《有机化学》课程教学资源（书籍文献）Topics in Current Chemistry, Carbohydrates in Sustainable Development II, A Mine for Functional Molecules and Materials, 2010

TOPICS IN CURRENT CHEMISTRY 295 Volume Editors A.P.Rauter.P.Vogel-Y.Queneau Carbohydrates in Sustainable Development ll A Mine for Functional Molecules and Materials ②Springer Urheberrechtlich geschutztes Material

Topics in Current Chemistry Recently Published and Forthcoming Volumes Carbohydrates in Sustainable Development II STM and AFM Studies on (Bio)molecular Volume Editors:Amelia P.Rauter, Systems:Unravelling the Nanoworld Samori,P Carbohvdrates in Sustainable Development I Volume Editors:Amilia P.Rauter. Amplification of Chirality aL29430i0esQucneau Functional Metal-Organic Frameworks:Gas Anthracycline Chemistry and Biology II Storage,Separation and Catalysis Mode of Action.Clinical Aspects and New Drug itor:Krohn.K. VL.283.2008 C-H Activation Volume Editors:Jin-Quan Yu,Zhangjie Shi Vol.292.2010 Anthracycline Chemistry and BiologyI Volume Editor:Krohn.K Vol.291.2010 Vol.282.2008 lonic Liquids Photochemist Volume Editors Balzani,V.Campagna,S. Orbitals in Chemistrv VoL281.200 Volume Editor:Satoshi Inagaki Vol.289,2009 sion Volume Editors:Baizani.V.Campagna.S. Stefan Oscarson Vol.280.20 Vol288.2009 Metal Catalyzed Reductive C-C Bond Formation Templates in Chemistry III A Departure from Preformed Organometallic Vol.287.2009 e Editor:Krische,M.J. Vol279.2007 Tubulin-Binding Agents Synthetic,Structural and Mechanistic Insights Combinatorial Chemistry on Solid Supports

Topics in Current Chemistry Recently Published and Forthcoming Volumes Carbohydrates in Sustainable Development II Volume Editors: Ame´lia P. Rauter, Pierre Vogel, Yves Queneau Vol. 295, 2010 Carbohydrates in Sustainable Development I Volume Editors: Ame´lia P. Rauter, Pierre Vogel, Yves Queneau Vol. 294, 2010 Functional Metal-Organic Frameworks: Gas Storage, Separation and Catalysis Volume Editor: Martin Schro¨der Vol. 293, 2010 C-H Activation Volume Editors: Jin-Quan Yu, Zhangjie Shi Vol. 292, 2010 Asymmetric Organocatalysis Volume Editor: Benjamin List Vol. 291, 2010 Ionic Liquids Volume Editor: Barbara Kirchner Vol. 290, 2010 Orbitals in Chemistry Volume Editor: Satoshi Inagaki Vol. 289, 2009 Glycoscience and Microbial Adhesion Volume Editors: Thisbe K. Lindhorst, Stefan Oscarson Vol. 288, 2009 Templates in Chemistry III Volume Editors: Broekmann, P., Do¨tz, K.-H., Schalley, C.A. Vol. 287, 2009 Tubulin-Binding Agents: Synthetic, Structural and Mechanistic Insights Volume Editor: Carlomagno, T. Vol. 286, 2009 STM and AFM Studies on (Bio)molecular Systems: Unravelling the Nanoworld Volume Editor: Samorı`, P. Vol. 285, 2008 Amplification of Chirality Volume Editor: Soai, K. Vol. 284, 2008 Anthracycline Chemistry and Biology II Mode of Action, Clinical Aspects and New Drugs Volume Editor: Krohn, K. Vol. 283, 2008 Anthracycline Chemistry and Biology I Biological Occurence and Biosynthesis, Synthesis and Chemistry Volume Editor: Krohn, K. Vol. 282, 2008 Photochemistry and Photophysics of Coordination Compounds II Volume Editors: Balzani, V., Campagna, S. Vol. 281, 2007 Photochemistry and Photophysics of Coordination Compounds I Volume Editors: Balzani, V., Campagna, S. Vol. 280, 2007 Metal Catalyzed Reductive C–C Bond Formation A Departure from Preformed Organometallic Reagents Volume Editor: Krische, M.J. Vol. 279, 2007 Combinatorial Chemistry on Solid Supports Volume Editor: Bra¨se, S. Vol. 278, 2007

Universidade de Lisboa rpemrnd Fac.Cien ias Asymmetric Synthesis(LGSA) Depto.Qu CH of Technology (EPFL) Ed.C8 5 Piso Switzerland pierre.vogel@epfl.ch aprauter@fc.uL.pt Prof.Dr.Yves Queneau de Chimie et Biochimie Laboratoire de Chimie Organique leurbann yves.queneau@insa.Iyon.fr ISSN0340-1022 e-ISSN1436-5049 e-ISBN978-3-642-15161-3 echt London New York Library of Congress Control Number:2010935852 rved whether the whole or part of the material is ber 9 protective laws and regulations and therefore free for general use. Cover design:WMXDesign GmbH,Heidelberg.Germany Printed on acid-free pape Springer is part of Springer Science+Business Media(www.springer.com

Editors Prof. Dr. Ame´lia P. Rauter Universidade de Lisboa Fac. Cieˆncias Depto. Quı´mica e Bioquı´mica Centro de Quı´mica e Bioquı´mica Ed. C8 5 Piso Campo Grande 1749-016 Lisboa Portugal aprauter@fc.ul.pt Prof. Dr. Yves Queneau Institut de Chimie et Biochimie Mole´culaires et Supramole´culaires UMR 5246 CNRS – Universite´ de Lyon Laboratoire de Chimie Organique INSA Lyon, Baˆt. J. Verne 69621 Villeurbanne France yves.queneau@insa.lyon.fr Prof. Dr. Pierre Vogel Laboratory of Glycochemistry and Asymmetric Synthesis (LGSA) Swiss Institute of Technology (EPFL) CH 1015 Lausanne Switzerland pierre.vogel@epfl.ch ISSN 0340-1022 e-ISSN 1436-5049 ISBN 978-3-642-15160-6 e-ISBN 978-3-642-15161-3 DOI 10.1007/978-3-642-15161-3 Springer Heidelberg Dordrecht London New York Library of Congress Control Number: 2010935852 # Springer-Verlag Berlin Heidelberg 2010 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer. Violations are liable to prosecution under the German Copyright Law. The use of general descriptive names, 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. Cover design: WMXDesign GmbH, Heidelberg, Germany Printed on acid-free paper Springer is part of Springer Science+Business Media (www.springer.com)

Volume Editor Prof.Dr.Amelia P.Rauter Prof.Dr.Pierre Vogel Universidade de Lisboa Laboratory of Glycochemistry and Fac.Ciencias Asymmetric Synthesis(LGSA) Depto.Quimicae Bioquimica Swiss Institute of Technology (EPFL) 1749-016 Lisboa pierre.vogel@epf.ch Prof.Dr.Yves Queneau Institut de Chimie et Biochimie Moleculaires et Supramoleculaires UMR 5246 CNRS-Universite de Lyon Laboratoire de Chimie Organique INSA Lyon,Bat.J.Verne France yves.queneau@insa.lyon.fr Editorial Board Prof.Dr.Armin de Meijere Prof.Dr.Jean-Marie Lehn Institut fur organische Chemie ISIS 8.allee Gaspard Monge BP70028 37077 Gottingen,Germany 67083 Strasbourg Cedex.France ameijerl@uni-goettingen.de lehn@isis.u-strasbgfr Prof.Dr.Kendall N.Houk Prof.Dr.Steven V.Ley University of Califomia University Chemical Laboratory Department of Chemistry and Biochemistry Lensfield Road 405 Hilgard Avenue Cambridge CB2 1EW Los Angeles.CA 90024-1589.USA Great Britain houk@chem ucla.edu Svl1000@cus.cam.ac uk Prof.Dr.Christopher A.Hunter Prof.Dr.Massimo Olivucci Department of Chemistry Universita di siena University of Sheffield Dipartimento di Chimica Sheffield S3 7HF.United Kingdom hunter(@sheffeld.ac.uk 100S ena,Italy olivucci@unisi.i

Volume Editor Prof. Dr. Ame´lia P. Rauter Universidade de Lisboa Fac. Cieˆncias Depto. Quı´mica e Bioquı´mica Centro de Quı´mica e Bioquı´mica Ed. C8 5 Piso Campo Grande 1749-016 Lisboa Portugal aprauter@fc.ul.pt Prof. Dr. Yves Queneau Institut de Chimie et Biochimie Mole´culaires et Supramole´culaires UMR 5246 CNRS – Universite´ de Lyon Laboratoire de Chimie Organique INSA Lyon, Baˆt. J. Verne 69621 Villeurbanne France yves.queneau@insa.lyon.fr Prof. Dr. Pierre Vogel Laboratory of Glycochemistry and Asymmetric Synthesis (LGSA) Swiss Institute of Technology (EPFL) CH 1015 Lausanne Switzerland pierre.vogel@epfl.ch Editorial Board Prof. Dr. Armin de Meijere Institut fu¨r Organische Chemie der Georg-August-Universita¨t Tammanstr. 2 37077 Go¨ttingen, Germany ameijer1@uni-goettingen.de Prof. Dr. Kendall N. Houk University of California Department of Chemistry and Biochemistry 405 Hilgard Avenue Los Angeles, CA 90024-1589, USA houk@chem.ucla.edu Prof. Dr. Christopher A. Hunter Department of Chemistry University of Sheffield Sheffield S3 7HF, United Kingdom c.hunter@sheffield.ac.uk Prof. Dr. Jean-Marie Lehn ISIS 8, alle´e Gaspard Monge BP 70028 67083 Strasbourg Cedex, France lehn@isis.u-strasbg.fr Prof. Dr. Steven V. Ley University Chemical Laboratory Lensfield Road Cambridge CB2 1EW Great Britain Svl1000@cus.cam.ac.uk Prof. Dr. Massimo Olivucci Universita` di Siena Dipartimento di Chimica Via A De Gasperi 2 53100 Siena, Italy olivucci@unisi.it

i Editorial Board Prof.Dr.Horst Kessler Prof.Dr.Joachim Thiem Institut fur Organische Chemie TU Munchen r-Kinas -Platz 6 86747 Garching.Germany 20146Ha kessler@ch.tum.de Prof.Dr.Barry M.Trost Prof.Dr.Henry Wong Department of Chemistry The Chinese University of Hong Kong Stanford University Stanford,CA94305-5080.USA Department of Chemistrv bmtrostleland stanford edu Shatin.New Territories hncwong@cuhk.edu.hk Prof.Dr.Margherita Venturi Dipartimento di Chimica Prof.Dr.Hisashi Yamamoto Universita di Bologna Arthur Holly Compton Distinguished via Selmi 2 Professor 40126 Bologna.Italy Department of Chemistry margherita.venturi@unibo.it The University of Chicage 5735 South Ellis Avenue Prof.Dr.Pierre Vogel Chicago,IL 0637 Laboratory of Glycochemistry USA 02-505 and Asymmetric Synthesis EPFL-Ecole polytechnique federale yamamoto@uchicago.edu 1015La p/.ch erland pierre.vog

Prof. Dr. Horst Kessler Institut fu¨r Organische Chemie TU Mu¨nchen Lichtenbergstraße 4 86747 Garching, Germany kessler@ch.tum.de Prof. Dr. Barry M. Trost Department of Chemistry Stanford University Stanford, CA 94305-5080, USA bmtrost@leland.stanford.edu Prof. Dr. Margherita Venturi Dipartimento di Chimica Universita` di Bologna via Selmi 2 40126 Bologna, Italy margherita.venturi@unibo.it Prof. Dr. Pierre Vogel Laboratory of Glycochemistry and Asymmetric Synthesis EPFL – Ecole polytechnique fe´derale de Lausanne EPFL SB ISIC LGSA BCH 5307 (Bat.BCH) 1015 Lausanne, Switzerland pierre.vogel@epfl.ch Prof. Dr. Joachim Thiem Institut fu¨r Organische Chemie Universita¨t Hamburg Martin-Luther-King-Platz 6 20146 Hamburg, Germany thiem@chemie.uni-hamburg.de Prof. Dr. Henry Wong The Chinese University of Hong Kong University Science Centre Department of Chemistry Shatin, New Territories hncwong@cuhk.edu.hk Prof. Dr. Hisashi Yamamoto Arthur Holly Compton Distinguished Professor Department of Chemistry The University of Chicago 5735 South Ellis Avenue Chicago, IL 60637 773-702-5059 USA yamamoto@uchicago.edu vi Editorial Board

Topics in Current Chemistry Also Available Electronically Topics in Current Chemistry is included in Springer's eBook package Chemistry and Materials Science.If a library does not opt for the whole package the book series ught on a subscription basis. Also,all back volumes are available al For all customers who have a standing order to the print version of Topics in Current Chemistry,we offer the electronic version via SpringerLink free of charge. If you do not have access,you can still view the table of contents of each volume and the abstract of each article by going to the SpringerLink homepage,clicking on "Chemistry and Materials Science,"under Subject Collection,then "Book Series,"under Content Type and finally by selecting Topics in Current Chemistry. You will find information about the cope Instructions for Authors -Sample Contribution at springer.com using the search function by typing in Topics in Current Chemistry. Color figures are published in full color in the electronic version on SpringerLink. Aims and Scope The series Topics in Current Chemistry presents critical reviews of the present and future trends in modem chemical research.The scope includes all areas of chemical science,including the interfaces with related disciplines such as biology,medicine, and materials science. The objective of each thematic volume is to give the non-specialist reader.whether at the un sity or in i ensive overvie of an area where new insights of interest to a larger scientific audience are emerging

Topics in Current Chemistry Also Available Electronically Topics in Current Chemistry is included in Springer’s eBook package Chemistry and Materials Science. If a library does not opt for the whole package the book series may be bought on a subscription basis. Also, all back volumes are available electronically. For all customers who have a standing order to the print version of Topics in Current Chemistry, we offer the electronic version via SpringerLink free of charge. If you do not have access, you can still view the table of contents of each volume and the abstract of each article by going to the SpringerLink homepage, clicking on “Chemistry and Materials Science,” under Subject Collection, then “Book Series,” under Content Type and finally by selecting Topics in Current Chemistry. You will find information about the – Editorial Board – Aims and Scope – Instructions for Authors – Sample Contribution at springer.com using the search function by typing in Topics in Current Chemistry. Color figures are published in full color in the electronic version on SpringerLink. Aims and Scope The series Topics in Current Chemistry presents critical reviews of the present and future trends in modern chemical research. The scope includes all areas of chemical science, including the interfaces with related disciplines such as biology, medicine, and materials science. The objective of each thematic volume is to give the non-specialist reader, whether at the university or in industry, a comprehensive overview of an area where new insights of interest to a larger scientific audience are emerging. vii

Topics in Current Chemistry Also Available Electronically Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole.The most significant developments of the last 5-10 years are presented,using selected examples to illus trate the principles discussed.A description of the laboratory procedures involved is often useful to the reader.The coverage is not exhaustive in data,but rather conceptual,concentrating on the methodological thinking that will allow the non- specialist reader to understand the information presented. Discussion of p ossible futur rch directions in the area is welco ama之 Review articles for the vited b n reference cited as a joumal Impact Factor 2009:4.291:Section"Chemistry,Multidisciplinary":Rank 20of 138

Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5–10 years are presented, using selected examples to illus￾trate the principles discussed. A description of the laboratory procedures involved is often useful to the reader. The coverage is not exhaustive in data, but rather conceptual, concentrating on the methodological thinking that will allow the non￾specialist reader to understand the information presented. Discussion of possible future research directions in the area is welcome. Review articles for the individual volumes are invited by the volume editors. In references Topics in Current Chemistry is abbreviated Top Curr Chem and is cited as a journal. Impact Factor 2009: 4.291; Section “Chemistry, Multidisciplinary”: Rank 20 of 138 viii Topics in Current Chemistry Also Available Electronically

Preface sts are well aware that it is urgent to develop sustainable processes and to chemical en s that e the effic env onmenta nt cla natural compound ormations into a variety of industrial products based on their multifunctionality and stereochemical diversity.Chemistry using carbohydrates,unprotected or functionalized,continues to be a challenging field of investigation.Because of the complexity of sugars,the issues of regio-and stereoselectivity are among the most difficult to monitor.The low solubility of carbohydrates in several solvents is often a handicap,but some times an op tunity.In this volume,entitled "Carbohydrates and Sustainable t,Part 2-A Mine for Funct and Materials,” vera aspects of the che of ca en pro ses in their conversion into ind ustrial products for cosmetics are ill ustrated b ward transformations using clean solvents and nontoxic catalysis.Othe r contribu tions focus on multistep sequences toward elaborated products,starting from these inexpensive and readily available materials.A survey on the state of the art of ionic liquids derived from sugars is also presented.Synthetic polymers can now be made based on carbohydrate building blocks.The potential of these biocompatible and biodegradable macromolecular materials to replace the polluting petrol um-based rs is also discussed Biod version ard rather c olecules of cal relev an e ha made a akth In all cha pters. and polysacchandes are indeedmine for functional moleculesn This volume,together with the first volume entitled"Carbohydrates and Sus. tainable Development,Part 1-Renewable Resources for Chemistry and Biotech- nology,"demonstrates that a variety of industrial products can be accessed using renewable and low-cost biomass.Both volumes are based on selected papers presented at"Carbohydrates as Organic Raw Materials V-Building a Sustainable Future"(CORM V),held in Lisbon in January 2009.The conferer as chaired by Amelia Pilar Rauter (University of Lisboa and Yves Ou ene au (Unive sity of Lyon.INSA Lyon),in collaboration with Frieder W.Lichtenthaler (Technische ix

Preface Chemists are well aware that it is urgent to develop sustainable processes and to design new chemical entities that improve the efficiency and the environmental impact of chemical transformations. Carbohydrates are the most abundant class of natural compounds: they offer unique structures for multiple transformations into a variety of industrial products based on their multifunctionality and stereochemical diversity. Chemistry using carbohydrates, unprotected or functionalized, continues to be a challenging field of investigation. Because of the complexity of sugars, the issues of regio- and stereoselectivity are among the most difficult to monitor. The low solubility of carbohydrates in several solvents is often a handicap, but some￾times an opportunity. In this volume, entitled “Carbohydrates and Sustainable Development, Part 2 – A Mine for Functional Molecules and Materials,” several aspects of the chemistry of carbohydrates are discussed. Green processes involving their conversion into industrial products for cosmetics are illustrated by straightfor￾ward transformations using clean solvents and nontoxic catalysis. Other contribu￾tions focus on multistep sequences toward elaborated products, starting from these inexpensive and readily available materials. A survey on the state of the art of ionic liquids derived from sugars is also presented. Synthetic polymers can now be made based on carbohydrate building blocks. The potential of these biocompatible and biodegradable macromolecular materials to replace the polluting petroleum-based polymers is also discussed. Bioconversions toward rather complex molecules of biological relevance have made a breakthrough. In all chapters, evidence is given that sugars and polysaccharides are indeed “a mine for functional molecules and materials.” This volume, together with the first volume entitled “Carbohydrates and Sus￾tainable Development, Part 1 – Renewable Resources for Chemistry and Biotech￾nology,” demonstrates that a variety of industrial products can be accessed using renewable and low-cost biomass. Both volumes are based on selected papers presented at “Carbohydrates as Organic Raw Materials V – Building a Sustainable Future” (CORM V), held in Lisbon in January 2009. The conference was chaired by Ame´lia Pilar Rauter (University of Lisboa) and Yves Queneau (University of Lyon, INSA Lyon), in collaboration with Frieder W. Lichtenthaler (Technische ix

Preface Universitit Darmstadt)as Honorary Chairman.The CORM meetings were started by Lichtenthaler in 1990.Both volumes highlight the importance of carbohydrates for sustainable processes as abundant,renewable,and low-cost materials and show how sugars contribute significantly to the indispensable new processes for tomorrow's chemistry.With the chemical and biochemical transformations of readily available carbohydrates,we are on the way toward a more sustainable future. Lisbon and Lyon,July 2010 Amelia P.Rauter,University of Lisbor Yves Queneau,University of Lyon

Universita¨t Darmstadt) as Honorary Chairman. The CORM meetings were started by Lichtenthaler in 1990. Both volumes highlight the importance of carbohydrates for sustainable processes as abundant, renewable, and low-cost materials and show how sugars contribute significantly to the indispensable new processes for tomorrow’s chemistry. With the chemical and biochemical transformations of readily available carbohydrates, we are on the way toward a more sustainable future. Lisbon and Lyon, July 2010 Ame´lia P. Rauter, University of Lisbon Yves Queneau, University of Lyon x Preface

Contents Knoevenagel Reaction of Unprotected Sugars. Marie-Christine Scherrmann Carbohydrate-Based Lactones:Synthesis and Applications19 Nuno M. Kavier.Amelia P.Rauter,and Yves Queneau Heterogeneously-Catalyzed Conversion of Carbohydrates................63 Karine De Oliveira Vigier and Frangois Jerome Palladium-Catalyzed Telomerization of Butadiene with Polyols: From Mono to Polysaccharides... .93 Sandrine Bouquillon.Jacques Muzart,Catherine Pinel,and Franck Rataboul Enzymatic Processing of Bioactive Glycosides from Natural Sources...121 Lenka Weignerova and Vladimir Kren Synthetic Poly s from Readily Available Monosaccharides 147 J.A.Galbis and M.G.Garcia-Martin Synthesis and Applications of Ionic Liquids Derived from N tural Suga 177 Cinzia Chiappe,Alberto Marra,and Andrea Mele Index 197 xi

Contents Knoevenagel Reaction of Unprotected Sugars ............................... 1 Marie-Christine Scherrmann Carbohydrate-Based Lactones: Synthesis and Applications . . . . . . . . . . . . . . . 19 Nuno M. Xavier, Ame´lia P. Rauter, and Yves Queneau Heterogeneously-Catalyzed Conversion of Carbohydrates . . . . . . . . . . . . . . . . 63 Karine De Oliveira Vigier and Franc¸ois Je´roˆme Palladium-Catalyzed Telomerization of Butadiene with Polyols: From Mono to Polysaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93 Sandrine Bouquillon, Jacques Muzart, Catherine Pinel, and Franck Rataboul Enzymatic Processing of Bioactive Glycosides from Natural Sources . . . 121 Lenka Weignerova´ and Vladimı´r Krˇen Synthetic Polymers from Readily Available Monosaccharides . . . . . . . . . . . 147 J.A. Galbis and M.G. Garcı´a-Martı´n Synthesis and Applications of Ionic Liquids Derived from Natural Sugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177 Cinzia Chiappe, Alberto Marra, and Andrea Mele Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197 xi