURE CITED;56
7.19;1.10 OPIUM AND MORPHINE;56
7.20;LITERATURE CITED;60
7.21;1.11 COLCHICUM AND COLCHICINE;60
7.22;LITERATURE CITED;62
7.23;1.12 ERYTHRINA INDICA AND ERYTHRINA ALKALOIDS;63
7.24;LITERATURE CITED;66
7.25;1.13 LYCORIS SPP. AND LYCORINE;66
7.26;LITERATURE CITED;70
7.27;1.14 CEPHAELIS IPECACUANHA AND EMETINE;70
7.28;LITERATURE CITED;72
8;Chapter 2 - Alkaloids Derived from Tryptophan;74
8.1;2.1 SEROTONIN;75
8.2;LITERATURE CITED;75
8.3;2.2 AUXIN AND INDOLE-3-ACETIC ACID;76
8.4;LITERATURE CITED;77
8.5;2.3 TEONANACATL AND PSILOCYBIN;77
8.6;LITERATURE CITED;78
8.7;2.4 INDIGO AND THE ANCIENT PURPLE;78
8.8;LITERATURE CITED;79
8.9;2.5 CALABAR BEANS AND PHYSOSTIGMINE;80
8.10;LITERATURE CITED;81
8.11;2.6 HARMALA AND HARMINE;81
8.12;LITERATURE CITED;82
8.13;2.7 PICRASMA SP. AND NIGAKINONE;82
8.14;LITERATURE CITED;84
8.15;2.8 CLERODENDRON AND TRICHOTOMINE;84
8.16;LITERATURE CITED;86
8.17;2.9 IBOGA AND IBOGAINE;86
8.18;LITERATURE CITED;87
8.19;2.10 RAUVOLFIA AND RESERPINE;87
8.20;LITERATURE CITED;89
8.21;2.11 YOHIMBE AND YOHIMBINE;89
8.22;LITERATURE CITED;91
8.23;2.12 CAMPTOTHECA AND CAMPTOTHECIN;91
8.24;LITERATURE CITED;93
8.25;2.13 UNCARIA AND RHYNCHOPHYLLINE;93
8.26;LITERATURE CITED;94
8.27;2.14 NUX VOMICA AND STRYCHNINE;94
8.28;LITERATURE CITED;95
8.29;2.15 CALABASH CURARE AND C-CURARINE AND C-TOXIFERINE I;95
8.30;LITERATURE CITED;96
8.31;2.16 ERGOT, ERGOT ALKALOIDS, AND LSD;96
8.32;LITERATURE CITED;99
8.33;2.17 CINCHONA AND QUININE;99
8.34;LITERATURE CITED;101
8.35;2.18 CATHARANTHUS ROSEUS AND VLB AND VCR;101
8.36;LITERATURE CITED;104
8.37;2.19 EUODIA RUTAECARPA AND EVODIAMINE AND RUTAECARPINE;104
8.38;LITERATURE CITED;106
8.39;2.20 ATHLETE’S FOOT AND PYRROLNITRIN;106
8.40;LITERATURE CITED;108
8.41;2.21 ANTHRAMYCIN AND TOMAYMYCIN;108
8.42;LITERATURE CITED;109
8.43;2.22 STREPTONIGRIN;110
8.44;LITERATURE CITED;111
8.45;2.23 STAUROSPORINE;112
8.46;LITERATURE CITED;113
9;Chapter 3 - Alkaloids Derived from Ornithine and Arginine;114
9.1;3.1 TOBACCO AND NICOTINE;114
9.2;LITERATURE CITED;117
9.3;3.2 BELLADONNA AND ATROPINE;117
9.4;LITERATURE CITED;122
9.5;3.3 COCA LEAVES AND COCAINE;122
9.6;LITERATURE CITED;125
9.7;3.4 SENECIO AND PYRROLIZIDINE ALKALOIDS;125
9.8;LITERATURE CITED;129
9.9;3.5 ALKALOIDS DERIVED FROM POLYAMINES;130
9.10;LITERATURE CITED;131
9.11;3.6 PUTRESCINE AND PIRIFERINE;132
9.12;LITERATURE CITED;132
9.13;3.7 SPERMIDINE AND AGROBACTIN;133
9.14;LITERATURE CITED;133
9.15;3.8 SPERMINE AND EPHEDRADINE;133
9.16;LITERATURE CITED;136
9.17;3.9 FUGU AND TETRODOTOXIN;136
9.18;LITERATURE CITED;138
10;Chapter 4 - Alkaloids Derived from Lysine;140
10.1;4.1 PEPPER (PIPER NIGRUM) AND PIPERINE;141
10.2;LITERATURE CITED;142
10.3;4.2 PUNICA GRANATUM AND PELLETIERINE;142
10.4;LITERATURE CITED;144
10.5;4.3 TOBACCO AND ANABASINE;145
10.6;LITERATURE CITED;146
10.7;4.4 LOBELIA INFLATA (INDIAN TOBACCO) AND LOBELINE;146
10.8;LITERATURE CITED;147
10.9;4.5 SOPHORA FLAVESCENS AND MATRINE;147
10.10;LITERATURE CITED;149
10.11;4.6 COMMON BROOM (CYTISUS SCOPARIUS) AND SPARTEINE;150
10.12;LITERATURE CITED;151
11;Chapter 5 - Alkaloids Derived from Proline;152
11.1;Anchor 40;152
11.2;LITERATURE CITED;153
11.3;5.1 SERRATIA AND PRODIGIOSIN;153
11.4;LITERATURE CITED;154
11.5;5.2 STACHYDRINE;155
11.6;LITERATURE CITED;155
11.7;5.3 PYRROLE-2-CARBOXYLIC ACID;155
11.8;LITERATURE CITED;156
12;Chapter 6 - Alkaloids Derived from Glutamic Acid;158
12.1;6.1 G-AMINOBUTYRIC ACID;158
12.2;LITERATURE CITED;159
12.3;6.2 DIGENEA SIMPLEX AND KAINIC ACID;160
12.4;LITERATURE CITED;161
12.5;6.3 CLITOCYBE ACROMELALGA AND ACROMELIC ACID;162
12.6;LITERATURE CITED;164
12.7;6.4 AMANITA PANTHERINA AND IBOTENIC ACID;164
12.8;LITERATURE CITED;165
13;Chapter 7 - Alkaloids Derived from Histidine;166
13.1;7.1 HISTAMINE;166
13.2;LITERATURE CITED;168
13.3;7.2 JABORANDI AND PILOCARPINE;168
13.4;LITERATURE CITED;168
14;Chapter 8 - Alkaloids Derived from 2,3-Diamino propionic Acid;170
14.1;8.1 QUISQUALIS INDICA FRUITS AND QUISQUALIC ACID;170
14.2;LITERATURE CITED;171
15;Chapter 9 - Compounds Derived from Anthranilic Acid;174
15.1;LITERATURE CITED;175
15.2;9.1 ORIXA JAPONICA AND QUINOLINE ALKALOIDS;175
15.3;LITERATURE CITED;178
15.4;9.2 QUINOLINE ALKALOIDS OF MICROBIAL ORIGIN;179
15.5;LITERATURE CITED;180
15.6;9.3 ACRONYCINE AND ACRIDONE ALKALOIDS;180
15.7;LITERATURE CITED;182
15.8;9.4 QUINOLINE ALKALOIDS ISOLATED FROM HIGHER PLANTS OTHER THAN THE RUTACEAE FAMILY;183
15.9;LITERATURE CITED;184
15.10;9.5 FEBRIFUGINE AND RELATED ALKALOIDS;184
15.11;LITERATURE CITED;186
15.12;9.6 HARMALA ALKALOIDS AND VASICINE (PEGANINE);187
15.13;LITERATURE CITED;188
15.14;9.7 PHENAZINE ALKALOIDS DERIVED FROM MICROORGANISMS;189
15.15;LITERATURE CITED;191
16;Chapter 10 - Alkaloids Derived from Nicotinic Acid;192
16.1;Anchor 79;192
16.2;LITERATURE CITED;194
16.3;10.1 NICOTINE AND ANABASINE;195
16.4;LITERATURE CITED;197
16.5;10.2 NIACIN AND VITAMIN B6;197
16.6;LITERATURE CITED;199
16.7;10.3 ARECA NUT AND ARECOLINE;200
16.8;LITERATURE CITED;201
16.9;10.4 CASTOR AND RICININE;201
16.10;LITERATURE CITED;203
17;Chapter 11 - Alkaloids Derived from Nucleic Acids and Related Compounds;204
17.1;11.1 PURINE BASES AND CAFFEINE;205
17.2;LITERATURE CITED;212
17.3;11.2 PYRIMIDINE BASES, 5-FLUOROURACIL, AND VITAMIN B1;213
17.4;LITERATURE CITED;217
17.5;11.3 PTERIDINE SKELETON AND FOLIC ACID;217
17.6;LITERATURE CITED;219
18;Chapter 12 - Alkaloids Possessing the Porphine Skeleton;220
18.1;LITERATURE CITED;221
18.2;12.1 HEME AND CHLOROPHYLL;221
18.3;LITERATURE CITED;226
18.4;12.2 VITAMIN B12;227
18.5;LITERATURE CITED;228
19;Chapter 13 - Alkaloids Derived from an m-C7N Unit;230
19.1;13.1 MITOMYCIN C;231
19.2;LITERATURE CITED;232
19.3;13.2 NAPHTHALENOID ANSAMYCINS AND RIFAMPICIN;233
19.4;LITERATURE CITED;236
19.5;13.3 BENZENOID ANSAMYCINS AND MAYTANSINE;236
19.6;LITERATURE CITED;239
19.7;13.4 THE BIOSYNTHESIS–STEREOCHEMISTRY MODEL (CELMER’S MODEL) OF THE ANSAMYCINS;239
19.8;LITERATURE CITED;243
20;Chapter 14 - Alkaloids Derived from Terpenoids;244
20.1;Anchor 173;244
20.2;LITERATURE CITED;247
20.3;14.1 ACTINIDIA POLYGAMA AND ACTINIDINE;247
20.4;LITERATURE CITED;249
20.5;14.2 GENTIANA SCABRA AND GENTIANINE;249
20.6;LITERATURE CITED;251
20.7;14.3 RHIZOME OF NUPHAR JAPONICUM AND SESQUITERPENE ALKALOIDS;251
20.8;LITERATURE CITED;252
20.9;14.4 ACONITUM AND ACONITINE ALKALOIDS;252
20.10;LITERATURE CITED;255
20.11;14.5 TAXUS CUSPIDATA AND TAXOL;255
20.12;LITERATURE CITED;257
20.13;14.6 PACHYSANDRA TERMINALIS AND BUXACEAE ALKALOIDS;257
20.14;LITERATURE CITED;259
20.15;14.7 HOLARRHENA ANTIDYSENTERICA AND CONESSINE;259
20.16;LITERATURE CITED;259
20.17;14.8 POTATO AND SOLANINE;259
20.18;LITERATURE CITED;261
20.19;14.9 FRITILLARIA AND VERATRUM ALKALOIDS;261
20.20;LITERATURE CITED;263
20.21;14.10 ARROW TOXINS, TOXIC BIRDS, AND BATRACHOTOXIN;264
20.22;LITERATURE CITED;266
21;Chapter 15 - Alkaloids Derived from Polyketides;268
21.1;15.1 HEMLOCK AND CONIINE;268
21.2;LITERATURE CITED;270
21.3;15.2 NIGRIFACTIN AND PIERICIDINS;271
21.4;LITERATURE CITED;272
22;Chapter 16 - Alkaloids Derived from a C6–C1 Unit;274
22.1;16.1 EPHEDRA ALKALOIDS;275
22.2;LITERATURE CITED;278
22.3;16.2 KHAT AND EPHEDRA ALKALOIDS;278
22.4;LITERATURE CITED;280
22.5;16.3 NAPHTHALENE-ISOQUINOLINE ALKALOIDS;281
22.6;LITERATURE CITED;282
22.7;16.4 RED PEPPER AND CAPSAICIN;282
22.8;LITERATURE CITED;284
23;INDEX;286

Leseproben

Introduction

Before describing the various groups of alkaloids individually, the place of alkaloids among the naturally occurring organic compounds, and in society will be discussed briefly in this chapter. An understanding of what an alkaloid is will be mentioned in the first section, and in the second section, the aspects of classifying alkaloids on the basis of their biosynthetic origin will be presented. This method will be compared with a classification based on their carbon or heterocyclic skeleton, such as indole, isoquinoline alkaloids, or a classification of the alkaloids based on a chemotaxonomic approach, such as Rutaceae and Apocynaceae alkaloids. A short history of the study of alkaloids and the crude drugs as the origin of various alkaloids, and their relevance in the history of natural products chemistry will be described. Through these discussions, it will be established that the natural products classified as alkaloids relate to our life deeply, and on an everyday basis, as medicines, as dyestuffs, as flavors, as stimulants, and as toxic substances. It is known that alkaloids show a broad range of biological activities. Among the biologically active compounds, there are especially many alkaloids which affect the central nervous system (CNS) and the autonomic nervous system. Some of the CNS stimulants will be described in the final sixth section. Readers of this book will discover that alkaloids are a very important group of organic compounds which show a variety of highly significant, clinically and biologically useful properties. Among these activities of alkaloids are hypotensive, cardiotonic, hormone, pheromone, growth acceleration, antimalarial, antitumor, antiparasitic, sedative, analgesic, anti-Alzheimer’s, and antimicrobial activities. There are probably over 25,000 alkaloids derived from higher plants as presented in the Dictionary of Alkaloids. This modest volume offers a brief overview of the main alkaloid groups, their structures, their activities, and their basic biosynthetic pathways from a historical perspective. 1 The Definition of An Alkaloid The word “alkaloid” was proposed in 1818 by K. F. W. Meissner (1792–1853), a pharmacist in Halle, Germany. The word alkaloid was coined from the word alkali (implying basicity), from “ ” (referring to soda) in Arabic. The “-oid” suffix, meaning “like”, derives from the Greek. The definition of an alkaloid has changed significantly over the years, as more “alkaloids” have been structurally elucidated and the sources of alkaloids have broadened. 1. At the beginning, alkaloids were discovered only from higher plants, and those compounds showed basic properties and strong biological activities. Consequently, at that time, an alkaloid was defined as “the plant component which shows basic properties and strong biological effect.” The basicity of alkaloids is derived from the presence of a nitrogen atom in the molecule in the form of an amine.     Such a definition is no longer possible for the alkaloids. First of all, alkaloids are obtained from an extremely broad range of natural sources, not just the plant kingdom. For example, retronecine, danaidone, and hydroxydanaidal (derivatives of pyrrolizidine alkaloids) were isolated from the hair pencil of the male butterfly of the Danaid genus. Batrachotoxin, a poison arrow toxin component, was isolated from the skin of a frog. In addition, there are many examples of alkaloids of microbial, marine, and human origin, including a vast array of nitrogen-containing antibiotics.
2. Alkaloids are not limited to those natural products which are basic in character. For example, colchicine isolated from Colchicum autumnale (Liliaceae) and used for the treatment of gout, etc. is not basic because the nitrogen atom in the molecule is present in a neutral amide group. However, the biosynthetic precursor of colchicine is autumnaline, a typical, basic phenethylisoquinoline alkaloid. Therefore any compound derived from such an intermediate should be classified as an alkaloid.
    Another example pertains to the close structural isomers, pteleprenine and isopteleprenine, which were isolated from Orixa japonica (Rutaceae). In pteleprenine, the nitrogen is in the form of an amide, and therefore it lacks basicity. On the other hand, in isopteleprenine the nitrogen atom, being in a quinoline ring, is weakly basic. Given their common biosynthetic origin both compounds are classified as alkaloids.
    In the case of the phenanthrine derivative aristolochic acid-I, the skeleton is derived from an aporphine alkaloid precursor which has undergone oxidation, to the point where the nitrogen atom exists as a nitro group. Biosynthetically, this compound is also classed as an alkaloid.
3. It is not appropriate to include the existence of biological activity in the definition for an alkaloid. Several years ago [1] it was shown that about 75% of known “alkaloids” had never been tested in a single bioassay. In addition, when an alkaloid with biological activity is isolated, compounds with a closely related chemical structure with no, or greatly diminished, biological activities will also be isolated. In such a case, all of these compounds are regarded as alkaloids, irrespective of whether they have a demonstrated biological activity. 4. Alkaloids are always compounds isolated from nature. However, there are many examples of alkaloid derivatives with a high profile which may be confused and sometimes classified as alkaloids. For example, Lyserg Säure Diäthylamid (LSD) (LSD-25) is prepared by the amidation of lysergic acid, itself derived from the ergot alkaloids. Methamphetamine is prepared by the reduction of (-)-ephedrine, and heroin is prepared by the acetylation of morphine, and there are many derivatives of alkaloids which are pharmaceutical products. These semisynthetic compounds can be classed as alkaloid derivatives.
5. There are a significant number of unusual amino acids, simple peptides, pyrrole derivatives, and comparatively simple nitrogen-containing organic compounds, including purines and pyrimidines, which may be excluded from classification as alkaloids.     For example, L-a-kainic acid, obtained from the red algae Digenea simplex (Rhodomelaceae), might not be regarded as an alkaloid. However, this unusual amino acid is biosynthesized from L-glutamic acid and an hemiterpenoid unit, and therefore it is classified as an alkaloid rather than unusual amino acid.
    The pyrazolopyrimidines, such as caffeine of tea and coffee origin, are alkaloids, as is the phytohormone zeatin from maize.
    Also, comparatively simple N-containing compounds (amines), such as serotonin and histamine, are alkaloids, as are mescaline, isolated from the peyote cactus, Lophophora williamsii, and (+)-coniine obtained from Conium maculatum.
    Based on the above discussion, the precise definition of an alkaloid is rather unclear. That is appropriate for such a broadly available, structurally diverse group of metabolites. It may be said that alkaloids are naturally occurring, nitrogen-containing compounds. The group excludes the amino acids of primary metabolism, complex peptides and proteins constructed from those amino acids, and nucleic acids. Thus we see alkaloids, not in terms of a comprehensive definition, but rather as a way to classify a large number of natural metabolites containing nitrogen possessing great structural diversity and derived from any natural source. As has been suggested previously, with experience, “you know one when you see one” [2]. Our task then is to classify them so that the breadth and depth of their molecular frameworks can be assimilated into the larger organization of natural product structures. Literature Cited
[1] Cordell G.A, Quinn-Beattie M.L, Farnsworth N.R. Phytother. Res. 2001;15:183–205. [2] Cordell G.A. Introduction to Alkaloids. A Biogenetic Approach. New York, NY: Wiley Interscience; 1981 1055 pages. 2 Classification of Alkaloids Several approaches to the classification of alkaloids are available, including, chemical, taxonomic, biological, and biosynthetic. At various times, each of these approaches has been used in terms of the presentation and discussion of alkaloid development. We will discuss these approaches in turn. Alkaloids were often classified on the basis of their chemical structure. According to this system, alkaloids are organized based on a common, typically heterocyclic, nucleus, such as isoquinoline, indole, quinolone, quinazoline, pyrrolizidine, and tropane alkaloids, etc. Another method to classify the alkaloids, is to use their natural origin. So we could organize them based on a plant family, such as Amaryllidaceae, Solanaceae, and Rutaceae alkaloids, or based on a genus, such the Catharanthus alkaloids. Classification may use the name of a prototypical alkaloid of the group such as aconitine-type or morphine-type alkaloids. Frequently, this approach also follows a common biosynthetic or biogenetic...