Italian Society of Chemistry Division of Organic Chemistry Division of Medicinal Chemistry Division of Mass Spectrometry TARGETS IN HETEROCYCLIC SYSTEMS Chemistry and Properties Volume 16 (2012) Reviews and Accounts on Heterocyclic Chemistry http://www.soc.chim.it/it/libriecollane/target_hs Editors Prof. Orazio A. Attanasi University of Urbino “Carlo Bo”, Urbino, Italy and Prof. Domenico Spinelli University of Bologna, Bologna, Italy Published by: Società Chimica Italiana Viale Liegi, 48 00198 Roma Italy ___________________________________________________________________________ Copyright © 2012 Società Chimica Italiana All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means (electronic, electrostatic, magnetic tape, mechanical, photocopying, recording or otherwise) without permission in writing from the publishers. A person may photocopy an article for personal use. Volume 1 (1997) First edition 1997 ISBN 88-86208-24-3 Second edition 1999 ISBN 88-86208-24-3 Volume 2 (1998) First edition 1999 ISBN 88-86208-11-1 Volume 3 (1999) First edition 2000 ISBN 88-86208-13-8 Volume 4 (2000) First edition 2001 ISBN 88-86208-16-2 Volume 5 (2001) First edition 2002 ISBN 88-86208-19-7 Volume 6 (2002) First edition 2003 ISBN 88-86208-23-5 Volume 7 (2003) First edition 2004 ISBN 88-86208-28-6 ISSN 1724-9449 Volume 8 (2004) First edition 2005 ISBN 88 86208-29-4 ISSN 1724-9449 Volume 9 (2005) First edition 2006 ISBN 88 86208-31-6 ISSN 1724-9449 Volume 10 (2006) First edition 2007 ISBN 978-88-86208-51-2 ISSN 1724-9449 Volume 11 (2007) First edition 2008 ISBN 978-88-86208-52-9 ISSN 1724-9449 Volume 12 (2008) First edition 2009 ISBN 978-88-86208-56-7 ISSN 1724-9449 Volume 13 (2009) First edition 2010 ISBN 978-88-86208-62-8 ISSN 1724-9449 Volume 14 (2010) First edition 2011 ISBN 978-88-86208-67-3 ISSN 1724-9449 Volume 15 (2011) First edition 2012 ISBN 978-88-86208-70-3 ISSN 1724-9449 Volume 16 (2012) First edition 2013 ISBN 978-88-86208-72-7 ISSN 1724-9449 Printed and bound in Italy by: Arti Grafiche Editoriali s.r.l. Via S. Donato, 148/C 61029 Urbino (Pesaro-Urbino) Italy June 2013 Editorial Advisory Board Members Prof. Jan Bergman Prof. Gianluca Giorgi Karolinska Institute University of Siena Huddinge, Sweden Siena, Italy Prof. Robert K. Boeckman Jr. Prof. Lucedio Greci University of Rochester University of Ancona Rochester, USA Ancona, Italy Prof. José A. S. Cavaleiro Prof. Laurence M. Harwood University of Aveiro University of Reading Aveiro, Portugal Reading, UK Prof. Leopoldo Ceraulo Prof. Victor G. Kartsev University of Palermo InterBioScreen Ltd Palermo, Italy Moscow, Russia Prof. Girolamo Cirrincione Prof. Steven V. Ley University of Palermo University of Cambridge Palermo, Italy Cambridge, UK Prof. Janine Cossy Prof. Alexander McKillop ESPCI University of East Anglia Paris, France Norwich, UK Dr. Daniele Donati Prof. Giovanni Sindona Glaxo Wellcome University of Calabria Verona, Italy Arcavacata di Rende, Italy Prof. José Elguero Prof. Branko Stanovnik CSIC University of Ljubljana Madrid, Spain Ljubljana, Slovenia Prof. Dieter Enders Prof. Richard J. K. Taylor RWTH University of York Aachen, Germany York, UK Prof. Leon Ghosez Prof. Eric J. Thomas Catholic University of Louvain University of Manchester Louvain la Neuve, Belgium Manchester, UK Indexed/Abstracted in: Chemical Abstracts; Current Contents; ISI/ISTP&B online database; Index to Scientific Book Contents; Chemistry Citation Index; Current Book Contents; Physical, Chemical & Earth Sciences; Methods in Organic Synthesis; The Journal of Organic Chemistry; La Chimica e l'Industria; Synthesis. Preface Heterocyclic derivatives are important in organic chemistry as products (including natural) and/or useful tools in the construction of more complicated molecular entities. Their utilization in polymeric, medicinal and agricultural chemistry is widely documented. Dyestuff, electronic, and tanning structures, as well as life molecules frequently involve heterocyclic rings that play an important role in several chemical and biochemical processes. Volume 16 (2012) keeps the international standard of TARGETS IN HETEROCYCLIC SYSTEMS – Chemistry and Properties (THS) series and contains eleven chapters, covering the synthesis, reactivity, and activity (including medicinal) of different heterorings. Authors from France, Germany, India, Italy, Poland, Russia, Slovakia, Sweden, and United Kingdom are present in this book. As yet, THS Volumes 1-16 published 221 reviews by 626 authors from 29 different countries for a total of about 7.000 pages. Comprehensive Reviews reporting the overall state of the art on wide fields as well as personal Accounts highlighting significative advances by research groups dealing with their specific themes have been solicited from leading Authors. The submission of articles having the above-mentioned aims and concerning highly specialistic topics is strongly urged. The publication of Chapters in THS is free of charge. Firstly a brief layout of the contribution proposed, and then the subsequent manuscript, may be forwarded either to a Member of the Editorial Board or to one of the Editors. The Authors, who contributed most competently to the realization of this Volume, and the Referees, who cooperated unselfishly (often with great patience) spending valuable attention and time in the review of the manuscripts, are gratefully acknowledged. The Editors thank very much Dr. Lucia De Crescentini for her precious help in the editorial revision of the book. Orazio A. Attanasi and Domenico Spinelli Editors Table of Contents (for the contents of Volumes 1–15 please visit: http://www.soc.chim.it) Recent applications of the intramolecular Diels-Alder furan (IMDAF) reaction 1 in natural product synthesis Frank W. Lewis and Laurence M. Harwood 1. Introduction 2. General aspects of the IMDAF reaction 2.1. Regioselectivity and stereoselectivity 2.2. Nature of the diene and dienophile 2.3. Influence of the tether 2.4. Activation of substrates toward IMDAF reaction 3. Recent applications of the IMDAF reaction in total synthesis 4. New synthetic methodology involving the IMDAF reaction 5. Asymmetric approaches 6. Conclusions References Asymmetric catalytic synthesis of corynanthe and ipecac alkaloids 31 Wei Zhang and Johan Franzén 1. Introduction 2. Synthetic methods for the synthesis of corynanthe and ipecac alkaloids 2.1. Route A: early enantioselective formation of the ring-junction stereocentre 2.2. Route B: late diastereoselective formation of the ring-junction stereocentre 3. Conclusions References The principle of vinylogy as applied to heterocyclic donor systems 56 Franca Zanardi, Gloria Rassu, Lucia Battistini, Claudio Curti, Andrea Sartori and Giovanni Casiraghi 1. Introduction 2. About this review 3. Indirect Mukaiyama-type methodologies 3.1. Furan-based silicon enolates 3.2. Pyrrole-based silicon enolates 3.3. Other silicon enolates 4. Direct catalytic methodologies 4.1. Furan-based pro-nucleophiles 4.2. Pyrrole-based pro-nucleophiles 4.3. Other heterocyclic pro-nucleophiles I 5. Closing remarks Acknowledgments References The Diels-alder reactivity of the furoxan ring of substituted benzofuroxans. 90 Synthesis of substituted imines and evidence of the intermediacy of ortho-dinitrosoarenes in the 1-oxide/3-oxide interconversion Cyril Jovené, Muriel Sebban, Jérome Marrot and Régis Goumont 1. Introduction 2. Trapping of ortho -dinitrosoarene: first evidences of the intermediacy of this intermediate in the 1-oxide/3-oxide interconversion 2.1. The case example of 4-aza-6-nitrobenzofuroxan H 2.2. Extension of the trapping process to other benzofuroxans 2.3. A recent result: the case of 6-fluoro-5-nitrobenzofuroxan 3. The 1-oxide/3-oxide interconversion: Diels-Alder reaction of both tautomers with isoprene and 2,3-dimethylbutadiene 3.1. Reaction of 5-nitrobenzofuroxan with 2,3-dimethylbutadiene 3.2. Reaction of 5-nitro-6-fluorobenzofuroxan with 2,3-dimethylbutadiene and isoprene 4. The reactivity of the benzofurazan N and O, analogues of J and M 4.1. Reaction of N and O with 2,3-dimethylbutadiene 4.2. Reaction of N and O with cyclohexa-1,3-diene 5. The heterodienic behaviour of the N3=C9 −C8=N1 system of the furoxan ring: an access to highly functionalized imines 5.1. The reaction of benzofuroxans B, C and E with cyclohexa-1,3-diene 5.2. The reaction of benzofuroxans C and E with isoprene 6. Conclusion Acknowledgments References Approaches to thiazole dipeptides for the synthesis of thiopeptide antibiotics 113 Armin Geyer and Sebastian Enck 1. Introduction 1.1. Thiazole units in peptide natural products 1.1.1. Ribosomal thiazole formation 1.1.2. Thiopeptide antibiotics 2. Chemical thiazole synthesis: strategies and problems 2.1. Two-component reactions 2.2. Cyclizations of linear precursors 2.3. C−C couplings and multicomponent reactions 2.4. Total syntheses of Xaa<Thz dipeptides present in thiopeptide antibiotics II 2.5. Sugar precursors of the dihydroxyglutamate side chain 3. Conclusion References 5-Hetaryl-pyrimidine-2,4(1 H,3 H)-diones: synthesis and functionalization 128 Dominika Jakubiec and Krzysztof Z. Walczak 1. Introduction 1.1. Uracil and cytosine 1.2. Biological activity 2. Methods of synthesis 2.1. Historical review 2.2. Condensation 2.2.1. Classical condensation 2.2.2. ANRORC 2.3. Metal-assisted reactions 2.3.1. Stille cross-coupling reaction 2.3.2. Suzuki-Miyaura cross-coupling reaction 2.3.3. Negishi coupling 2.3.4. Direct arylation reaction 2.4. Cycloaddition reactions 2.4.1. 1,3-Dipolar cycloaddition 2.4.2. Diels-Alder cycloaddition 2.5. Miscellaneous 3. Applications 4. Summary Acknowledgments References Intramolecular tranformations of 4-(2-substituted aryl)-1,2,3-thia and selenadiazoles. 157 Synthesis of benzo[ b]furans, indoles, benzo[ b]thiophenes, benzo[ b]selenophenes and others heterocycles Dmitry A. Androsov and Mikhail L. Petrov František Mathia, Peter Zálupský and Peter Szolcsányi 1. Introduction 2. Benzo[ b]furans 2.1. Benzo[ b]furan-2-sulfides 2.1.1. 4-(2-Hydroxyaryl)-1,2,3-thiadiazoles 2.1.2. Benzo[ b]furan-2-thiolates.