New Methodologies and Techniques for a Sustainable Organic Chemistry PDF
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New Methodologies and Techniques for a Sustainable Organic Chemistry NATO Science Series A Series presenting the results of scientific meetings supported under the NATO Science Programme. The Series is published by IOS Press, Amsterdam, and Springer (formerly Kluwer Academic Publishers) in conjunction with the NATO Public Diplomacy Division. Sub-Series I. Life and Behavioural Sciences IOS Press II. Mathematics, Physics and Chemistry Springer (formerly Kluwer Academic Publishers) III. Computer and Systems Science IOS Press IV. Earth and Environmental Sciences Springer (formerly Kluwer Academic Publishers) The NATO Science Series continues the series of books published formerly as the NATO ASI Series. The NATO Science Programme offers support for collaboration in civil science between scientists of countries of the Euro-Atlantic Partnership Council. The types of scientifi c meeting generally supported are “Advanced Study Institutes” and “Advanced Research Workshops”, and the NATO Science Series collects together the results of these meetings. The meetings are co-organized by scientists from NATO countries and scientists from NATO’s Partner countries – countries of the CIS and Central and Eastern Europe. Advanced Study Institutes are high-level tutorial courses offering in-depth study of latest advances in a fi eld. Advanced Research Workshops are expert meetings aimed at critical assessment of a fi eld, and identifi cation of directions for future action. As a consequence of the restructuring of the NATO Science Programme in 1999, the NATO Science Series was re-organized to the Four Sub-series noted above. Please consult the following web sites for information on previous volumes published in the Series. http://www.nato.int/science http://www.springer.com http://www.iospress.nl Series II: Mathematics, Physics and Chemistry – Vol. 246 New Methodologies and Techniques for a Sustainable Organic Chemistry Edited by Alessandro Mordini Istituto di Chimica dei Composti Organometallici-CNR Firenze, Italy and Ferenc Faigl Research Group for Organic Chemical Technology H.A.S. Budapest University of Technology and Economics, Hungary Proceedings of the NATO Advanced Study Institute on New Methodologies and Techniques in Organic Chemistry: Sustainable Development in a Secure Environment Certosa di Pontignano, Siena, Italy 14-23 October 2005 A C.I.P. Catalogue record for this book is available from the Library of Congress. ISBN 978-1-4020-6792-1 (PB) ISBN 978-1-4020-6791-4 (HB) ISBN 978-1-4020-6793-8 (e-book) Published by Springer, P.O. Box 17, 3300 AA Dordrecht, The Netherlands. www.springer.com Printed on acid-free paper All Rights Reserved © 2008 Springer Science + Business Media B.V. No part of this work may be reproduced, stored in a retrieval system, or transmitted in any form-or by any means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written permission from the Publisher, with the exception of any material supplied s pecifically for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the work. PREFACE The NATO–ASI NeMeTOC was proposed and organized with the aim of upgrading the participants on the new methods and techniques in organic chemistry which are presently available to achieve the goal of production of chemicals in a secure environment. This is an ambitious task that we decided to undertake being absolutely convinced that it is necessary to give to the young generations of chemists all those new tools which will allow them to make their research work in the most efficient and, at the same time, least environmentally demanding way. It is indeed nowadays widely acknowledged that there is a growing need for more sustainable processes in the chemical industry, and organic chem- ists have to face such need finding new solutions to avoid, or minimize, waste in chemical processes and the use of toxic and/or hazardous substances, to reduce the energy required for carrying chemical transformations, to increase as much as possible efficiency and yields. All these targets seem very difficult to reach at present, but there are already some useful methods and techniques we can use to overcome these problems, at least partially. In this NATO – ASI, we have tried to deeply discuss on all these topics taking advantage of the experience of the most prominent scientists working in the field nowadays and pushing all participants to reflect upon, and eject ideas and own experiences into open debates on this topics and in spaces dedicated to the presentation of their own research activities (short and flash presenta- tions, poster sessions). During the intense ten days of activities, four main themes have been addressed in a deliberate potpourri fashion. (cid:127) New efficient and selective catalytic processes All the most important aspects of catalysis have been covered: the search for new chiral ligands, transition metals and catalysts, the application of catal- ysis in different reactions (Ojima, Echavarren) and particularly in industri- ally relevant processes (Cabri, Westerduin), the use of non-usual media such as water (Genet) or non-usual activation techniques such as microwaves, the choice of homogeneous or heterogeneous phase catalysis (Lipshutz), the most recent advances on organocatalysis (Barbas III). All these aspects have been also discussed in a “Panel discussion” entitled Why is asymmetric catalysis not being used more in industry? (moderator: Bolm) by all participants. (cid:127) Use of non-usual media or environmentally benign reagents The change from organic solvents or reagents to more benign ones reduces at the same time the impact on the environment and hazards. These v vi PREFACE important topics have been extensively developed in the school. A general description of the concepts associated with these aspects of organic synthesis has been first presented (Sheldon, Tundo) and then the most important items such as the use of water as a solvent (Genet), the technology involved in the use of supercritical fluids (Licence), the advantages of employing biphasic systems (Horvath) and solventless processes (Ricci), and the use of solid phase-supported reagents (Taddei) have been all fully developed. The top- ics have been also the subject of a “Panel discussion” entitled Non-conventional reagents and media (moderator: Sheldon). (cid:127) New selective and efficient synthetic methods New processes characterized by a high degree of efficiency (chemical yields), a reduced amount of required chemicals (high atom economy) and reduced waste of materials are essential in order to achieve the goal of a sustainable development coupled with an effective protection of the envi- ronment. These topics have been the subject of lectures which have covered several different aspects in the field of organometallic chemistry, separation technologies and “click chemistry” (Sharpless, Faigl, Mordini). In addition, the development of a new technology based on microreactors has been also illustrated (Wahl). (cid:127) New techniques based on alternative energy sources Important recent progresses have been made by the scientific community on the use of alternative energy sources characterized by high efficiency together with the use of milder and safer conditions. This has been deeply developed at the ASI in the course of lectures mainly dealing with the use of microwaves in organic synthesis (Kappe, Ricci, Lipshutz) and photo- irradiation (Albini), and has been also treated in a “Panel discussion” entitled Microwave effects (moderator: Kappe). The understanding of all the above-mentioned topics has been greatly improved by the exhibition of all the most updated technical equipments to perform such sustainable processes in a laboratory scale. Participants have had the opportunities to see and try all the newest microwave, parallel synthesis and programmable reactors, and the most efficient apparatus for fast and efficient separations and purifications. We do hope that this book which contains the contributions of most of the lecturers who participated the ASI will reflect all the aspects mentioned above providing a report on the current status of the art in diversified fields having in common the target of answering to virtually any question which may arise during the development of a new environmentally benign organic synthesis. All these intense and exciting activities have been carried out in a won- derful, secluded but very comfortable and cosy old monastery in the mar- PREFACE vii vellous countryside of Siena. Such a peaceful and enchanting surrounding has c ertainly helped in inspiring high-level scientific interactions while the delicious food and the wonderful wine have been the catalysts for creating a very nice and confidential atmosphere among all participants. People coming from more than twenty different countries have had the opportunity to dis- cuss and exchange different experiences, cultures and ideas in a relaxing and very friendly atmosphere. The long time spent together has been responsible for establishing new friendships and to allow interactions between lecturers and students. Evening spent together have shown either simply people talk- ing and discussing while drinking wine or even very young students and less young but equally enthusiastic lecturers dancing together. I think all those who have spent with us the ten days at Certosa di Pontignano would agree with us saying that it has been a wonderful, pleasant experience that we will remember for very long time. For this event we like to warmly thank many people, the lecturers for having given us outstanding and comprehensive lectures, the chairmen and the exhibitors for their availability and willingness in promoting discussions and most of all the participants who have attentively followed all the activities of the ASI making our tasks easy and pleasant. The success of the ASI is of course due to many people. We are really in debt with them and we wish to warmly thank them for having shared with us such a beautiful adventure. First of all Gianna Reginato who has been the real engine for moving everything. She has participated the whole preparation process with always perfect scientific and practical suggestions and she has then faced with us all the problems that inevitably rise when you organize such an event. Besides Gianna all the Florence group (Alice, Assunta, Barbara, Chiara, Daniela, Francesco, Gabriella, Lorenzo, Maria Pia, Massimo) deserves our best gratitude. They have not only helped taking care of transpor- tation of lecturers and students, projection of lectures, preparation of lecture notes, helping in all social events, but also with their enthusiasm they have catalyzed the establishment of a friendly and relaxing atmosphere among all people. Warm thanks are due also to the Congress Office of the University of Siena and particularly to Roberta Corsi who has organized almost everything concerning the practical aspects of the school and to the staff at Certosa di Pontignano who have been always very kind and helpful. The Organizing Committee (C. Bolm, J. P. Genet, B. Lipshutz, A. Ricci, M. Taddei) not only took part in establishing the scientific content of the school, but also took part in developing the scientific and the social activities at Certosa di Pontignano. They have chaired oral and flash communication sessions creating a very relaxing but also stimulating atmosphere among the students, they have promoted discussions during the panel sessions, and they viii PREFACE have been always available and very helpful. Maurizio Taddei deserves our special thanks as being also the local organizer, he has taken on his shoulder most of the practical and financial problems. Thanks are due to the Ministero della Ricerca Scientifica e Tecnologica for financial support, to the Società Chimica Italiana, Divisione di Chimica Organica, to the Consiglio Nazionale delle Ricerche and to Regione Toscana for their highly appreciated patronage. Last but not least we warmly thank NATO – Science for Peace and Security (SPS). They have first of all given us the opportunity to organize this beautiful event and they have been always very helpful and patient trying to answer always to our numerous and sometimes difficult questions and to solve all our problems. We are particularly grateful to Fausto Pedrazzini and Alison Trapp for their continuous assistance. CONTENTS Preface ........................................................................................................v Reactions In Non-Conventional Media For Sustainable Organic Synthesis ..............................................................1 Roger A. Sheldon Catalytic Asymmetric Synthesis With Novel Monodentate Phosphorus Ligands .................................................................................29 Bruno D Chapsal and Iwao Ojima New Cyclization and Cycloaddition Reactions in Organic Synthesis .................................................................................55 Wen-Hua Chiou and Iwao Ojima New Chiral Catalysts for C–C-bond Formations ......................................85 Carsten Bolm Intramolecular Reactions of Alkynes with Alkenes Catalyzed by Platinum and Gold ..............................................................99 Antonio M. Echavarren, Cristina Nevado, Cristina Nieto-Oberhuber, M. Paz Muñoz, and Salomé López Industrial Synthesis Design with Low Environmental Impact in the Pharma Industry ...........................................................................119 Walter Cabri New Efficient Catalytic Processes in Water: An Environmental Bening Solvent..........................................................131 Jean-Pierre Genet Homogeneous and Heterogeneous Catalysis Using Base Metals From Groups 10 And 11 .........................................................................155 Bruce H. Lipshutz An Introduction To Supercritical Fluids: From Bench Scale to Commercial Plant ...............................................................................171 Peter Licence and Martyn Poliakoff ix
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