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Domino and Intramolecular Rearrangement Reactions as Advanced Synthetic Methods in GlycoscienceEdited by
Zbigniew J. WitczakRoman Bielski
With a Foreword by Professor Samuel F. Danishefsky
DOMINO ANDINTRAMOLECULARREARRANGEMENTREACTIONS AS ADVANCEDSYNTHETIC METHODS INGLYCOSCIENCE
DOMINO ANDINTRAMOLECULARREARRANGEMENTREACTIONS AS ADVANCEDSYNTHETIC METHODS INGLYCOSCIENCE
Edited by
ZBIGNIEW J. WITCZAKROMAN BIELSKI
Copyright © 2016 by John Wiley & Sons, Inc. All rights reserved.
Published by John Wiley & Sons, Inc., Hoboken, New Jersey.Published simultaneously in Canada.
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Library of Congress Cataloging-in-Publication Data:
Names: Witczak, Zbigniew J., 1947– , editor. | Bielski, Roman, 1946– , editor.Title: Domino and intramolecular rearrangement reactions as advanced synthetic methods in
glycoscience / edited by Zbigniew J. Witczak, Roman Bielski.Description: Hoboken, New Jersey : John Wiley & Sons Inc., [2016] | Includes bibliographical
references.Identifiers: LCCN 2015039879 | ISBN 9781119044208 (cloth)Subjects: | MESH: Glycosides–chemistry–Laboratory Manuals. | Chemistry Techniques,
Synthetic–methods–Laboratory Manuals.Classification: LCC QP702.G577 | NLM QU 25 | DDC 572/.567–dc23 LC record available at
http://lccn.loc.gov/2015039879
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
We dedicate this book to our wives, Wanda and Barbara.
CONTENTS
Foreword xiii
Preface xv
Acknowledgments xix
List of Contributors xxi
Abbreviations xxv
1 Introduction to Asymmetric Domino Reactions 1Helene Pellissier
1.1 Introduction, 11.2 Asymmetric Domino Reactions using Chiral Carbohydrate Derivatives, 3
1.2.1 Stereocontrolled Domino Reactions of ChiralCarbohydrate Derivatives, 3
1.2.2 Enantioselective Domino Reactions Catalyzed by ChiralCarbohydrate Derivatives, 8
1.3 Conclusions, 12References, 13
2 Organocatalyzed Cascade Reaction in Carbohydrate Chemistry 16Benjamin Voigt and Rainer Mahrwald
2.1 Introduction, 162.2 C-Glycosides, 172.3 Amine-Catalyzed Knoevenagel-Additions, 20
vii
viii CONTENTS
2.4 Multicomponent Reactions, 322.5 Amine-Catalyzed Cascade Reactions of Ketoses with
1,3-Dicarbonyl Compounds, 402.6 Conclusions, 44References, 44
3 Reductive Ring-Opening in Domino Reactions of Carbohydrates 49Raquel G. Soengas, Sara M. Tome, and Artur M. S. Silva
3.1 Introduction, 493.2 Bernet–Vasella Reaction, 50
3.2.1 Domino Reductive Fragmentation/Reductive Amination, 513.2.2 Domino Reductive Fragmentation/Barbier-Type Allylation, 523.2.3 Domino Reductive Fragmentation/Barbier-Type
Propargylation, 573.2.4 Domino Reductive Fragmentation/Vinylation, 593.2.5 Domino Reductive Fragmentation/Alkylation, 603.2.6 Domino Reductive Fragmentation/Olefination, 613.2.7 Domino Reductive Fragmentation/Nitromethylation, 62
3.3 Reductive Ring Contraction, 643.3.1 Ring Opening/Ketyl-Olefin Annulation, 653.3.2 Ring Opening/Intramolecular Carbonyl Alkylation, 69
3.4 Conclusions, 73References, 73
4 Domino Reactions Toward Carbohydrate Frameworks forApplications Across Biology and Medicine 76Vasco Cachatra and Amelia P. Rauter
4.1 Introduction, 764.2 Domino Reactions Toward Butenolides Fused to Six-Membered
Ring Sugars and Thio Sugars, 774.3 Exploratory Chemistry for Amino Sugars’ Domino Reactions, 804.4 Domino Reactions Toward Sugar Ring Contraction, 84
4.4.1 Pyrano–Furano Ring Contraction, 844.4.2 Ring Contraction of Furans to Oxetanes, 87
4.5 Macrocyclic Bislactone Synthesis via Domino Reaction, 914.6 Sugar Deoxygenation by Domino Reaction, 924.7 Conclusions, 94References, 94
5 Multistep Transformations of BIS-Thioenol Ether-ContainingChiral Building Blocks: New Avenues in Glycochemistry 97Daniele D’Alonzo, Giovanni Palumbo, and Annalisa Guaragna
5.1 Introduction, 97
CONTENTS ix
5.2 (5,6-Dihydro-1,4-dithiin-2-yl)Methanol: Not Simply aHomologating Agent, 98
5.3 Sulfur-Assisted Multistep Processes and Their Use in the De NovoSynthesis of Glycostructures, 1015.3.1 Three Steps in One Process: Double Approach to 4-Deoxy
l-(and d-)-Hexoses, 1015.3.2 Five Steps in One Process: The Domino Way to l-Hexoses
(and Their Derivatives), 1025.3.3 Up to Six Steps in One Process: 4′-Substituted Nucleoside
Synthesis, 1055.3.4 Eight Steps in One Process: Beyond Achmatowicz
Rearrangement, 1095.4 Concluding Remarks, 1115.5 Acknowledgments, 111References, 111
6 Thio-Click and Domino Approach to Carbohydrate Heterocycles 114Zbigniew J. Witczak and Roman Bielski
6.1 Introduction, 1146.2 Classification and Reaction Mechanism, 1146.3 Conclusions, 119References, 120
7 Convertible Isocyanides: Application in Small Molecule Synthesis,Carbohydrate Synthesis, and Drug Discovery 121Soumava Santra, Tonja Andreana, Jean-Paul Bourgault, and Peter R. Andreana
7.1 Introduction, 1217.2 Convertible Isocyanides, 125
7.2.1 CIC Employed in the Ugi Reaction, 1257.2.2 Resin-Bound CICs, 1677.2.3 CIC Employed in the Ugi–Smile Reaction, 1727.2.4 CIC Employed in the Joullie–Ugi Reaction, 1727.2.5 CIC Employed in the Passerini Reaction, 1757.2.6 CIC Employed in the Groebke–Blackburn–Bienayme
Reaction, 1787.2.7 CIC Employed in the Diels–Alder Reaction, 1827.2.8 Monosaccharide Isocyanides Employed in the Ugi and
Passerini Reaction, 1837.2.9 Methyl isocyanide in the Preparation of the Hydroxy DKP
Thaxtomin A, 1867.3 Conclusions, 187References, 187
x CONTENTS
8 Adding Additional Rings to the Carbohydrate Core: Access via(SPIRO) Annulation Domino Processes 195Daniel B. Werz
8.1 Introduction, 1958.2 Spiroketals via a Domino Oxidation/Rearrangement Sequence, 1968.3 Chromans and Isochromans via Domino Carbopalladation/
Carbopalladation/Cyclization Sequence, 200References, 208
9 Introduction to Rearrangement Reactions in CarbohydrateChemistry 209Zbigniew J. Witczak and Roman Bielski
9.1 Introduction, 2099.2 Classification, 2109.3 Chapman Rearrangement, 2119.4 Hofmann Rearrangement, 2119.5 Cope Rearrangement, 2119.6 Ferrier Rearrangement, 2129.7 Claisen Rearrangement, 2139.8 Overman Rearrangement, 2149.9 Baeyer–Villiger Rearrangement, 2159.10 Ring Contraction, 2159.11 Conclusions, 216References, 217
10 Rearrangement of a Carbohydrate Backbone Discovered“En Route” to Higher-Carbon Sugars 219Sławomir Jarosz, Anna Osuch-Kwiatkowska, Agnieszka Gajewska,and Maciej Cieplak
10.1 Introduction, 21910.2 Rearrangements Without Changing the Sugar Skeleton, 22010.3 Rearrangements Connected with the Change of Sugar Unit(s), 22110.4 Rearrangements Changing the Structure of a Sugar Skeleton, 22410.5 Rearrangement of the Sugar Skeleton Discovered En Route to
Higher-Carbon Sugars, 22610.5.1 Synthesis of Higher-Carbon Sugars by the Wittig-Type
Methodology, 22610.5.2 The Acetylene/Vinyltin Methodology in the Synthesis of
HCS, 22710.5.3 The Allyltin Methodology in the Synthesis of HCS, 22710.5.4 Rearrangement of the Structure of HCS, 23010.5.5 Synthesis of Polyhydroxylated Carbocyclic Derivatives
with Large Rings, 235
CONTENTS xi
10.6 Conclusions, 237Acknowledgments, 237References, 237
11 Novel Levoglucosenone Derivatives 240Roman Bielski and Zbigniew J. Witczak
11.1 Introduction, 24011.2 Additions to the Double Bond of the Enone System Leading to
the Formation of New Rings, 24111.3 Reductions of the Carbonyl Group Followed by Various Reactions
of the Formed Alcohol, 24111.4 Functionalization of the Carbonyl Group by Forming
Carbon-Nitrogen Double Bonds (Oximes, Enamines, Hydrazines), 24211.5 Additions (But Not Cycloadditions) (Particularly Michael
Additions) to the Double Bond of the Enone, 24311.6 Enzymatic Reactions of Levoglucosenone, 24411.7 High-Tonnage Products from Levoglucosenone, 244
11.7.1 Overman and Allylic Xanthate Rearrangement, 24511.8 Conclusions, 246References, 247
12 The Preparation and Reactions of 3,6-Anhydro-d-Glycals 248Vikram Basava, Emi Hanawa, and Cecilia H. Marzabadi
12.1 Introduction, 24812.2 Preparation of 3,6-Anhydro-d-Glucal Under Reductive Conditions, 25012.3 Addition Reactions of 3,6-Anhydro-d-Glucal, 25112.4 Preparation of 6-O-Tosyl-d-Galactal and Reduction with Lithium
Aluminum Hydride, 25212.5 Conclusions, 254References, 254
13 Ring Expansion Methodologies of Pyranosides to Septanosides andStructures of Septanosides 256Supriya Dey, N. Vijaya Ganesh, and N. Jayaraman
13.1 Introduction, 25613.2 Synthesis of Septanosides, 258
13.2.1 Synthesis of Septanosides via Hemiacetal Formation, 25813.2.2 Knoevenagel Condensation, 26013.2.3 Baeyer–Villiger Oxidation of Cyclohexanone Derivatives, 26013.2.4 Electrophile-Induced Cyclization, 26013.2.5 Metal-Catalyzed Cyclization, 26113.2.6 Nicolas–Ferrier Rearrangements, 26213.2.7 Ring Opening of Carbohydrate-Derived Cyclopropanes, 263
xii CONTENTS
13.2.8 Ring Opening of Glycal-Derived 1,2-Cyclopropane, 26313.2.9 Ring Opening of Oxyglycal Derived 1,2-Cyclopropane, 265
13.2.10 Functionalization of Oxepines, 26813.3 Structure and Conformation of Septanosides, 269
13.3.1 Solid-State Structures and Conformations, 27013.3.2 Solution-Phase Conformations, 273
13.4 Conclusions, 275Acknowledgments, 276References, 276
14 Rearrangements in Carbohydrate Templates to the Way toPeptide-Scaffold Hybrids and Functionalized Heterocycles 279Bernardo Herradon, Irene de Miguel, and Enrique Mann
14.1 Introduction, 27914.2 Synthesis of the Chiral Building Blocks: Applications of the
Claisen–Johnson and Overman Rearrangements, 28014.3 Peptide–Scaffold Hybrids, 28214.4 Sequential Reactions for the Synthesis of Polyannular Heterocycles, 28414.5 The First Total Synthesis of Amphorogynine C, 284Acknowledgments, 293References, 293
15 Palladium- and Nickel-Catalyzed Stereoselective Synthesis ofGlycosyl Trichloroacetamides and Their Conversion to 𝛂- and𝛃-Urea Glycosides 297Nathaniel H. Park, Eric T. Sletten, Matthew J. McKay, and Hien M. Nguyen
15.1 Introduction, 29715.2 Development of the Palladium(II)-Catalyzed Glycal
Trichloroacetimidate Rearrangement, 30015.3 Stereoselective Synthesis of Glycosyl Ureas from Glycal
Trichloroacetimidates, 30715.4 Development of the Stereoselective Nickel-Catalyzed
Transformation of Glycosyl Trichloroacetimidates toTrichloroacetamides, 310
15.5 Transformation of Glycosyl Trichloroacetimidates into α- andβ-Urea Glycosides, 317
15.6 Mechanistic Studies on the Nickel-Catalyzed Transformation ofGlycosyl Trichloracetimidates, 317
15.7 Conclusions, 323References, 323
Index 325
FOREWORD
The development of novel methods for coupling molecules in the area of carbohy-drate chemistry provides access to complex oligosaccharides, glycopeptides, and evenglycoproteins of modest size, using synthetic methods. Attaching small moleculessuch as mono- or oligosaccharides to other carbohydrates, amino acids (or proteins),and other natural products is a challenging and important target in today’s glyco-sciences. Another challenging task is that of a carefully designed modification ofmonosaccharides before introducing them into a larger structure.
Both of these capabilities require chemistry that must be performed with a highlevel of regio- and stereocontrol. In recent years, several novel strategies enablingthese delicate manipulations have been introduced. One of these takes advantage ofvarious rearrangement reactions and another utilizes domino reactions. Both pro-cesses offer substantial atom economy and hopefully stereo- and regiocontrol. Thecombination of domino/cascade/rearrangement reactions has become a very powerfultool for constructing complex structures in enantiomerically pure forms. The method-ology is also very productive in the synthesis of many targets in which a well-definedsteric outcome at specific positions is desired. The Editors did well by combiningdomino and cascade reactions with rearrangements. Indeed, one or even several rear-rangements are often involved in the domino/cascade. Furthermore, a rearrangementreaction is one that takes place within a limited number of atoms belonging to onemolecule. In a domino reaction, the number of available atoms is also strictly limitedand mechanisms of the rearrangement and domino components are often similar.
Another very interesting category of the domino/cascade reactions worth men-tioning is that of three component reactions. Its application to the synthesis of manymolecules of biological interest and templates for natural products synthesis is par-ticularly appealing. This strategy is well exemplified and detailed in Chapter 7.
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xiv FOREWORD
While there are excellent books devoted to domino reactions and rearrangements inorganic chemistry in general, there have been no corresponding comprehensive worksdescribing “the State of the Art” in domino/cascade reactions and rearrangements inthe carbohydrate field. Witczak and Bielski have recognized the strategic importanceof designing/preserving chirality of molecules and applying tools of modern syntheticmethodology to carbohydrate chemistry. Happily, the Editors were able to recruit agroup of outstanding scientists to contribute excellent chapters addressing importantaspects of the molecular transformations with a combination of rearrangements andcascade/domino options to cover most topics of value in glycosciences. Given itsvery careful selection of subjects and their sequential presentation in a collection of15 chapters, this book constitutes a valuable source of practical information to allcarbohydrate chemists.
I am sure that there will be a great interest in this book.
Samuel Danishefsky
Professor of ChemistryMemorial Sloan-Kettering Cancer Center
PREFACE
Synthesis of organic molecules designated to fulfill special requirements or exhibitspecific properties has belonged and will belong to the most important targets oforganic chemistry. This area of synthesis, particularly when applied to synthesisof constructs containing carbohydrates, has experienced a dramatic acceleration inrecent years. One factor explaining the observed new developments has been a betterunderstanding of the function and structure of glycoproteins and other naturally occur-ring glycorandomized derivatives. The present book attempts to offer an insight intothese new developments created by coupling domino reactions with rearrangementreactions to achieve specifically designated/functionalized carbohydrate chemistries.
Carbohydrates represent a unique family of polyfunctional molecules, which canbe chemically or enzymatically modified in a multitude of ways. They have beenextensively used as starting materials in enantioselective syntheses of many, complexnatural products with a plurality of chirality centers. Synthetic organic chemistrythat utilizes these carbohydrate building blocks continues to spawn revolutionarydiscoveries in glycobiology, medicinal chemistry, pharmacology, molecular biology,and medicine, simply by providing not only the raw materials but also the accuratemechanistic insight of modem molecular sciences.
The coupling of synthetic approaches of domino reactions combined with rear-rangement steps is always complex with multiple possible outcomes. In syntheticcarbohydrate chemistry, it is even more difficult as it is often unpredictable andalways requires very careful selection of starting templates, reagents, and reactionconditions to achieve the best approach to the target compound.
The book originates from the symposium “Domino Reactions and Rearrangementin Glycosciences,” which we organized during the 248th Meeting of the AmericanChemical Society in San Francisco, CA, in Fall 2014. It attracted several prominent
xv
xvi PREFACE
speakers, had a relatively large attendance, and was met with a lot of interest. Some ofthe chapters in this book are based on the presentations delivered at the symposium.Other contributions are from leading experts in the field of carbohydrate chemistry.Some of the chapters are reviews of the recent literature; some describe recentexperimental data from the author’s laboratories. We believe that all chapters are ofa very high standard and offer a novel perspective on the discussed subjects.
Thus, it is not surprising that almost all of the chapters in the book are, to someextent, concerned with applications. It confronts the editors with a dilemma that isimpossible to address satisfactorily—how to divide the book into consistent segments.By no means are we satisfied with our choice, but some kind of division had to beintroduced.
Each chapter in the book covers issues related to the title reactions and dis-cusses multiple synthetic methodologies and potential applications of the synthesizedconstructs.
The introductory chapter, written by internationally recognized expert in dominoreactions Pellissier, discusses various aspects of selected examples of carbohydratedomino chemistry methodologies and proposes a novel strategy applicable to synthe-sizing certain molecular targets. It also describes the definition of domino reactionthat was originally introduced by Thietze.
Chapter 2, authored by Mahrwal, deals with organocatalyzed cascade reactionstrategies employed to the synthesis of important carbohydrate templates. The mostefficient methodologies compiled in this review were developed before the birth ofofficial combined domino/cascade reaction chemistry.
Chapter 3, authored by Soengas, describes intriguing results of the various elimi-nation reaction strategies in domino reactions.
The development and application of original framework strategy of domino reac-tion for synthesis of biological targets were thoroughly explored by Rauter in Chap-ter 4. The chapter discusses most types of natural molecules, including complexcarbohydrates.
In Chapter 5, Guaragna reviews an important topic of original strategy of synthesesof thioenol ether containing systems and their multistep cyclization mediated byDDQ.
In Chapter 6, Witczak and Bielski offer a different perspective on closelyrelated subject of thio-click and domino approach to the synthesis of carbohydrateheterocycles.
Chapter 7, by Santra and coworkers, addresses microwave-assisted multicompo-nent cascade coupling of various compounds, including carbohydrates.
Chapter 8, by Werz, is a very broad review of spiroannulation domino reactions forthe attachment of additional carbohydrate functionalities. The review discusses pro-cesses belonging to domino reactions as well as other important annulation couplingreactions traditionally used for the construction of various natural product targets.
In the second section of the book, titled “Rearrangements Reactions of Func-tional Sugar Templates,” Witczak and Bielski explore, in Chapter 9, selected topicsto introduce the reader to the subject of rearrangement reactions in carbohydratechemistry.
PREFACE xvii
Jarosz and coworkers contribute in Chapter 10 with a discussion of novel syntheticapplications of rearrangement of carbohydrate backbone discovered en route to highercarbon sugars.
Chapter 11, by Bielski and Witczak, describes a new chemistry of levoglucosenonederivatives prepared via Overman and related rearrangements.
Marzabadi and coworkers describe in Chapter 12 an important study of the rear-rangement products of 3,6-anhydro-d-glycals. The review highlights a synthesis ofprototypes of simple functionalized molecules with high chemotherapeutic potential.
Chapter 13, by Narayanaswamy and coworkers, provides a general overview of thepotential applications of ring expansion and rearrangement reactions in the synthesisof highly valuable, septanoses as bioactive, carbohydrate-based ligands with multiplebiomedical applications.
Chapter 14, by Herradon and coworkers, describes rearrangements of carbohydratetemplates as the pathway to functionalized heterocycles and peptide–scaffold hybrids.
The last chapter, by Nguyen and coworkers, explores an extremely important topicof a stereoselective transformation of glycals and glycosyl trichloroacetimidates andtheir application to the synthesis if important urea-linked glycosides.
With the increasing complexity of modern sciences in the 21st century, a needto educate industrial leaders, public, and governmental funding agencies about theintellectual and technical potential and economic importance of specific areas of lifesciences has become more and more crucial. One such area is the part of glycoscienceemerging as a result of a marriage between the concept of domino and rearrangementapproaches in the synthetic carbohydrate chemistries. We hope that this book will fillthis need, at least to some extent.
In conclusion, we are convinced that the present collection of diverse chaptersoffers an insight into the present stage of domino and rearrangement approaches inglycoscience and will help steer future discoveries to fulfill the enormous potentialin the area of synthetic carbohydrate chemistry.
ACKNOWLEDGMENTS
We thank all the authors for excellent contributions to this volume. We also thank thepeer reviewers of the chapters for their high level of expertise and helpful efforts toimprove the overall quality of all the manuscripts.
We dedicate this book to our wives, Wanda and Barbara.
Zbigniew J. Witczak, PhDDepartment of Pharmaceutical SciencesNesbitt School of PharmacyWilkes University, Wilkes-Barre, PA 18766, USA
Roman BielskiValue Recovery, Inc.510 Heron DriveSuite 301, Bridgeport, NJ 08014, USADepartment of Pharmaceutical SciencesWilkes UniversityWilkes-Barre, PA 18766, USA
xix
LIST OF CONTRIBUTORS
Peter R. Andreana, Department of Chemistry and Biochemistry and School ofGreen Chemistry and Engineering, University of Toledo, 2801 W. Bancroft St.,Wolfe Hall 2232B, Toledo, OH 43606-3390, USA; phone: 409-530-1930; e-mail:[email protected]
Tonja Andreana, Department of Chemistry and Biochemistry and School of GreenChemistry and Engineering, University of Toledo, 2801 W. Bancroft St., WolfeHall 2232B, Toledo, OH 43606-3390; USA
Vikram Basava, Department of Chemistry and Biochemistry, Seton Hall University,400 South Orange Ave., South Orange, NJ 07079, USA
Roman Bielski, Department of Pharmaceutical Sciences, Wilkes University, 84W. South Street, Wilkes-Barre, PA, USA; phone: 610-573-4804; e-mail [email protected]
Jean-Paul Bourgault, Department of Chemistry and Biochemistry and School ofGreen Chemistry and Engineering, University of Toledo, 2801 W. Bancroft St.,Wolfe Hall 2232B, Toledo, OH 43606-3390, USA
Vasco Cachatra, Universidade de Lisboa, Faculdade de Ciencias, Departamento deQuımica e Bioquımica, Centro de Quımica e Bioquımica, Carbohydrate ChemistryGroup, Ed. C8, Piso 5, Campo Grande, 1749-016 Lisboa, Portugal
Maciej Cieplak, Institute of Organic Chemistry, Polish Academy of Sciences,Kasprzaka 44/52, 01-224 Warsaw, Poland
Supriya Dey, Department of Organic Chemistry, Indian Institute of Science, Ban-galore, Karnataka, India
xxi
xxii LIST OF CONTRIBUTORS
Daniele D’Alonzo, Department of Chemical Sciences, University of Napoli Fed-erico II, via Cintia 21, I-80126 Napoli, Italy
Agnieszka Gajewska, Institute of Organic Chemistry, Polish Academy of Sciences,Kasprzaka 44/52, 01-224 Warsaw, Poland
Annalisa Guaragna, Department of Chemical Sciences, University of Napoli Fed-erico II, via Cintia 21, I-80126 Napoli, Italy; phone: +39-081-674119; e-mail:[email protected]
Emi Hanawa, Department of Chemistry and Biochemistry, Seton Hall University,400 South Orange Ave., South Orange, NJ 07079, USA
Bernardo Herradon, Instituto de Quımica Organica General, CSIC, c/ Juande la Cierva 2, 28006 Madrid, Spain; phone: +34915618806; e-mail:[email protected]
Sławomir Jarosz, Institute of Organic Chemistry, Polish Academy of Sciences,Kasprzaka 44/52, 01-224 Warsaw, Poland; phone: +4822-3432320; fax: +4822-6326681; e-mail: [email protected]
N. Jayaraman, Department of Organic Chemistry, Indian Institute of Science, Ban-galore, Karnataka, India
Rainer Mahrwald, Institut fur Chemie der Humboldt-Universitat zu Berlin,Brook-Taylor-Str. 2, 12 489 Berlin, Germany; phone: +49-30-2093-8397; e-mail:[email protected]
Enrique Mann, Instituto de Quımica Organica General, CSIC, c/ Juan de la Cierva2, 28006 Madrid, Spain
Cecilia H. Marzabadi, Department of Chemistry and Biochemistry, Seton Hall Uni-versity, 400 South Orange Ave., South Orange, NJ 07079, USA; phone: (973)761-9032; fax: (973)761-9772; e-mail: [email protected]
Matthew J. McKay, Department of Chemistry, University of Iowa, Iowa City, Iowa52242, USA
Irene de Miguel, Instituto de Quımica Organica General, CSIC, c/ Juan de la Cierva2, 28006 Madrid, Spain
Hien M. Nguyen, Department of Chemistry, University of Iowa, Iowa City, IA52242, USA; phone: (+1) 319-384-1887; e-mail: [email protected]
Anna Osuch-Kwiatkowska, Institute of Organic Chemistry, Polish Academy ofSciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
Giovanni Palumbo, Department of Chemical Sciences, University of Napoli Fed-erico II, via Cintia 21, I-80126 Napoli, Italy
Nathaniel H. Park, Department of Chemistry, University of Iowa, Iowa City, IA52242, USA
LIST OF CONTRIBUTORS xxiii
Helene Pellissier, Aix Marseille Universite, Centrale Marseille, CNRS iSm2 UMR7313, 13397 Marseille, France
Amelia P. Rauter, Universidade de Lisboa, Faculdade de Ciencias, Departamento deQuımica e Bioquımica, Centro de Quımica e Bioquımica, Carbohydrate ChemistryGroup, Ed. C8, Piso 5, Campo Grande, 1749-016 Lisboa, Portugal; phone: +351217500952; e-mail: [email protected] or [email protected]
Soumava Santra, Department of Chemistry and Biochemistry and School of GreenChemistry and Engineering, University of Toledo, 2801 W. Bancroft St., WolfeHall 2232B, Toledo, OH 43606-3390, USA
Artur M. S. Silva, Department of Chemistry & QOPNA, University of Aveiro,3810-193 Aveiro, Portugal
Eric T. Sletten, Department of Chemistry, University of Iowa, Iowa City, IA 52242,USA
Raquel G. Soengas, Department of Chemistry & QOPNA, University of Aveiro,3810-193 Aveiro, Portugal; phone: +351-234-370084; e-mail: [email protected]
Sara M. Tome, Department of Chemistry & QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal
N. Vijaya Ganesh, Department of Organic Chemistry, Indian Institute of Science,Bangalore, Karnataka, India
Benjamin Voigt, Institut fur Chemie der Humboldt-Universitat zu Berlin, Brook-Taylor-Str. 2, 12 489 Berlin, Germany
Daniel B. Werz, Institut fur Organische Chemie, Technische Universitat Braun-schweig, Hagenring 30, 38106 Braunschweig, Germany; phone: (+) 49-531-3915266; e-mail: [email protected]
Zbigniew J. Witczak, Department of Pharmaceutical Sciences, Wilkes University,84 W. South Street, Wilkes-Barre, PA, USA; phone: 570-408-4276; e-mail: [email protected]
ABBREVIATIONS
1D one-dimensional2D two-dimensionalA adenineAc acetylAIBN azobisisobutyronitrileAr arylBINAP 2,2′-bis(diphenylphosphino)-1,1′-binaphthylBn benzylBoc tert-butoxycarbonylBSA bis(trimethylsilyl) acetamidoBz benzoylC cytosineCAN ceric ammonium nitrateCbz carboxybenzylCp cyclopentanylD-A donor–acceptorDABCO 1,4-diazabicyclo[2.2.2]octaneDBU 1,8-diazabicyclo[5.4.0]undec-7-eneDCC N,N′-dicyclohexylcarbodiimideDCE dichloroethaneDCM dichloromethaneDDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinoneDHP dihydropyranDIAD di(isopropyl) azodicarboxylateDMAP 4-dimethylaminopyridine
xxv
xxvi ABBREVIATIONS
DME dimethoxyethaneDMF N,N-dimethylformamideDMF dimethylformamideDMP dimethoxypropaneDMS dimethylsulfideDMSO dimethysulfoxideDOS diversity-oriented synthesisdppb 1,4-bis(diphenylphosphino)butanedppe 1,2-bis(diphenylphosphino)ethanedppp 1,3-bis(diphenylphosphino)propaneDTBP 2,6-di-tert-butylphosphineEDC 1-ethyl-3-(3-dimethylaminopropyl)carbodiimideEDTA ethylenediaminetetraacetic acidEt ethylGal galactoseGlc glucoseHCS higher carbon sugarsHMPA hexamethylphosphoramideHNA 1′,5′-anhydro-arabino-hexitol nucleic acidshomoDNA 2′,3′-dideoxy-β-erythro-hexopyranosyl nucleic acidsIBX 2-iodoxybenzoic acidIMDA intramolecular Diels-Alder reactioni-Pr isopropylLAH lithium aluminum hydrideLDA lithium diisopropylamidem-CPBA m-chloroperoxybenzoic acidMCR multicomponent reactionMe methylMS molecular sievesMTBE methyl tert-butyl ethermw microwaveMWI microwave irradiationNIS N-iodosuccinimideNMMO N-methylmorpholine-N-oxideNMO N-methylmorpholine-N-oxideNMP N-methylpyrrolidoneNMR nuclear magnetic resonanceNOE Nuclear Overhauser effectP-3CR Passerini three-component reactionPCC pyridinium chlorochromatePDC pyridinium dichromatePG protecting groupPh phenylPMB 4-methoxybenzylPPTS pyridinium p-toluenesulfonate
ABBREVIATIONS xxvii
Py pyridineRCM ring-closing metathesisrt room temperatureSET single-electron transferT thymineTBAF tetrabutylammonium fluorideTBDPS tert-butyldiphenylsilylTBSOTf tert-butyldimethylsilyl trifluoromethanesulfonatetBu tert-butylTEA triethylamineTEBAC benzyltriethylammonium chlorideTFDO methyl(trifluoromethyl)dioxiraneTHF tetrahydrofuranTHP tetrahydropyranTIBAL triisobutylaluminumTLC thin layer chromatographyTMEDA tetramethylethylenediamineTMS trimethylsilylTMSCN trimethylsilyl cyanideTMSOTf trimethylsilyl trifluoromethanesulfonateTosyl para-toluenesulfonate esterTPAP tetrapropylammonium perruthenateTS para-toluenesulfonate esterTs 4-methylphenylsulfonyl (tosyl)TTMPP tris(trimethoxyphenyl)phosphineU-4CR Ugi four-component reaction
