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Fortschritte der Chemie organischer Naturstoffe Progress in the Chemistry of Organic Natural Products Founded by L. Zechmeister Editors: A. D. Kinghorn, Columbus, OH H. Falk, Linz J. Kobayashi, Sapporo Honorary Editor: W. Herz, Tallahassee, FL Editorial Board: V. Dirsch, Vienna S. Gibbons, London N. H. Oberlies, Research Triangle Park, NC Y. Ye, Shanghai
89 Fortschritte der Chemie organischer Naturstoffe Progress in the Chemistry of Organic Natural Products Authors: B. Kräutler N. P. Sahu, S. Banerjee, N. B. Mondal, and D. Mandal SpringerWienNewYork
Prof. A. Douglas Kinghorn, College of Pharmacy, Ohio State University, Columbus, OH, USA em. Univ.-Prof. Dr. H. Falk, Institut für Organische Chemie, Johannes-Kepler-Universität, Linz, Austria Prof. Dr. J. Kobayashi, Graduate School of Pharmaceutical Sciences, Hokkaido University, Sapporo, Japan 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. # 2008 Springer-Verlag=Wien Printed in Germany SpringerWienNewYork is part of Springer Science þ Business Media springer.at Product Liability: The publisher can give no guarantee for the information contained in this book. This also refers to that on drug dosage and application thereof. In each individual case the respective user must check the accuracy of the information given by consulting other pharmaceutical literature. The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Library of Congress Catalog Card Number AC 39-1015 Typesetting: Thomson Digital, Chennai Printing and binding: Strauss GmbH, 69509 Mörlenbach, Germany Printed on acid-free and chlorine-free bleached paper SPIN: 12100125 With 7 partly coloured Figures ISSN 0071-7886 ISBN 978-3-211-74018-7 SpringerWienNewYork
Contents List of Contributors.... VII Chlorophyll Catabolites B. Kräutler.... 1 1. Introduction.... 2 2. Chlorophyll Catabolites from Vascular Plants.... 6 2.1. Green Chlorophyll Degradation Products in Vascular Plants....... 6 2.1.1. Chlorophyllide a and b from Chlorophylls by Loss of the Phytol Side Chain... 6 2.1.2. Reductive Path from b- to a-type Chlorophyll(ide)s........ 8 2.1.3. Pheophorbide a from Chlorophyllide a by Removal of the Magnesium Ion... 8 2.1.4. 13 2 -Carboxy-pyropheophorbide a from Hydrolysis and Pyropheophorbide a from Overall Loss of the Methoxycarbonyl Group from Pheophorbide a.... 9 2.2. Non-green Chlorophyll Degradation Products from Vascular Plants..... 10 2.2.1. Discovery and Structure Analysis of Fluorescent Chlorophyll Catabolites.... 11 2.2.2. Preparation of the Elusive Red Chlorophyll Catabolite by Partial Synthesis..... 13 2.2.3. An Enzyme-bound Red Chlorophyll Catabolite from Enzymatic Oxygenation of Pheophorbide a... 16 2.2.4. Fluorescent Chlorophyll Catabolites from Enzymatic Reduction of the Red Chlorophyll Catabolite... 18 2.2.5. Model Experiments for the Reduction of the Red Chlorophyll Catabolite to Fluorescent Chlorophyll Catabolites.... 19 2.2.6. Non-fluorescent Colourless Chlorophyll Catabolites..... 21 2.2.7. A Non-enzymatic Tautomerization Achieves the Final Transformation of Fluorescent Chlorophyll Catabolites to Non-fluorescent Colourless Chlorophyll Catabolites..... 22 2.2.8. Peripheral Functional Groups and Conjugations Found in Non-fluorescent Colourless Chlorophyll Catabolites...... 24 2.2.9. Evidence for Further Breakdown of the Non-fluorescent Colourless Chlorophyll Catabolites in Higher Plants........ 28 3. Chlorophyll Catabolites from the Green Alga Chlorella protothecoides.... 30 4. Chlorophyll Catabolites from Marine Organisms....... 32
VI Contents 5. Conclusions and Outlook...... 34 Acknowledgements.... 37 References... 37 Steroidal Saponins N. P. Sahu, S. Banerjee, N. B. Mondal, and D. Mandal... 45 1. Introduction... 45 2. Isolation.... 46 3. Structure Elucidation.... 49 3.1. Conventional Methods..................................... 50 3.2. Spectrometry Coupled with Chemical Methods................... 52 3.3. Modern Spectrometric Methods.............................. 55 3.3.1. Mass Spectrometry... 55 3.3.2. NMR Spectroscopy... 57 3.3.2.1. 1 H NMR Spectroscopy... 57 3.3.2.2. 13 C NMR Spectroscopy.... 58 3.3.2.3. 2D NMR Spectroscopy... 59 4. Biological Activity... 62 4.1. Cytotoxic Activity Against Cancer Cell Lines.................... 63 4.2. Antifungal Activity.... 66 4.3. Miscellaneous Effects...................................... 68 5. Biosynthesis of Steroidal Glycosides..... 69 6. Report of New Steroidal Saponins (1998 Mid-2006).......... 70 7. Conclusion... 126 Acknowledgement..... 126 References... 127 Author Index... 143 Subject Index... 153 Listed in Medline
List of Contributors Banerjee, Dr. S., Indian Institute of Chemical Biology, 4 Raja S C Mullick Road, Jadavpur, Kolkata 700 032, India Kräutler, Prof. Dr. B., Institut für Organische Chemie, Universität Innsbruck, Innrain 52a, 6020 Innsbruck, Austria e-mail: bernhard.kraeutler@uibk.ac.at Mandal, Dr. D., Indian Institute of Chemical Biology, 4 Raja S C Mullick Road, Jadavpur, Kolkata 700 032, India Mondal, Dr. N. B., Indian Institute of Chemical Biology, 4 Raja S C Mullick Road, Jadavpur, Kolkata 700 032, India Sahu, Dr. N. P., Indian Institute of Chemical Biology, 4 Raja S C Mullick Road, Jadavpur, Kolkata 700 032, India e-mail: npsahu@iicb.res.in