Carbohydrate chemistry volume 40

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Published on 20 March 2014 on | doi:10.1039/9781849739986-FP001

Carbohydrate Chemistry

Chemical and Biological Approaches

Volume 40


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Published on 20 March 2014 on | doi:10.1039/9781849739986-FP001

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Published on 20 March 2014 on | doi:10.1039/9781849739986-FP001

A Specialist Periodical Report

Carbohydrate Chemistry
Chemical and Biological
Approaches
Volume 40
Editors
Amelia Pilar Rauter, Universidade de Lisboa, Portugal
Thisbe K. Lindhorst, Christiana Albertina University of Kiel,
Germany

Yves Queneau, Universite
´ de Lyon, France
Authors
Isabelle Andre
´, Universite
´ de Toulouse, France
Jean-Marie Aubry, Universite
´ Lille Nord de France, France
Jacques Auge
,
University
of
Cergy-Pontoise, France
´
Caroline Ballet, Ecole Nationale Supe
´rieure de Chimie de Rennes,
France
Chantal Barberot, Universite
´ de Reims Champagne-Ardenne,
France
Jean-Marie Beau, Universite
´ Paris-Sud, Orsay, and CNRS, Gif-sur-Yvette,
France
Thierry Benvegnu, Ecole Nationale Supe
´rieure de Chimie de Rennes,
France
Davide Bini, Universita degli Studi di Milano-Bicocca, Italy
Yves Ble
´riot, Universite
´ de Poitiers, France

Julie Bouckaert, Universite
´ Lille Nord de France, France
Yann Bourdreux, Universite
´ Paris-Sud, Orsay, France
Francois-Didier Boyer, CNRS, Gif-sur-Yvette, and INRA, Versailles,
France
Alexandre Cavezza, L’Ore
´al Research & Innovation, Aulnay-sous-Bois,
France
Yves Chapleur, Universite
´ de Lorraine, Nancy, France
Laura Cipolla, Universita degli Studi di Milano-Bicocca, Italy
Claire Coiffier, Universite
´ de Reims Champagne-Ardenne, France
Florent Colomb, Universite
´ Lille Nord de France, France
Xavier Coqueret, Universite
´ de Reims Champagne Ardenne, France
Stephen Cowling, University of York, UK
Maria Dalko-Csiba, L’Ore
´al Research & Innovation, Aulnay-sous-bois,
France


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Richard Daniellou, Universite d’Orle

´ans, France
Samuel J. Danishefsky, Sloan-Kettering Institute for Cancer Research
and Columbia University, New York, USA
David Daude
´, Universite
´ de Toulouse, France
Edward Davis, University of York, UK
Philippe Delannoy, Universite
´ Lille Nord de France, France
Gilles Doisneau, Universite
´ Paris-Sud, Orsay, France
Sandrine Donadio-Andre
´ i, Siamed’Xpress, Gardanne, France
Nassima El Maı¨, Siamed’Xpress, Gardanne, France
Alberto Ferna´ndez-Tejada, Sloan-Kettering Institute for Cancer
Research, New York, USA
Vincent Ferrie
` res, Ecole Nationale Supe
´rieure de Chimie de Rennes,
France
Luca Gabrielli, Universita degli Studi di Milano-Bicocca, Italy
Charles Gauthier, Universite
´ de Poitiers, France
Markus Glaffig, Johannes Gutenberg-Universita¨t Mainz, Germany
Peter Goekjian, Universite
´ de Lyon, France
John Goodby, University of York, UK
Alexandra Gouasmat, Universite
´ Paris-Sud, Orsay, France
Eric Grand, Universite

de
Picardie
Jules Verne, Amiens, France
´
Jaros"aw M. Granda, Institute of Organic Chemistry, Polish Academy of
Sciences, Warsaw, Poland
Sophie Groux-Degroote, Universite
´ Lille Nord de France, France
Ce
line
Guillermain,
Universite
de
Reims
Champagne Ardenne, France
´
´
Laure Guillotin, Universite
d’Orle
ans,
CNRS,
France
´
´
Dominique Harakat, Universite
de
Reims
Champagne
Ardenne, France
´

Sebastian Hartmann, Johannes Gutenberg-Universita¨t Mainz,
Germany
Arnaud Haudrechy, Universite
´ de Reims Champagne-Ardenne, France
Eric He
non,
Universite
de
Reims
Champagne-Ardenne, France
´
´
S"awomir Jarosz, Institute of Organic Chemistry, Polish Academy of
Sciences, Warsaw, Poland
Janusz Jurczak, Institute of Organic Chemistry, Polish Academy of
Sciences, Warsaw, Poland
Jose
´ Kovensky, Universite
´ de Picardie Jules Verne, Amiens, France
Micha" Kowalski, Institute of Organic Chemistry, Polish Academy of
Sciences, Warsaw, Poland
Horst Kunz, Johannes Gutenberg-Universita¨t Mainz, Germany
Laure L’Haridon, Ecole Normale Supe
´rieure, Paris, France
Pierre Lafite, Universite d’Orle
ans,
CNRS,
France
´
Laurent Legentil, Ecole Nationale Supe

rieure
de Chimie de Rennes,
´
France
Aure
´ lie Leme
´ tais, Universite
´ Paris-Sud, Orsay, France
Loı¨c Lemie
` gre, Ecole Nationale Supe
´rieure de Chimie de Rennes, France
Nade
` ge Lubin-Germain, University of Cergy-Pontoise, France
Jun Luo, Tongji School of Pharmacy, Huazhong University of Science
and technology, Wuhan, P. R. China
Carine Maalaki, Universite
´ de Namur, Belgium
Jean-Maurice Mallet, Ecole Normale Supe
´rieure, Paris, France


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Alberto Marra, Ecole Nationale Supe
´rieure de Chimie de Montpellier,
France
Olivier Massinon, Universite

´ de Namur, Belgium
Aure
´ lie Mathieu, CNRS, Gif-sur-Yvette, France
Yong Miao, Universite
´ Lille Nord de France, France
Jean-Claude Michalski, Universite
´ Lille Nord de France, France
Vale
´ rie Molinier, Universite
´ Lille Nord de France, France
Pierre Monsan, Universite
´ de Toulouse, France
Andre
Mortreux,
Universite
´
´ Lille Nord de France, France
Magali Nicollo, Siamed’Xpress, Gardanne, France
Francesco Nicotra, Universita degli Studi di Milano-Bicocca, Italy
Ste
´ phanie Norsikian, CNRS, Gif-sur-Yvette, France
Caroline Nugier-Chauvin, Ecole Nationale Supe
´rieure de Chimie de
Rennes, France
Jean-Marc Nuzillard, Universite
´ de Reims Champagne-Ardenne, France
Bjo
rn
Palitzsch,
Johannes

Gutenberg-Universita
¨
¨t Mainz, Germany
Nadia Pellegrini-Moı¨se, Universite
de
Lorraine,
Nancy, France
´
Michel Philippe, L’Ore
al
Research
&
Innovation,
Aulnay-sous-Bois,
´
France
Patrick Pichaud, L’Ore
´al Research & Innovation, Aulnay-sous-Bois,
France
Loı¨c Pichavant, Universite
´ de Reims Champagne Ardenne, France
Daniel Plusquellec, Ecole Nationale Supe
´rieure de Chimie de Rennes,
France
Mykhaylo A. Potopnyk, Institute of Organic Chemistry, Polish Academy
of Sciences, Warsaw, Poland
Yvan Portier, Ecole Nationale Supe
´rieure de Chimie de Rennes, France
Gwladys Pourceau, Universite
de

Picardie
Jules Verne, Amiens, France
´
Magali Remaud-Sime
on,
Universite
de
Toulouse,
France
´
´
Myle
ne
Richard,
Universite
de
Lorraine,
Nancy,
France
`
´
Catherine Robbe-Masselot, Universite
´ Lille Nord de France, France
Maria C. Rodrı´guez, Center for Biomolecular Chemistry, Havana, Cuba
Catherine Ronin, Siamed’Xpress, Gardanne, France
Laura Russo, Universita degli Studi di Milano-Bicocca, Italy
Ram Sagar, Universite
´ de Poitiers, France
Mathieu Sauthier, Universite
´ Lille Nord de France, France

Marie-Christine Scherrmann, Universite
´ Paris-Sud, Orsay, France
Antonella Sgambato, Universita degli Studi di Milano-Bicocca, Italy
Jean-Francois Soule
´ , CNRS, Gif-sur-Yvette, France
Arnaud Stevenin, CNRS, Gif-sur-Yvette, France
Isabelle Suisse, Universite
´ Lille Nord de France, France
Sylvestre Toumieux, Universite
´ de Picardie Jules Verne, Amiens, France
Sylvain Tranchimand, Ecole Nationale Supe
´rieure de Chimie de Rennes,
France
Simon Trouille, L’Ore
´al Research & Innovation, Aulnay-sous-Bois, France
Dominique Urban, Universite
´ Paris-Sud, Orsay, France
Yury Valde
´ s Balbin, Center for Biomolecular Chemistry, Havana, Cuba
Boris Vauzeilles, Universite
´ Paris-Sud, Orsay, and CNRS, Gif-sur-Yvette,
France


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Vicente Verez Bencomo, Center for Biomolecular Chemistry, Havana,

Cuba
Ste
´ phane P. Vincent, Universite
´ de Namur, Belgium
Anne Wadouachi, Universite
´ de Picardie Jules Verne, Amiens, France
Qian Wan, Tongji School of Pharmacy, Huazhong University of Science
and technology, Wuhan, P. R. China
Amandine Xolin, CNRS, Gif-sur-Yvette, France
Rui Xu, Universite
´ de Lyon, France
Philippe Zinck, Universite
´ Lille Nord de France, France


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to the chapters online. Please contact with proof of
purchase to arrange access to be set up.

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Thank you.

ISBN: 978-1-84973-965-8
ISSN: 0306-0713
DOI: 10.1039/9781849739986
A catalogue record for this book is available from the British Library

& The Royal Society of Chemistry 2014
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Preface

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Published on 20 March 2014 on | doi:10.1039/9781849739986-FP009

DOI: 10.1039/9781849739986-FP009

Volume 40 of the Specialist Periodical Reports entitled Carbohydrate
Chemistry – Chemical and Biological Approaches is dedicated to the
´ Lubineau. This chemist, well known amongst
memory of Prof. Andre
organic, carbohydrate, and green chemists for his work, left behind him
not only his innovative work applied in industry and recognized for its
excellence and uniqueness, but also many, many friends among his
colleagues and students. His former Ph.D. student, Dr. Yves Queneau,
had the initiative to dedicate this volume to his memory and is very
welcome as guest editor.
The first book chapter describes the industrial development of
Lubineau’s C-glycosylation reaction to access a product for skin anti´als, a leading company in cosmetics. The
ageing marketed by L’Ore
principles of green chemistry concerning water-promoted reactions such
as cycloaddition, N-glycosylation and C-glycosyl compound formation,
´ Lubineau, are well documented in Chapter 2.
implemented by Andre
The use of carbohydrates in sustainable chemistry is highlighted in
´ Lubineau’s contributions in this field with
Chapter 3, exemplifying Andre
various applications, namely carbohydrates as surfactants. In Chapter 4,
synthesis and properties of sugar-based hydrotropes are revised. These
compounds exhibit amphiphilicity and can be regarded as weak
surfactants, being considered promising alternatives to the currently
used hydrotropes from petroleum origin. Chapter 5 shows how green

catalysis can be used in carbohydrate etherification.
A diversity of synthetic strategies are described in Chapters 6–10,
focusing particularly on anomeric functionalization, either using exoglycals or glycosylation catalysed with iron salts or by gold, supplemented
by electrochemical or enzymatic (thio)glycosylation.
Recent protocols for the synthesis of anionic oligosaccharides, that
exhibit interesting biological activities in cell proliferation, angiogenesis
and cancer, host-pathogen interactions, Alzheimer’s disease and plant
protection are presented in Chapter 11. Synthesis of macrocycles from
sucrose with interesting complexing properties, of carbohydrate-based
dendrimers, and of polymers via radical free polymerization starting
from allyl or vinyl pentosides, or by organo-catalysed polymerization of
polyester-functionalized carbohydrates, is covered by Chapters 12–15.
This volume illustrates the importance of glycochemistry for the production of biomolecular entities that are innovative regarding structure
and usefulness. Covering from simple sugars to polymeric structures and
to glyco-conjugated biomolecules, this volume also demonstrates the
importance of glyco-structures and technology for innovation in
molecular glycobiology and health. Glycolipid liquid crystals are revised
in Chapter 16 giving a particular attention to their self-assembling
properties, while Chapter 17 shows how glycolipid-containing nanosystems can be applied for novel nanotherapeutic strategies based on
Carbohydr. Chem., 2014, 40, ix–x | ix

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drug/gene delivery systems or on adjuvants for vaccine applications. Also
a new approach to describe furanose ring conformational dynamics is
revealed, based on inherent ring motions rather than arbitrarily
restrictive descriptors, which is better able to describe unsymmetrical
conformations that are lost by pseudo-rotational analysis (Chapter 18).
In Chapter 19, glycofuranosyl-containing conjugates are reviewed as
molecular tools for understanding enzyme activity as well as related
biochemical pathways. Chapters 20 and 21 include conformationally
restricted glycosides as inhibitors of sugar-processing enzymes and receptors, as well as anion receptors having their binding pocket modified
with monosaccharides. It was shown how incorporation of a sugar into
the backbone of a host molecule affects structural and binding properties
of anion receptors.
Therapeutic glycoprotein hormone gonadotropins and anti-cancer
multivalent constructs are documented in Chapters 22 and 23, respectively, while the field of carbohydrate-based vaccines is covered in the next
three chapters, focusing on anti-cancer vaccines (Chapters 24 and 25),
and antibacterial and antifungal vaccines (Chapter 26).
Chapters on the role of mucins and mucin glycosylation in bacterial
adhesion (Chapter 27), and on bioengineering of glucansucrases
(Chapter 28) complete the collection of topics assembled in this volume.
The described achievements in glycochemistry and glycobiology
demonstrate the importance of the glycosciences for innovation in health
and in the corresponding societal challenges facing us. More than that,
´ Lubineau as a scientist, and as a
they show the charisma of Andre
colleague and a friend. Those who had the privilege of working or
collaborating with him confirmed, through their contributions in this
volume, their devotion to his memory.
As editors of the Specialist Periodical Reports: Carbohydrate
Chemistry – Chemical and Biological Approaches, we are very honored to

´ Lubineau.
dedicate this book to the memory of Andre
´lia P. Rauter, Thisbe K. Lindhorst
Ame
and Yves Queneau

x | Carbohydr. Chem., 2014, 40, ix–x


Andre
´ Lubineau: a life dedicated to
carbohydrate chemistry
d
b
Yves Queneau,a,b,c Jacques Auge
´, Ge
´rard Descotes and
e
David Bonnaffe
´

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DOI: 10.1039/9781849739986-FP011

The aim of this volume 40 of Carbohydrate Chemistry, Chemical and
Biological Approaches is to illustrate how wide is the scope of carbohydrate
chemistry, from synthetic methodology to chemical biology, and to
acknowledge Professor Lubineau’s contributions to the field.

´ Lubineau was born on June 12, 1943 in Paris. He was
Andre
soon interested by chemistry and entered the well-known Ecole
´rieure de Chimie de Paris. After his diploma in 1966, he
Nationale Supe
was appointed as an assistant teacher in the university of Paris-Sud,
Orsay where he concomitantly pursued doctoral studies in the field
of nucleosides, under the guidance of Professor Serge David, a great
figure of carbohydrate chemistry who has passed away last year
(1921–2013). After having graduated as Docteur `
es Sciences in 1973,
a

INSA Lyon, ICBMS, Bat J. Verne, 69621 Villeurbanne Cedex, France.
E-mail:
b
Institut de Chimie et de Biochimie Mole´culaires et Supramole´culaires,UMR 5246;
ˆt. Curien,
CNRS, Universite´ de Lyon; Universite´ Lyon 1; INSA-Lyon; CPE-Lyon; Ba
43 Bd du 11 Novembre 1918, F 69622 Villeurbanne, France.
E-mail:
c
Department of Chemistry, University of Hull, Cottingham Road, Hull HU6 7RX, UK
d
University of Cergy-Pontoise, 5 mail Gay-Lussac, Neuville-sur-Oise, 95031
Cergy-Pontoise, France. E-mail:
e
Institut de Chimie Mole´culaire et des Mate´riaux d’Orsay, UMR 8182, LabEx
LERMIT, Bat. 420, Universite´ Paris-Sud, 91405 Orsay Cedex, France.

E-mail: david.bonnaff
Carbohydr. Chem., 2014, 40, xi–xiv | xi

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´ Lubineau together with Serge David then embraced a new field in
Andre
the laboratory, i.e. the exploration of hetero Diels-Alder reaction as a new
tool to build dihydropyrans. Successfully applied to the formation of
disaccharides starting from a monosaccharide dienyl ether, this strategy
was a breakthrough in asymmetric cycloadditions in which the chiral
induction was brought by a chiral diene. They developed this method to
build the D-galacto unit of the antigenic blood groups, such as the A
trisaccharide, on the gram scale. This was the beginning of a long story
concerning the synthesis of oligosaccharides of biological interest,
in close collaboration with Professor Ten Feizi, at Harrow Hospital,
England.
In 1979, interested in widening his knowledge in new methodologies
´ Lubineau’s joined for one year the group of
and total synthesis, Andre
Professor Barry M. Trost in Madison, Wisconsin. After returning to Orsay
and being appointed as Assistant Professor then Full Professor, he started his research on the use of water as solvent for cycloadditions. He

succeeded rapidly in this field and was able to propose a new paradigm,
i.e. all reactions with a negative activation volume should be prone to be
accelerated in water. Confirmed in the case of other reactions such as
aldolisation, Michael and Baylis-Hillman reactions, the acceleration was
demonstrated to originate mainly from an entropic effect. Though green
methodologies were at that time not as fashionable as they are today, he
also showed strong interest for carbohydrate-based synthons and
chemicals.
´ Lubineau and his team joined a mixed
In the mid 1980’s, Andre
academic-industrial consortium which evolved from an initial
collaboration between the University of Lyon and the sugar company
´ghin-Say under the auspices of the CNRS. This consortium gathered
Be
carbohydrate chemists located in the universities of Bordeaux, ClermontFerrand, Grenoble, Lille, Lyon, Orsay and Poitiers, as well as industrial
researchers specialised in chemical and biotechnological sugar processes.
It was also at this time that, in a friendly and stimulating thematic
community including groups such as those of L. Hough and F. W.
Lichtenthaler, the meetings ‘‘Carbohydrates as organic Raw Materials’’
on innovative processes (ultrasound, microwaves, electrochemistry,
enzymes. . .) and industrial applications (detergents, emulsifiers, polymers,
food additives. . .) took place in Darmstadt, Lyon, Wageningen and Vienna.
´ Lubineau with his exceptional experience and his
The presence of Andre
contagious positive spirit was precious to these meetings and to the
´’s percollaborative work achieved within the French consortium. Andre
manent joviality and friendly availability impressed all colleagues during
this 10-year collaboration. We associate all former members of this group,
´’s: Alain Bouchu, Jacques
notably their founders and friends of Andre

´las, Claude Lamy, Julio
Defaye, Alain Deffieux, Bernard Fournet, Jacques Ge
´ Mortreux, Serge Perez and Bernard Thiriet.
Mentech, Andre
From this time, while also deeply involved in projects related to
´ Lubineau never stopped being interested
biological applications, Andre
in the industrial side of glycochemistry. Actually, for both types of
projects, he followed the same strategy, always looking for solutions to
xii | Carbohydr. Chem., 2014, 40, xi–xiv


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problems, not for problems to solutions, always asking: is this new, is
this useful?
´ Lubineau deThe chemoenzymatic approaches Serge David and Andre
´
veloped with Claudine Auge and Christine Le Narvor are perfect
illustrations of the way he conceived challenges in organic synthesis, especially for the total syntheses of bioactive oligosaccharides: ‘‘use chemistry when it is the most efficient route and enzymes when they do the job
better’’. If no clear option was obvious, both methods were explored convinced that the answers would be precious to future generation of glycochemists. This even led to a contest in the lab for determining the most
efficient access to sialic acid, either by extraction from edible swallow’s
´ who was a gourmet), or by aldolisation of N-acetylnests, (enjoyed by Andre
D-mannosamine using sialylaldolase. At that time, extracting sufficient
amounts of glycosyltransferases for the synthesis of an oligosaccharide on
the multi-milligram ‘‘chemist scale’’ was a tedious and time consuming
´ Verbert, Andre

´ Lubineau met the
work. Together with the late Andre
challenge and promoted an interdisciplinary consortium on Recombinant
GlycosylTransferases (the GTREC) and within few years, recombinant a2,6- and a-2,3-sialyltransferases and a-1,3/4-fucosyltransferase were available in Orsay, giving the group a decisive advantage in the synthesis of
Lewis type antigens at the origin of seminal discoveries in the field together with Ten Feizi. In the selectin domain, thanks to his chemist’s eye
which considered a sulphate group mimicking the carboxylate moiety of
sialic acid, he foresaw that the sulphated versions of the Lewis antigens
identified by glycobiologists were not artefacts and demonstrated, through
unambiguous total synthesis, that 3 0 -sulfo-Lewis was the most potent ligand of E-Selectin known at that time.
From sulphated Lewis antigens to glycosaminoglycans (GAG), the path
may seem straightforward. However, addressing the challenge of GAGs
´
molecular diversity was like finding a needle in a haystack, and for Andre
Lubineau, the answer should arise from modern developments in organic synthesis. At that time, combinatorial synthesis was rising and
´ was among the first ones to think about applying this strategy for
Andre
designing complex oligosaccharides. Twenty years later, this paradigm
has been well established although much work remains to be done: this
´ Lubineau’s determination to invent
offers good reasons to follow Andre
new chemistries able to offer solutions to the exciting challenges faced by
carbohydrate chemists.
´ Lubineau will be rememIn addition to his scientific legacy, Andre
bered as a charismatic pedagogue and a demanding and rewarding
mentor by his students. Always pushing them to widen their scientific
culture while continuingly digging deeper into their field to reach the
best possible level once they fly with their own wings, encouraging them
to take risks as he always did throughout his life.

Acknowledgements

We are extremely grateful to the Specialist Periodic Reports Board and to
the Editors of the series Carbohydrate Chemistry, Professor Amelia P. Rauter
Carbohydr. Chem., 2014, 40, xi–xiv | xiii


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and Thisbe K. Lindhorst, for their kind invitation to elaborate this
book dedicated to the memory of Professor Lubineau. We thank all
the authors who have contributed to this volume, and we also associate
´’s former friends, colleagues and students
in this tribute all other Andre
who could not join on this occasion.

xiv | Carbohydr. Chem., 2014, 40, xi–xiv


CONTENTS

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Cover
Tetrahydropyran-enclosed ball-andstick depiction of a glucose
molecule, and (in the background)
part of an a-glycosyl-(1-4)-D-glucose
oligosaccharide and a glycosidase, all

representative of the topics covered
in Carbohydrate Chemistry Chemical
and Biological Approaches.
Cover prepared by R. G. dos Santos.

Preface
Ame´lia P. Rauter, Thisbe K. Lindhorst and Yves Queneau

ix

´ Lubineau: a life dedicated to carbohydrate chemistry
Andre
Yves Queneau, Jacques Auge´, Ge´rard Descotes and David Bonnaffe´
Acknowledgements

xi

C-glycosylation invented by Pr Lubineau’s team: a key-reaction for
innovation in cosmetics
Michel Philippe, Alexandre Cavezza, Patrick Pichaud, Simon Trouille
and Maria Dalko-Csiba
1 Introduction
2 Eco-design of new biomimetic carbohydrates:
fundamental interest of Lubineau’s C-glycosylation
reaction
3 Synthesis of new eco-designed C-glycosyl
derivatives
4 Biological activities of synthesized C-glycosyl derivatives:
major interest of a C-b-xylosyl compound
5 From a biomimetic approach to an industrial

development of a new eco-friendly active ingredient in
cosmetics
Acknowledgements
References

xiii

1

1
2

3
7
7

8
9

Carbohydr. Chem., 2014, 40, xv–xxiii | xv

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Lubineau’s green synthons
Jacques Auge´ and Nade`ge Lubin-Germain
1 Introduction
2 Hetero Diels Alder reactions as a new tool to build
dihydropyrans
3 Glycosylamines
4 The Lubineau reaction: a new access to C-glycosyl
derivatives
5 Conclusion
References

How the polarity of carbohydrates can be used in chemistry
Rui Xu and Yves Queneau
1 Introduction
2 Water solubility assistance for reactions in aqueous
media
3 Carbohydrate-water mixtures as solvents for organic
reactions
4 Polarity as a targeted property in functional biobased
molecules
5 Conclusion
Acknowledgements
References

Sugar-based hydrotropes: preparation, properties and
applications
Vale´rie Molinier and Jean-Marie Aubry
1 Hydrotropes
2 Sugar-based hydrotropes

3 Physico-chemical properties of sugar-based hydrotropes
4 Conclusion
References

From conventional to greener catalytic approaches for
carbohydrates etherification
Mathieu Sauthier, Andre´ Mortreux and Isabelle Suisse
1 Introduction
2 Stoichiometric use of alkyl halides – The Williamson
reaction
3 Salt free catalyzed alkylation reactions
4 Conclusion
Acknowledgements
References
xvi | Carbohydr. Chem., 2014, 40, xv–xxiii

11
11
12
17
22
26
26

31
31
32
37
41
47

47
47

51

51
54
60
69
69

73

73
74
77
93
94
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Exo-glycals as useful tools for anomeric functionalization of
sugars
Nadia Pellegrini-Moı¨se, Myle`ne Richard and Yves Chapleur
1 Introduction

2 Functionalization of exo-glycal double bond
3 Addition reactions on the exo-glycal double bond
4 Conclusions
Abbreviations
Acknowledgement
References

Recent results in synthetic glycochemistry with iron salts at
Orsay-Gif
Jean-Marie Beau, Yann Bourdreux, François-Didier Boyer, Ste´phanie
Norsikian, Dominique Urban, Gilles Doisneau, Boris Vauzeilles,
Alexandra Gouasmat, Aure´lie Leme´tais, Aure´lie Mathieu,
Jean-François Soule´, Arnaud Stevenin and Amandine Xolin
1 Introduction
´ Lubineau’s
2 Brief historical background including Andre
contribution
3 Iron(III) chloride hexahydrate-promoted cascade
cyclization to bioactive dihydropyrans
4 Tandem catalysis with iron(III) chloride hexahydrate
5 Direct synthesis of b-D-N-acetyl glucosamine motifs using
catalytic iron(III) triflate
Conclusion
References

Recent advances in gold-catalyzed glycosylation
Jun Luo and Qian Wan
1 Introduction
2 Gold(III)-catalyzed glycosylation
3 Gold(I)-catalyzed glycosylation

4 Gold-catalyzed glycosylation in natural product
synthesis
5 Conclusions
Acknowledgments
References

99

99
100
105
113
113
114
114

118

118
119
121
127
131
136
136

140
140
140
148

157
157
158
158

Electrochemical glycosylation

160

Alberto Marra and Marie-Christine Scherrmann
1 Introduction
2 Electrooxidative glycosylation

160
160

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3 Electroreductive glycosylation
4 Conclusion
References

174
175

175

Enzymatic thioglycosylation: current knowledge and challenges
Laure Guillotin, Pierre Lafite and Richard Daniellou
1 S-glycosyltransferases
2 Glycoside Hydrolases to thioglycoligases:
A mechanism-based evolution of natural enzymes
3 Conclusions & perspectives
References

178

Anionic oligosaccharides: synthesis and applications
Eric Grand, Jose´ Kovensky, Gwladys Pourceau, Sylvestre Toumieux
and Anne Wadouachi
1 Introduction
2 Synthesis
3 Polysaccharide depolymerisation
4 Applications
5 Concluding remarks
Abbreviations
References

195

Sucrose as chiral platform in the synthesis of macrocyclic
receptors
S!awomir Jarosz, Mykhaylo A. Potopnyk and Micha! Kowalski
1 Introduction
2 Synthesis of sucrose based precursors by selective

modification at primary positions
3 Synthesis and properties of sucrose based
macrocycles
4 Complexation studies
5 Conclusion
Acknowledgments
References

236

Carbohydrate-based dendrimers
Laure L’Haridon and Jean-Maurice Mallet
1 Introduction
2 Assembling full carbohydrate dendrimer by glycosylation
3 Assembling full carbohydrate dendrimer by amide
coupling
xviii | Carbohydr. Chem., 2014, 40, xv–xxiii

178
182
191
192

195
196
221
223
228
229
230

236
238
243
252
253
254
254

257
257
258
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‘Click’ type approaches for assembling full
carbohydrate dendrimer
5 Conclusion
References

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4

Reactivity of allyl and vinyl pentosides in photo-initiated donoracceptor copolymerization
Loı¨c Pichavant, Dominique Harakat, Ce´line Guillermain and
Xavier Coqueret

1 Introduction
2 State-of-art for carbohydrate-based monomers
3 Homopolymerization and copolymerization of
vinyl and allyl ethers
4 Donor-acceptor copolymerization of allyl and vinyl
pentosides
5 Conclusion
6 Perspectives
Acknowledgements
References

Polyester functionalized carbohydrates via organocatalyzed ringopening polymerization
Yong Miao, Andre´ Mortreux and Philippe Zinck
1 Introduction
2 Polyesters functionalized mono-, di- and
tri-saccharides via organocatalyzed ring-opening
polymerization
3 Polyesters functionalized cyclodextrins (CD) via
organocatalyzed ring-opening polymerization
4 Polyesters functionalized polysaccharides via
organocatalyzed ring-opening polymerization
5 Conclusion
References

263
267
267

270

270
271
275
278
293
294
294
294

298

298
300

302
305
308
309

Liquid crystal glycolipids

312

John Goodby, Stephen Cowling, Edward Davis and Yves Queneau
1 Introduction
2 Lamellar phases
3 Hexagonal (columnar) phases
4 Cubic phases – micellar and bicontinuous
5 Complex systems
6 Conclusion

Acknowledgements
References

312
316
325
332
333
337
338
338

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Glycolipid-based nanosystems for the delivery of drugs,
genes and vaccine adjuvant applications
Thierry Benvegnu, Loı¨c Lemie`gre, Caroline Ballet, Yvan Portier and
Daniel Plusquellec
1 Introduction
2 Glycolipid-based drug delivery nanosystems
3 Glycolipid-based gene delivery nanosystems
4 Glycolipid-based adjuvants for vaccine
nanosystems
5 Conclusion

Abbreviations
References

Ring dihedral Principal Component Analysis of furanose
conformation
Claire Coiffier, Chantal Barberot, Jean-Marc Nuzillard, Peter
Goekjian, Eric He´non and Arnaud Haudrechy
1 Introduction
2 The Altona model: scope and limitations
3 Results for static quantum mechanics investigations
of C-xylosyl compounds
4 Results for classical and quantum molecular dynamics
investigations for b-D-xylosyl derivatives
5 Dihedral PCA on the five endocyclic angles of the
dihydroxylated b-D-xylosyl derivatives: an orientation table
to fully explore the conformational landscape
6 Conclusions and perspectives
Computational details
Acknowledgements
References

How recent knowledge on furano-specific enzymes has
renewed interest for the synthesis of glycofuranosyl-containing
conjugates
Vincent Ferrie`res, Caroline Nugier-Chauvin, Laurent Legentil and
Sylvain Tranchimand
1 Introduction
2 Furanosyl conjugates and mutases
3 Furanosyl conjugates and transferases and
polymerases

4 Glycofuranoside hydrolases as green biocatalysts for the
synthesis of furanosides
5 Conclusion
References
xx | Carbohydr. Chem., 2014, 40, xv–xxiii

341

341
344
359
367
372
373
374

378

378
380
382
385
388

394
395
397
398

401

401
402
405
411
413
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Conformationally restricted glycoside derivatives as
mechanistic probes and/or inhibitors of sugar processing enzymes
and receptors
Carine Maaliki, Charles Gauthier, Olivier Massinon, Ram Sagar,
Ste´phane P. Vincent and Yves Ble´riot
1 Introduction
2 Conformationally restricted sugar analogues targeting
glycosidases
3 Constrained glycosides as conformational probes for
non-hydrolytic biochemical processes
4 Conclusions
References

Sugar decorated receptors for chiral anions
Jaros!aw M. Granda and Janusz Jurczak
1 Introduction

2 Monosaccharides in anion binding
3 Sugar decorated anion receptors in chiral recognition
4 Conclusion
Acknowledgements
References

418

418
419
429
437
438

445
445
448
453
458
459
459

Carbohydrate-targeted optimization of therapeutic gonadotropins
Sandrine Donadio-Andre´i, Nassima El Maı¨, Magali Nicollo and
Catherine Ronin
1 Introduction
2 Physiology of gonadotropins
3 Structure of gonadotropins
4 Therapeutic use of gonadotropins
5 Bioactivity of gonadotropins

6 Engineering recombinant gonadotropins
7 Conclusions
References

461

Multivalent glycidic constructs toward anti-cancer therapeutics
Francesco Nicotra, Luca Gabrielli, Davide Bini, Laura Russo,
Antonella Sgambato and Laura Cipolla
1 Carbohydrate-based anticancer therapeutics: general
considerations
2 Multivalent glycidic constructs
3 Glyco-nanotools for cancer therapy
4 Conclusion
References

491

461
461
463
468
471
474
483
484

491
493
497

502
503

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Tumour-associated glycopeptide antigens and their modification
in anticancer vaccines
Sebastian Hartmann, Bjo¨rn Palitzsch, Markus Glaffig and Horst Kunz
1 Introduction
2 Synthesis of glycosyl amino acid building blocks
3 Solid-phase syntheses of tumour-associated mucin
glycopeptide antigens
4 Fully synthetic two- and three-component glycopeptide
vaccines
5 Vaccines obtained by conjugation of glycopeptide
antigens to carrier proteins
6 Conclusion
References

Development of cancer vaccines from fully synthetic mucin-based
glycopeptide antigens. A vision on mucins from the bioorganic
chemistry perspective
´ndez-Tejada and Samuel J. Danishefsky
Alberto Ferna

1 Introduction
2 Synthetic strategies for the preparation of mucin-related
glycopeptide vaccines
3 Synthesis and evaluation of antigen clusters as mucin
mimics for glycopeptide-based cancer vaccines
4 Conclusion
References

506

506
507
512
517
522
529
530

533

533
535
540
560
560

Antibacterial and antifungal vaccines based on synthetic
oligosaccharides
Yury Valde´s Balbin, Maria C. Rodrı´guez and Vicente Verez Bencomo
1 Introduction

2 Bacterial meningitis and pneumonia
3 Diarrheal disease
4 Hospital-acquired infections
5 Fungal disease
6 Mycobacterium tuberculosis
7 Borrelia burgdorferi
8 Concluding remarks
References

564
565
578
581
585
586
588
588
588

Epithelial mucins and bacterial adhesion

596

Florent Colomb, Catherine Robbe-Masselot, Sophie Groux-Degroote,
Julie Bouckaert, Philippe Delannoy and Jean-Claude Michalski
1 Introduction

596

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2
3
4

Structure of epithelial mucin O-glycans
Biosynthesis of epithelial mucin O-glycan chains
Tissue and physio-pathological specific glycosylation
repertoire of mucins
5 Role of mucin glycans in bacterial adhesion
6 Conclusion
Abbreviations
Acknowledgement
References

Successes in engineering glucansucrases to enhance
glycodiversification
David Daude´, Isabelle Andre´, Pierre Monsan and
Magali Remaud-Sime´on
1 Introduction
2 Random approach for glucansucrase overproduction or
engineering

3 Structure-based engineering of glucansucrases
4 Screening methods applied to detect novel or improved
glucansucrases
5 Prospects
References

596
599
608
609
615
616
616
616

624

625
631
635
639
640
641

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Published on 20 March 2014 on | doi:10.1039/9781849739986-00001

C-glycosylation invented by Pr Lubineau’s
team: a key-reaction for innovation in
cosmetics
Michel Philippe,* Alexandre Cavezza, Patrick Pichaud,
Simon Trouille and Maria Dalko-Csiba
DOI: 10.1039/9781849739986-00001

The aim of this chapter is to provide a brief description of why and how the Research
Group of L’Ore
´al, a leading company in cosmetics, has developed on an industrial scale
the C-glycosylation reaction invented by Pr. Lubineau’s team. This first example of industrial development in the world comes from the compliance of this technology with the
principles of green chemistry and the access to original structures of high interest for skin
anti-ageing. From various C-6 and C-5 saccharides, original C-glycosyl derivatives were
synthesized for evaluating their potential role as activators of the biosynthesis of glycosylaminoglycans, polysaccharides that are essential to maintain the mechanical properties
of skin. A b-C-xylosyl derivative combined the highest activity in vitro with confirmation
in vivo. This eco-designed compound was developed using the calculation of green indicators and further marketed under the name of Pro-Xylanet.

1

Introduction

Carbohydrates are of fundamental importance to human skin. For instance, proteoglycans (PGs) and glycosaminoglycans (GAGs) are pivotal in
dermal matrix structure that embeds and sustains collagen fibers network.1 A decrease in the content of GAGs has been linked to changes in
the mechanical properties of human skin with ageing and aged skin

contains less GAGs than young skin.2 GAGs also play a basic role in
structural arrangement of water supply at a molecular level, in cell
adhesion and in signalling through their ability to interact with cells,
growth factors and cytokines at both dermal and epidermal levels. The
major way to maintain dermal matrix structure during ageing or to
restore its functions following alteration is to stimulate GAGs synthesis.
As a consequence, the discovery of a new class of molecules active on the
stimulation of GAGs biosynthesis was a key-objective in the field of antiageing formulae. In most GAGs found in human skin, xylose is an
essential carbohydrate unit. It is involved in their biosynthesis and in
their linking to a protein core via a b-O-glycoside bond between xylose
and the hydroxyl group of a specific serine amino acid of protein core to
form PGs (Fig. 1 and Fig. 2).
´al’s Research
Here, we report a brief description of the work of L’Ore
group in the eco-design of a new class of activators of GAGs biosynthesis
based on xylose and close carbohydrate units.3

L’Ore´al Research & Innovation, 1, Avenue Eugene Schueller, 93600 Aulnay-sous-Bois,
France. E-mail:
Carbohydr. Chem., 2014, 40, 1–10 | 1

c

The Royal Society of Chemistry 2014