Italian Society of Chemistry Division of Organic Chemistry Division of Medicinal Chemistry Division of Mass Spectrometry TARGETS IN HETEROCYCLIC SYSTEMS Chemistry and Properties Volume 17 (2013) 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 © 2013 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 Volume 17 (2013) First edition 2014 ISBN 978-88-86208-75-8 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 2014 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. Steven V. Ley University of Palermo University of Cambridge Palermo, Italy Cambridge, UK Prof. Girolamo Cirrincione Prof. Pedro Merino University of Palermo University of Zaragoza Palermo, Italy Zaragoza, Spain Prof. Janine Cossy Prof. Renato Noto ESPCI University of Palermo Paris, France Palermo, Italy 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 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 17 (2013) keeps the international standard of TARGETS IN HETEROCYCLIC SYSTEMS – Chemistry and Properties (THS) series and contains eight chapters, covering the synthesis, reactivity, and activity (including medicinal) of different heterorings. Authors from Canada, France, Italy, Spain, and Ukraine are present in this book. As yet, THS Volumes 1-17 published 229 reviews by 646 authors from 30 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 1–16 please visit: http://www.soc.chim.it) Recent advances in pyrimidine derivatives as luminescent, photovoltaic 1 and non-linear optical materials Sylvain Achelle and Christine Baudequin 1. Introduction 2. Pyrimidines 2.1. Arylpyrimidines and arylethynylpyrimidines 2.2. Arylvinylpyrimidines and aryliminepyrimidines 2.3. Organometallic and coordinated pyrimidine derivatives 3. Quinazolines 4. Pyrrolo[2,3-d]pyrimidines 5. Other fused pyrimidines 6. Conclusions References A unified strategy for the synthesis of bridged indole alkaloids and their close analogues 35 M.-Lluïsa Bennasar 1. Introduction 2. Construction of the ervitsine ring system 3. First total synthesis of apparicine 3.1. Initial studies 3.2. Completion of the total synthesis 4. Synthesis of cleavamine-type indole alkaloids and their 5-nor derivatives 4.1. Construction of the 5-nor cleavamine skeleton 4.2. Total synthesis of cleavamines 5. Conclusion Acknowledgments References Recent advances in the synthesis of selected indolizidine and quinolizidine alkaloids 57 Sunil V. Pansare and Rakesh G. Thorat 1. Introduction 2. Scope and organization of the review 3. Synthetic strategies for selected indolizidine and quinolizidine alkaloids 3.1. Ring formation via nucleophilic displacement or addition reactions 3.1.1. Nitrogen-carbon cyclizations with preformed azacycles as starting materials 3.1.2. Nitrogen-carbon cyclizations with open chain precursors 3.1.3. Carbon-carbon cyclizations with preformed azacycles as starting materials I 3.1.4. Carbon-carbon cyclizations via azacyclic intermediates 3.2. Syntheses employing ring closing metathesis as a key transformation 3.3. Asymmetric cycloaddition-based strategies 3.4. Iminium ion-based approaches 3.5. Syntheses involving organocatalysis 4. Closing remarks Acknowledgments References Thiazolo[5,4-d]thiazole-based compounds: emerging targets in materials science, 87 organic electronics and photovoltaics Lorenzo Zani, Massimo Calamante, Alessandro Mordini and Gianna Reginato 1. Introduction 2. Synthesis, elaboration and characterization of thiazolo[5,4-d]thiazoles and related materials 2.1. Synthesis and functionalization of thiazolo[5,4-d]thiazoles 2.2. Thiazolothiazole-based polymers 2.3. Structural, photophysical and spectroscopic properties 3. Applications of thiazolo[5,4-d]thiazole-based materials 3.1. Biological activity 3.2. Preparation of metal complexes and crystal engineering 3.3. Non-linear optics and fluorescent sensors/emitters 3.4. Organic light-emitting diodes 3.5. Organic field-effect transistors 3.6. Organic and polymeric solar cells 3.7. Dye-sensitized solar cells 4. Conclusions Acknowledgments References Synthesis and photophysical properties of the green fluorescent 125 protein chromophore and analogues David Martínez-López and Diego Sampedro 1. Introduction 2. Synthesis of GFP chromophore analogues 2.1. Synthesis of oxazolones 2.2. Synthesis of imidazolinones 2.3. Synthesis of other derivatives 3. Photophysical properties of GFP and GFP derivatives 3.1. Absorption 3.1.1. Oxazolones II 3.1.2. Imidazolinones 3.2. Fluorescence 3.2.1. Oxazolones 3.2.2. Imidazolinones 3.3. Photoisomerisation 3.4. Photophysical properties of other derivatives 4. Applications 5. Conclusions Acknowledgments References Synthesis, chemical and biological properties of trifluoromethylated 147 pyrimidin-2-ones(thiones) and their fused analogues Veronika M. Shoba, Viktor M. Tkachuk, Volodymyr A. Sukach and Mykhailo V. Vovk 1. Introduction 2. Synthesis of trifluoromethylated pyrimidin-2-ones(thiones) 2.1. Biginelli reaction 2.2. [NCN]+[CCC] cyclization 2.3. [CCCN]+[CN] cyclization 2.4. [CNC]+[NCC] cyclization 3. Chemical properties of trifluoromethylated pyrimidin-2-ones(thiones) 3.1. Nucleophilic addition reactions 3.2. Photochemical reactions and processes involving free radicals 4. Biological properties of trifluoromethylated pyrimidin-2-ones(thiones) 5. Conclusions References Biocatalysis applied to the synthesis of valuable triazole-contaning derivatives 176 Aníbal Cuetos, Fabricio R. Bisogno and Iván Lavandera 1. Introduction 2. Biocatalytic approaches over triazole-containing derivatives 2.1. 1,2,3-Triazoles 2.1.1. Using hydrolases