Carbohydrate chemistry Volume 35

370 Pages·6.927 MB·English

Specialist Periodical Reports
Edited by A Pilar Rauter and T K Lindhorst
Carbohydrate Chemistry
Chemical and Biological Approaches
Volume 35
Carbohydrate Chemistry
Chemical and Biological Approaches
Volume 35

A Specialist Periodical Report
Carbohydrate Chemistry
Chemical and Biological
Approaches
Volume 35
A Review of the Literature Published between
January 2004 and December 2008
Editors
Amelia Pilar Rauter, Universidade de Lisboa, Portugal
Thisbe K. Lindhorst, Christian-Albrechts-Universia¨t zu Kiel, Germany
Authors
Jose´ A. S. Cavaleiro, University of Aviero, Portugal
Ramo´n J. Este´vez, Universidade de Santiago de Compostela, Spain
Ana M. Go´mez, CSIC, Madrid, Spain
Anne Imberty, Masaryk University, Brno, Czech Republic
Sławomir Jarosz, Polish Academy of Sciences, Warsaw, Poland
Jesu´s Jime´nez-Barbero, CSIC, Madrid, Spain
Vladim´ırKrˇen,AcademyofSciencesoftheCzechRepublic,Prague,CzechRepublic
J. Cristo´bal Lo´pez, CSIC, Madrid, Spain
Francesco Nicotra, University of Milan, Italy
Yves Queneau, Universite´de Lyon, Villeurbanne, France
Inmaculada Robina, University of Seville, Spain
Patrick Rollin, Universite´d’Orle´ans, France
Pierre Vogel, Ecole Polytechnique Fe´de´rale de Lausanne, Switzerland
Alla Zamyatina, University of Natural Resources and Applied Life Sciences,
Vienna, Austria
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ISBN: 9781847558800
ISSN: 0306-0713
A catalogue record for this book is available from the British Library
r The Royal Society of Chemistry 2009
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Preface
DOI: 10.1039/b908035j
The Specialist Periodical Reports volumes on Carbohydrate Chemistry,
publishedbytheRoyalSocietyofChemistry,havebecomeverywellknown
and recognized in recent decades as an extremely useful book series for
researchers in the field of carbohydrate chemistry. These volumes provide
review coverage of all publications relevant to the chemistry of mono- and
oligosaccharidesinagivenyear,andeachvolumeoftheserieshasbrought
together references to all published work in given areas of the subject and
served as a comprehensive database for the active research chemist.
Prof. Robin Ferrier, the previous scientific editor, gave an outstanding
contribution tothesuccess ofthis series up tohisretirementin2002, when
volume 34 was published. This series has lapsed since then, but the Royal
Society of Chemistry is now re-initiating the publication of Specialist
Periodical Reports volumes on Carbohydrate Chemistry, with a new
philosophy for the series. Considering the easy access that researchers
now have to published work in their area of interest, this series aims to
bring together the latest developments in topical highlights and critical
reviews, covering the related subjects from chemistry to biology in the last
five years. This new approach will be of great advantage to any researcher
whowishestofind,inasinglebook,chemicalandbiologicalsciencerelated
tothetopicthathasbeenselectedforthatparticularissueoftheseries,thus
avoiding time-consuming literature searches involving journals specialized
in chemistry, biology or other related areas.
The first volume of this re-invigorated series is volume 35, which covers
firstlyvariousaspectsofthechemistryattheanomericcenter,startingwith
acriticalrevisionoftheenthalpic,conformationalandalsokineticanomeric
effectsinpyranosides.Methodologiesfor1,2-cis-O-and1,2-cis-C-glycosylation,
stereoselective synthesis of biologically relevant glycosyl phosphates and
synthetic approaches for C-1 glycals, which are currently used for
C-glycosylation, are also discussed. Nitro sugars and transformations
affectingtheiranomericcenterleadingtoadiversityofmolecularstructures
arereviewedaswell.Inaddition,theimportanceofthechemistryatC-1for
the preparation of carbohydrate scaffolds involving bicyclic lactones or
thionocarbamatesishighlighted.Furthermore,itisshownhowtheproduc-
tion of fine chemicals and of bioactive molecules containing sugars and
porphyrines can take advantage of the chemistry at the anomeric center.
Blocking the anomeric reactivity allows one not only to inhibit enzymes,
which interfere with biological functions, but also to mimic glycosides by
stable compounds of pharmacological relevance. Hence, modifications of
the anomeric centre of carbohydrates are also reviewed, as well as
compounds of that type which have found application as drugs.
Glycosidic bond formation by enzymes is particularly attractive for the
preparation of oligosaccharides, avoiding tedious protection, activation,
and deprotection strategies. Thus, a chapter of this volume is dedicated to
the enzymatic synthesis of oligosaccharides by glycosidases, also using
modified substrates and including glycosidase mutants.
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Carbohydrate conformation plays a key role for molecular recognition
processes, and their determination contributes to the understanding of
many biological processes. The latest NMR methodological developments
for conformation determination are discussed here, and representative
examples are given.
The final chapter is dedicated to the state-of-the-art methods for deter-
mining lectin affinity and specificity for oligosaccharides. These play a key
role in many biological processes relevant to cell communication and
disease states, and are involved in cancer development and metastasis,
inflammation and host-pathogen recognition.
Overall, this volume, covering various approaches for syntheses, NMR
conformational studies and methods for determining lectin–carbohydrate
interactions essential for recognition processes, demonstrates the inter-
disciplinary character of modern carbohydrate research, together with the
importance of combining chemical and biological approaches to achieve
innovation in glycomics. It is our hope, that with this new Specialist
PeriodicalReportsvolumeonCarbohydrateChemistry,wehaveassembled
acollectionofcontributionsthatcapturethethrivingnatureofcarbohydate
research.
Last not least, we wish to thank the authors of this volume for their
commitment in writing their contributions within such a short period of
time, allowing its publication in time for presentation at Eurocarb XV in
Vienna!
The scientific editors,
Amelia Pilar Rauter and Thisbe K. Lindhorst
The next volume
Volume 36 will be dedicated to carbohydrate-based vaccines and to the
utilizationoftheazidefunctionalityinchemicalandbiologicalareasofthe
glycosciences.Therearerecentreportsoninterestingapplicationsofazides
in this area, and as starting materials for a variety of important bioactive
carbohydrates. Hence, the synthesis, reactivity and application of azides in
glycomics will also be included in this volume.
Somepromisingcontributionshavealreadybeenconfirmed,andwethus
can already look forward to the next volume!
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CONTENTS
Cover
Tetrahydropyran-enclosed
ball-and-stickdepictionofa
glucosemolecule,and
(inthebackground)partofan
a-glycosyl-(1-4)-D-glucose
oligosaccharideanda
glycosidase,allrepresentative
ofthetopicscoveredin
CarbohydrateChemistry–
ChemicalandBiological
Approaches.
Coverprepared
byR.G.dosSantos.
Preface 7
Amelia Pilar Rauter and Thisbe K. Lindhorst
Anomeric effects in pyranosides and related acetals 13
Sandrine Gerber-Lemaire and Pierre Vogel
Introduction 13
The enthalpic anomeric effect 13
The conformational anomeric effect 16
The kinetic anomeric effect 24
Conclusion 29
Stereoselective synthesis of 1,2-cis-glycosylic linkages 33
Ana T. Carmona, Antonio J. Moreno-Vargas and Inmaculada Robina
Introduction 33
Stability of 1,2-cis-glycosylic linkages 35
Factors influencing anomeric control in 1,2-cis-glycosylations 36
Methods for the preparation of 1,2-cis-O-glycosides 37
Methods for the preparation of 1,2-cis-C-glycosyl compounds 48
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Synthesis of anomeric phosphates of aldoses and 2-ulosonic acids 71
Alla Zamyatina and Paul Kosma
Introduction 71
Instalment of glycosyl phosphate linkage by glycosylation 72
Synthesis of glycosyl phosphates by exposure of hemiacetals to 81
activated derivatives of phosphoric acid
ApproachestoglycosylphosphatesbasedonP(III)-intermediates 85
Synthesis of anomeric phosphates of aldulosonic acids 93
Conclusions 94
Glycosidic bicyclic lactones as new carbohydrate scaffolds 99
Yves Queneau, Ste´phane Chambert, Sylvie Moebs,
Arkadiusz Listkowski and Rouba Cheaib
Carbohydrate-based bicyclic lactones: an introduction 99
Carboxymethyl glycoside lactones (CMGLs): synthesis 108
Uses of CMGLs towards mono- and difunctional systems 114
Conclusion 121
Thionocarbamates on carbohydrate scaffolds—from synthesis 127
to bioactivity
Ana Catarina Sima˜o, Jolanta Rousseau, Sandrina Silva,
Amelia Pilar Rauter, Arnaud Tatiboue¨t and Patrick Rollin
Introduction 127
Synthesis of thionocarbamates on carbohydrate scaffolds 128
Reactivity of thionocarbamates on carbohydrate scaffolds 147
Bioactivity 160
Conclusions 165
Recent advances in nitro sugar chemistry 173
Raquel G. Soengas, Juan C. Este´vez, Amalia M. Estevez,
Fernando Ferna´ndez and Ramo´n J. Este´vez
Introduction 173
Preparation of nitro sugars 173
Reactivity of nitro sugars 180
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Porphyrinyl-type sugar derivatives: synthesis and biological 199
applications
Jose´ A. S. Cavaleiro, Maria A. F. Faustino and Joa˜o P. C. Tome´
Introduction 199
Synthesis of porphyrinyl-type sugar derivatives 200
Biological applications 223
Concluding remarks 227
Sugars as chiral synthons in the preparation of fine chemicals 232
Szawomir Jarosz, Marta Magdycz and Bartosz Lewandowski
Introduction 232
From simple sugars to cyclic (non-sugar) derivatives: 232
transfer of chirality
Modified carbohydrates 243
Transformation of disaccharides 252
Conclusion 255
Blocking the anomeric reactivity, how and why 259
Francesco Nicotra, Laura Cipolla, Barbara La Ferla and
Ana Catarina Arau´jo
Introduction 259
Replacement of the anomeric oxygen 260
Replacement of the endocyclic oxygen 275
Other modifications 283
Conclusions 284
Recent strategies for the preparation of C-1 glycals 289
Ana M. Go´mez and J. Cristo´bal Lo´pez
C-1 Glycals – an introduction 289
From cyclic precursors 289
From acyclic precursors 302
Conclusions 306
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