Fortschritte der Chemie Organischer Naturstoffe / Progress in the Chemistry of Organic Natural Products PDF
Preview Fortschritte der Chemie Organischer Naturstoffe / Progress in the Chemistry of Organic Natural Products
FORTSCHRITTE DER CHEMIE ORGANISCHER NATURSTOFFE PROGRESS IN THE CHEMISTRY OF ORGANIC NATURAL PRODUCTS BEGRÜNDET VON · FOUNDED BY L. ZECHMEISTER HERAUSGEGEBEN VON· EDITED BY W. HERZ H. GRISEBACH G. W. KIRBY T ALLAHASSEE, FLA. FREIBURG i. BR. GLASGOW VOL. 33 VERFASSER· AUTHORS G. CIMINO · R. M. COATES · S. OE STEFANO · A. FONTANA P.HEMMERICH · L.MINALE · K.L.RINEHART,JR. · L.S.SHIELD G. SODANO · C. TONIOLO 1976 SPRINGER-VERLAG WIEN GMBH Mit 48 Abbildungen · With 48 Figures This work is subject to copyright All rights are reserved, whether the whole or part of the material is concerned, specifically those of translation, reprinting, re-use of illustrations, broadcasting, reproduction by photocopying machine or similar means, and storage in data banks © 1976 by Springer-Verlag Wien Originally published by Springer-Verlag Wien-New York in 1976 Softcover reprint of the bardeover 1st edition 1976 Library of Congress Catalog Card Number AC 39-1015 ISBN 978-3-7091-3264-7 ISBN 978-3-7091-3262-3 (eBook) DOI 10.1007/978-3-7091-3262-3 Inhaltsverzeichnis. Contents List of Contributors. Mitarbeiterverzeicbnis ..................................... VIII ;'lo/atural Products from Porifera. By L. MINALE, G. CIMINO, S. DE STEFANO, and G. SooANO I. Introduction . . . . . . . . . . . . . . . . . . . . ................ . 2 li. Structure Determination and Chemistry . 2 I. Bromo-Compounds ................. . 2 1.1 Tyrosine-Derived Bromo-Compounds 3 1.2 Miscellaneous Bromo-Compounds 9 2. Terpenes .......... . II 2.1 Sesquiterpenes ..... . 12 2.2 Diterpenes . . . . ....... . 21 2.3 The C2 1 Furanoterpenes .................. . 22 2.4 Sesterterpenes ..... 28 3. Compounds of Mixed Biogenesis: Mevalonate-Benzenoid Precursor 33 4. Sterols ....................... . 41 4.1 "Conventional" Sterols ......................................... . 42 4.2 "Unusual" Sterols 46 4.3 Sterol Biosynthesis in Sponges 51 5. Miscellaneous Compounds ......... . 51 III. Distribution ...................... . 55 IV. Pharmacological Properlies 58 Addendum. . ............ . 59 References 64 Biogenetic-Type Rearrangements of Terpenes. By R. M. COATES ... 73 A. Introduction 74 B. Monoterpenes. . ..................... . 83 I. Chrysanthemanes, Lavandulanes, Artemisanes, and Santalinanes 83 2. Menthanes, Pinanes, Camphanes, Fenchanes, and Thujanes 88 IV Inhaltsverzeichnis. C:ontents C. Sesquiterpenes 96 1. Bisabolanes, Sesquicamphanes, Santalanes, and C:arotanes ................ . 96 2. Germacranes. Eudesmanes, Guaianes, C:adinanes, and C:ubebanes 101 3. H umulanes, C:aryophyllanes, and Himachalanes . . . . . . . . . . . . . . . . . . . . . 110 4. l,n-Hydrogen Eliminationsand 1,n-Hydrogen Rearrangements 113 5. Eremophilanes, Vetispiranes, Yalcrancs, and C:yperanes 130 6. C:uparanes, Chamigranes, Thujopsanes, and Widdranes 138 7. Patchoulanes and Seychellanes . 142 8. Copaanes, C:opabornanes, Ylanganes, and Sativanes .. 145 9. Longipinanes. Longibornanes, and Longifolanes 149 I 0. Acoranes, Cedranes, and Zizaanes 151 D. Ditcrpenes . 156 I. Labdanes, Clerodanes, Pimaranes, and Rosanes 156 2. Abietanes, Strobane, and Cleistanthane . 161 3. Beyeranes, Kauranes, Atisanes, and Trachylobanes 164 4. Gibberellanes, Grayanes. and Aconanes. 168 E. Triterpenes 172 1. Squalene . 172 2. Lanostanes, C:ycloartanes, Euphanes, and Tirucallanes 178 3. Melianes, Cucurbitacins, and 9( I 0--+ 19)Abeo-pregnanes 183 4. Lupanes, Germanicanes, Taraxastanes, 01eananes. and Ursanes 187 5. Taraxeranes, Multiflorane, Glutinanes, Friedelanes, lsoursane, Phyllanthane. Baueranc, and Shionanes. . . . . . . . . . . . . . . 194 6. Hopanes, Fernanes, Adinanes, and Filicanes. . 202 References. 205 Chemistry of the Ansamycin Antibiotics. By K. L. RINEHART, JR., and L. S. SHIELD .. 231 I. Introduction ............ . 232 II. Structures of the Naturally Occurring Ansamycins 234 A. Streptovaricins 234 B. Rifamycins .... 237 C. Halomicins 239 D. To1ypomycins .... 240 E. Naphthomycin 241 F. Geldanamycin ............ . 241 G. Maytansinoids 242 H. Three-dimensional Structures 242 III. Reactions of the Ansamycins 244 A. Streptovaricins ........ . 245 l. Degradations ......... . 245 2. Derivatizations ....... . 251 Inhaltsverzeichnis. Contents V B. Rifamycins ... 256 l. Degradations 256 2. Derivatizations ..................... . 263 C. Halomicins .......................... . 270 D. Tolypomycin . . . . . . . . . . . . . . . . . . . . . . . . . . . .......................... . 271 I. Degradations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........ . 271 2. Derivatizations . . . . . . . . . . . . . . . . . . . . . ........ . 274 E. Naphthomycin ....................... . 274 F. Geldanamycin ........... . 275 I. Degradations ............................................. . 275 2. Derivatizations ........................................... . 275 G. Maytansinoids 278 H. Conclusions Regarding Bioactivity .......... . 280 IV. Physical Properties of the Ansamycins 281 A. Ultraviolet, Rotatory, Infrared Spectra 281 B. Magnetic Resonance Spectra ... 283 C. Mass Spectra 288 V. Biosynthesis of the Ansamycins .... 289 A. Streptovaricins ............... . 291 B. Rifamycins 297 C. Geldanamycin ..... 298 References 300 The Chemistry of Tryptophan io Peptidesand Proteins. By A. FONTANA and C. TONIOLO 309 Acknowledgements 311 l. Introduction 311 li. General ............ . 312 I. Structure and Reactivity .... 312 2. Chemical Synthesis 314 3. Biosynthesis ............................ . 318 4. Aspects of Metabolism ............................................. . 320 !I I. Chemistry of the Modification and Cleavage of the Tryptophanyl Peptide Bond 323 I. Chemical Oxidation . . . . . . . . . . . . . . . . . . . 324 1.1. Peracids . . . . . . . . . . . . . . . . . . . . . . . . . . 324 1.2. Ozone. . . . . . . . . . . . . . . . . 328 I. 3. Miscellaneous Oxidations . 329 2. Photooxidation............. . . . . . . . . . . . 331 2.1. Irradiation by Ultravialet Light . . . . . . . . . . . . . . . . . 331 2.2. Dye-Sensitized Photooxidation . . . . . . . . . . . . . . . 333 2.2.1. Conversion of Tryptophan to Hexahydropyrroloindole 335 2.2.2. Conversion of Tryptophan to Quinazolines . . . . . . . . . . . 337 2.2.3. Conversion of Tryptophan to Carbolines 338 2.3. Ionizing Radiation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339 VI Inhaltsverzeichnis. Contents 3. Brominating Agents ..... .140 3.1. N-Bromosuccinimide. .140 3.2. BNPS-skatole .... .146 3.3. Tribromocresol. .148 4. 2-Hydroxy-5-nitrobenzyl Bromide (Koshland's Reagent). 349 4.1. Chemistry of the Reaction .... 349 4.2. Othcr Nitrobenzyl Reagents 353 5. Sulfenyl Halides ..... 356 5. I. General 356 5.2. Chemistry of the 2-Thioether-indole Function. 358 6. Isotopic LabeHing 363 7. C-Acylation. 365 8. N-Formylation 367 9. Cyclodehydration .. 368 10. Reaction with Nitrite ............. . 369 II. Reaction with Tetranitromethane ... . 369 12. Reaction with Diazonium Salts. 371 13. Reaction with 3-Acetoxyxanthine . 371 14. Reaction with Trichloroisocyanuric Acid 372 15. Miscellaneous 372 IV. Analytical Determination 374 I. Acid Hydrolysis 375 2. Basic Hydrolysis ..... . 378 3. Spectrophotometry. . ........... . 378 4. Colorimetry ... 381 4 .I. p-Dimethylaminobenzaldehyde 381 4 .2. Sulfenyl Halides . . . . . ........ . 383 4.3. Koshland's Reagent ........... . 383 5. Other Methods 384 5.1. N-Bromosuccinimide .. 384 5.2. Miscellaneous ..... . 386 V. Structure Determination 387 I. Ultraviolet Absorption 387 2. Circular Dichroism .. 389 2. I. Magnetic Circular Dichroism 3<!0 2.2. Circular Polarization of Luminescence 393 3. Nuclear Magnetic Resonance .......... 396 3.1. 1H-NMR ... 396 3.2. 13C-NMR 398 3.3. 14N-NMR 399 4. X-Ray and Conformational Energy Calculation Studies 400 4.1. X-Ray Structure Determination ... 400 4.2. Confotmational Energy Calculations .. 402 5. Charge Transfer Interactions .. 403 Inhaltsverzeichnis. Contents VII VI. Synthesis of Tryptophan Peptides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405 I. Synthesis in Solution and in the Solid Phase . . . . . . . . . . . . . . . . . . . . . . 405 2. Special Cases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407 2.1. Glucagon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407 2.2. Valine-gramicidin A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409 2.3. Luteinizing Hormone-Releasing Hormone . . . . . . . . . . . . . . . . . . . . . . . . . 410 2.4. Toxins of Amanita Phalloides .................................... 414 VII. The RoJe of Tryptophan in the Biological Function of Enzymes ........... 416 I. Lysozyme . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 22 2. Dehydrogenases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422 VIII. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424 Note Added in Proof ....................................................... 424 References ............................................................... 426 The Present Status of Flavin and Flavocoenzyme Chemistry. By P. HEMMERICH .... 451 I. Introduction: History and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451 II. N omenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456 III. Mechanism of Flavin-Dependent Oxido-Reduction ........................ 460 IV. Flavoquinone ......................................................... 466 V. Flavin Radicals ....................................................... 467 VI. Dihydroflavins ........................................................ 471 VII. Flavin-Substrate Complexes ............................................. 478 VIII. F1avin-Acceptor-Complexes ............................................. 481 IX. New Flavocoenzymes ................................................. 488 X. Flavin Photochemistry ................................................. 506 XI. F1avin-Dependent Photobiology . . . . . . . . . . . . . . . . . ...................... . 514 XII. Concluding Remarks ................................................... 516 Note Added in Proof . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 7 References .............................................................. . 517 Namenverzeichnis. Author Index ............................................. . 529 Sachverzeichnis. Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 553 Mitarbeiterverzeichnis. List of Contributors Cimino, Dr. G., Researcher, Laboratorio per Ia Chimica di Molecole di Interesse Biologico del C.N.R., I-80072 Arco Felice, Napoli, ltaly. Coates, Prof. Dr. R. M., Department of Chemistry, University of Illinois at Urbana- Champaign, Urbana, IL 61801, U.S.A. De Stefano, Dr. S., Researcher, Laboratorio per Ia Chimica di Molecole di Interesse Biologico del C.N.R., I-80072 Arco Felice, Napoli, ltaly. Fontana, Prof. Dr. A., Istituto di Chimica Organica dell'Universita, Via Marzolo, I, I-35100 Padova, ltaly. Hemmerich, Prof. Dr. P., Fachbereich Biologie, Universität Konstanz, Postfach 733, D-7750 Konstanz, Bundesrepublik Deutschland. Minale, Prof. L., Professor of Organic Chemistry, Director, Laboratorio per Ia Chimica di Molecole di Interesse Biologico del C.N.R., I-80072 Arco Felice, Napoli, Italy. Rinehart Jr., K. L., B. S., Ph. D., Roger Adams Laboratory, University of Illinois, Urbana, IL 61801, U.S.A. Shield, L. S., A. B., Sc. M., Roger Adams Laboratory, University of Illinois, Urbana, IL 61801, U.S.A. Sodano, Dr. G., Researcher, Laboratorio per Ia Chimica di Molecole di Interesse Biologico del C.N.R., I-80072 Arco Felice, Napoli, ltaly. Toniolo, Prof. C., Istituto di Chimica Organica deii'Universitit, Via Marzolo, I, I-35100 Padova, Italy. Natural Products from Porifera By L. MINALE, G. CIMINO, S. DE STEFANO and G. SoDANO, Laboratorio per Ia Chimica di Molecole di Interesse Biologico del C. N. R., Arco Felice (N apoli), Italy Contents I. Introduction .................. . 2 II. Structure Determination and Chemistry ....... . 2 I. Bromo-Compounds 2 1.1 Tyrosine-Derived Bromo-Compounds ... . 3 1.2 Miscellaneous Bromo-Compounds ............. . 9 2. Terpenes ....... . 11 2.1 Sesquiterpenes ..................... . 12 2.2 Diterpenes .... 21 2.3 The C21 Furanoterpenes ........................ . 22 2.4 Sesterterpenes . . . . ......... . 28 3. Compounds of Mixed Biogenesis: Mevalonate-Benzenoid Precursor 33 4. Sterols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41 4.1 "Conventional" Sterols ........ . 42 4.2 "Unusual" Sterals .... 46 4.3 Sterol Biosynthesis in Sponges 51 5. Miscellaneous Compounds .. 51 III. Distribution 55 IV. Pharmacological Properlies .................. . 58 Addendum.. . .............. . 59 References 64 Acknowledgements It is our privilege to thank Professors E. LEDERER (Gif-sur-Yvette, France), president of the Scientific Committee of this Laboratory, for his encouragement and interest in this work, and R. H. THOMSON (Aberdeen, Scotland) for advice and revision of the manuscript. Fortschritte d. Chem. arg. Naturst. 33
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