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
FortsehriHe del' Chemie organiseher Naturstoffe Progress in the Chemist~ of Organie Natural Produets 60 Founded ~ L Zeehmeister Edited ~ W. Berz, G. W. Kir~, R. E. Moore, W. Ste,lieh, and Ch. Tamm Authors: C. A. A. van Bfield, A.-M. Eklund, M. Petitou, I. Wahlberg Springer-Verlag Men NewYorll lqqZ Prof. W. HERZ, Department of Chemistry, The Florida State University, Tallahassee, Florida, U.S.A. Prof. G. W. KIRBY, Chemistry Department, The University, Glasgow, Scotland Prof. R. E. MOORE, Department of Chemistry, University of Hawaii at Manoa, Honolulu, Hawaii, U.S.A. Prof. Dr. W. STEGLlCR, Institut fiir Organische Chemie und Biochemie der Universitiit Bonn, Bonn, Federal Republic of Germany Prof. Dr. CR. TAMM, Institut fiir Organische Chemie der Universitiit Basel, Basel, Switzerland 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 machines or similar means, and storage in data banks. © 1992 by Springer-Verlag/Wien Library of Congress Catalog Card Number AC 39-1015 Typesetting: Macmillan India Ltd., Bangalore-25 Printed on acid free paper With 59 Figure ISBN-13: 978-3-7091-9227-6 e-ISBN- 978-3-7091-9225-2 DOl: 10.1007/978-3-7091-9225-2 Contents List of Contributors. . . . . . . . . . . . . . . . . . . . . . . VII Cyclized Cembranoids of Natural Occurrence. By I. WAHLBERG and A.-M. EKLUND I. Introduction 2 A. Nomenclature and Structural Representation. 3 II. Cyc1ized Cembranoids from Tobacco. 5 III. Cyc1ized Cembranoids from Insects 9 A. Nasutitermitinae. . . 10 1. Bulbitermes Species . 10 2. Cortaritermes Species 10 3. Grallatotermes Species 13 4. Hospitalitermes Species. 13 5. Longipeditermes Species 14 6. Nasutitermes Species. 15 7. Subilitermes Species . 15 8. Trinervitermes Species 16 9. Velocitermes Species. 17 IV. Cyc1ized Cembranoids from Marine Invertebrates 17 A. Gorgonacea . . . . . . . . . . . . 43 1. Astrogorgia, Calicogorgia, Eunicella and Muricella Species 43 2. Briareum Species. . . . . . . 44 3. Erythropodium Species. . . . . 47 4. lunceella and Plexaureides Species. 48 B. A1cyonacea. . . . . 49 1. Alcyonium Species 49 2. Cespitularia Species . 51 3. Cladiella, Litophyton, Sclerophytum and Sinularia Species. 51 4. Gersemia Species. . 52 5. Minabea Species . . 52 6. Sarcophyton Species . 52 C. Stolonifera. . . . . 53 D. Pennatulacea. . . . 54 1. Cavernulina, Pteroides, Ptilosarcus, Renilla, Scytalium and Stylatula Species 54 2. Veretillum Species. . . . . . . . . . . . . 55 VI Contents Addendum. 120 Acknowledgements. 132 References. . . . 132 Chemical Synthesis of Heparin Fragments and Analogues. By M. PETITOU and C.A.A. VAN BOECKL 143 1. Introduction. . . . 144 1.1 Heparin . . . . 144 1.2 Heparin Fragments 146 2. Synthesis of the Antithrombin Binding Site 147 2.1 Strategy . . . . . . . . . . . 148 2.2 Preparation of D-Glucuronic Acid Derivatives. 150 2.3 Preparation of L-Iduronic Acid Derivatives. . 151 2.4 Synthesis of the Fully Protected Pentasaccharides 154 2.5 Synthesis of Building Blocks from Natural Disaccharides . 155 2.5.1 Synthesis from Cellobiose. . 155 2.5.2 Synthesis from Maltose. . . . . . . . . . . 157 2.6 Deprotection and Functionalisation . . . . . . . . 158 2.7 Recent Results in the Synthesis of the Antithrombin Binding Site 160 2.7.1 Synthesis of the ex-Methyl Glycoside of the Antithrombin Binding Site. . . . . . . . . . ... . . . . . . . 160 2.7.2 Synthesis of the N-Acetylated Antithrombin Binding Sequence . 161 3. Synthesis and Biological Properties of Analogues of the Antithrombin Binding Site . . . . . . . . . . . . . . . . . . . . 162 3.1 Analogues lacking N, O-Sulphate Groups at Defined Positions. 162 3.2 Analogues with Modifications of the Carboxylate Groups at Defined Positions. . . . . . . . . . . . . . . . . 167 3.3 A Potent Analogue with Extra 3-0-Sulphate Group at Unit H . 170 3.4 Analogues of the Extra Sulphated, Potent Analogue (81) 175 3.5 Analogues Containing "Opened" Uronic Acid Moieties 178 3.6 Analogues with Various Modifications . . . . 182 3.7 Alkylated Analogues of Heparin Pentasaccharides . . 186 4. Conformational Properties. . . . . . . . . . . . 194 5. Interaction of Heparin Pentasaccharide Fragments with Antithrombin III 200 Acknowledgements. 203 References. . 203 Author Index. 211 Subject Index. 217 General Index Vol. 21-60 225 List of Contributors VAN BOECKL, Dr. C.A.A., Organon Scientific Development Group P.O. Box 20, NL-5340 Oss, The Netherlands. EKLUND, Dr. A.-M., Reserca AB, Box 17007, S-I04 62 Stockholm, Sweden. PETITOU, Dr. M., Sanofi Research, Rue de President S. Allende, F-94256 Gentilly, France. WAHLBERG, Dr. I., Reserca AB, Box 17007, S-I04 62 Stockholm, Sweden. Cyclized Cembranoids of Natural Occurrence I. WAHLBERG and A.-M. EKLUND, Reserca AB, Stockholm, Sweden Contents I. Introduction . . . . . . . . . . . . . 2 A. Nomenclature and Structural Representation. 3 II. Cyclized Cembranoids from Tobacco. 5 III. Cyclized Cembranoids from Insects 9 A. Nasutitermitinae. . . 10 1. Bulbitermes Species . 10 2. Cortaritermes Species 10 3. Grallatotermes Species 13 4. H ospitalitermes Species. 13 5. Longipeditermes Species 14 6. Nasutitermes Species. 15 7. Subulitermes Species. 15 8. Trinervitermes Species 16 9. Velocitermes Species. 17 IV. Cyclized Cembranoids from Marine Invertebrates 17 A. Gorgonacea . . . . . . . . . . . . 43 1. Astrogargia, Calicogargia, Eunicella and Muricella Species 43 2. Briareum Species. . . . . . . 44 3. Erythrapadium Species. . . . . 47 4. Junceella and Plexaureides Species. 48 B. Alcyonacea. . . . 49 1. Alcyanium Species . . . . . . 49 2. Cespitularia Species. . . . . . 51 3. Cladiella, Litophyton, Sclerophytum and Sinularia Species. 51 4. Gersemia Species. . 52 5. Minabea Species . . 52 6. Sarcophyton Species. 52 C. Stolonifera. . . . . 53 D. Pennatulacea. . . . 54 1. Cavernulina, Pteroides, Ptilosarcus, Renilla, Scytalium and Stylatula Species 54 2. Veretillum Species. 55 Addendum .... 120 Acknowledgements. 132 References. . . . 132 2 I. WAHLBERG and A.-M. EKLUND I. Introduction The structure of eunicillin (89), a carbobicyclic diterpenoid isolated from the Mediterranean gorgonian Eunicella stricta, was reported in 1968 (1). At that time chlorine-containing diterpenoids had been dis- covered in the gorgonian Briareum asbestinum (2, 3), but it was not until 1977 that the structure of the first briaran, briarein A (211), was resolved by X-ray analysis (4). The first trinervitane diterpenoid (26), which was isolated from Trinervitermes termites, was reported in 1976 (5). OAc OAc ACO'···· OH 0 89 211 26 The discovery of these compounds marked the appearance of a large and growing group of diterpenoids which are commonly viewed as being formed from cembrane precursors by secondary carbon-carbon bond closures. It should be emphasized, however, that in the absence of biosynthetic evidence the question of which groups of diterpenoids that should be classified as cyclized cembranoids remains ambiguous. In the present article we have included five tobacco diterpenoids (1-5) which. possess prerequisite structural features and co occur with appropriate cembrane precursors in tobacco. Although structurally reminiscent of cyclized cembranoids, verticillanes, taxanes and cleomeolide are not dealt with, since these diterpenoids of plant origin are not believed to arise via preformed cembranoids (6-11). The bi-, tri- and tetracyclic secotrinervitanoids, trinervitanoids and kempanoids, which are present in the defensive secretions of soldiers of higher termites, are most likely formed via cyclization of cembrane precursors (12). It is also generally agreed that diterpenoids such as briarans, cladiellins and asbestinins are correctly characterized as cyc- lized cembranoids (13-15). These compounds, which show a large struc- tural diversity, are constituents of marine invertebrates. We have previously reviewed the cembranoids of natural occurrence (16). Our intention in the present review is to follow a similar outline and to give a comprehensive compilation of the naturally occurring cyclized cembranoids as defined above, that have appeared in the literature References, pp. 132-141 Cyc1ized Cembranoids of Natural Occurrence 3 through December 1991. Biogenetic relationships are also discussed. It should be added that a review on cyclized cembranoids was published by RALDUGIN and SHEVTSOV in 1987 (17), but their selection of diterpene classes differs from ours. The cyclized cembranoids are frequently heavily substituted and contain several asymmetric centers. It has therefore been necessary to use X-ray diffraction methods for elucidation of the stereostructures of many compounds. References to these X-ray studies are given in Tables 1-3. Like their presumed cembrane precursors, many cyclized cern bran- oids and particularly those of marine origin exhibit important biological and pharmacological effects, this being one of the reasons for the great interest in their structures and chemistry. Available references are given in Table 3. Very few cyclized cembranoids have been prepared synthetically. KATO et al. (18-20) have completed the syntheses of two secotrinervitan- oids (7, 9) and DAUBEN et al. (21) have recently published the total synthesis of ( ± )-kempene-2 (59). Another diterpenoid of insect origin, longipenol (64), has been the target of a synthetic study (22) as has the tobacco basmanoid 3 (see Tables 1 and 2) (23, 24). A. Nomenclature and Structural Representation The present article includes more than two hundred compounds belonging to as many as sixteen different diterpene classes. The nomen- clature systems and principles employed in the literature vary among the classes and also within certain classes. In the case of the cyclized cembranoids of insect origin, the secotrinervitane, trinervitane and kem- pane nomenclatures are generally accepted (25). Nomenclatures for the diterpene classes found in tobacco have also been established (26-28). In addition to existing trivial names, we have therefore introduced a semi- systematic nomenclature based on skeletal type for the tobacco and insect constituents listed in Tables 1 and 2, respectively. The R- and S-system has been adopted to describe the configuration of each compound. The situation is different for the cyclized cembranoids of marine origin. This is illustrated by the fact that some authors (14, 29, 30) employ a briaran or briarein nomenclature based on the oxygen-containing skeleton A, while a briarane nomenclature based on the carbon skeleton B has been adopted by others (31). Similarly, both the asbestinin (C) and asbestinane (D) nomenclatures are found in the literature (14, 32, 33). Because of this lack of consensus, we have only included trivial names 4 I. WAHLBERG and A.-M. EKLUND A B C D PrOco OAc HO 0 ACO"····· 0 0 191a 192a OAc HO o ACO"····· o o 191 192 and configurational R- and S-descriptors in Table 3. For unnamed compounds, however, a semi-systematic nomenclature based on the skeletal types defined in Section IV has been adopted. The graphical representation of macrocyclic rings is not always straightforward. This may lead to confusion as is illustrated for ptilosar- cone and brianthein X. Both compounds have (2S,9S)-configurations and References, pp. 132-141
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