Synthetic glycomes

486 Pages·2019·48.157 MB·English

by  Guan, Wanyi, Li, Lei, Wang, Peng George

Synthetic Glycomes
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Chemical Biology
Editor-­in-c­hief:
Tom Brown, University­of­Oxford,­UK
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5- Kira J. Weissman, Lorraine­University,­France
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65 Sabine Flitsch, University­of­Manchester,­UK
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80 Nick J. Westwood, University­of­St­Andrews,­UK
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97 Titles­in­the­series:
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3 1: High Throughput Screening Methods: Evolution and Refinement
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0. 2: Chemical Biology of Glycoproteins
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oi: 3: Computational Tools for Chemical Biology
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g | 4: Mass Spectrometry in Chemical Biology: Evolving Applications
c.or 5: Mechanisms of Primary Energy Transduction in Biology
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s.r 6: Cyclic Peptides: From Bioorganic Synthesis to Applications
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Synthetic Glycomes
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01 Wanyi Guan
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78 Hebei­Normal­University,­China
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78 Email: [email protected]
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1 Lei Li
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oi: Georgia­State­University,­USA
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5- Preface
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0.1 Carbohydrates (or glycans), one of the most complex and diversified com-
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oi: ponents of all living organisms, were once thought to be more for struc-
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g | tures than for function. Tremendous advances made during the last several
or decades have now made it clear that glycans play critical roles in virtually
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s.rs every aspect of biological processes. In addition, many glycans or glycocon-
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u jugates have proved to have promising diagnostic and therapeutic poten-
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01 The development of routine procedures for automated chemical synthesis
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pril of oligonucleotides and peptides has revolutionized modern biology. Unfor-
A tunately, no general methods are available for the preparation of complex
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d on and the multiple connectivities and branching nature of glycans. Regard-
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h less of tremendous efforts and advances made over the past three decades
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glycans remain relegated to small quantities and specialized laboratories.
Most problematically, the synthesis of even a single complex glycan can
take a well- trained researcher months to years to accomplish. Transforming
strategies and approaches that streamline the synthesis of complex glycans
and are sufficiently robust to permit the preparation of large collections of
various types of glycans (what we name “synthetic glycomes”) are in urgent
demand for glycoscience to move ahead.
The book Synthetic Glycomes contains descriptions of the most recent
advances in accessing complex glycans and glycoconjugates, including
state- of- art approaches such as streamlined chemoenzymatic synthe-
sis, reverse-s ynthesis (separation) and carbohydrate amplification. It also

Chemical Biology No. 11
Synthetic Glycomes
Edited by Wanyi Guan, Lei Li and Peng George Wang
© The Royal Society of Chemistry 2019
Published by the Royal Society of Chemistry, www.rsc.org
v
View Online
vi Preface
summarizes chemical methodologies for generating glycosidic bonds, useful
synthetic enzymes, and commercial availabilities of glycans as well as glycan
microarrays.
The book begins with an introduction to the glycomics and developed
glyco- toolboxes (Chapter 1), as well as an overall summary of chemical
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57 preparation of mammalian glycans (Chapter 3). The following eight chap-
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78 ing the preparation of various mammalian glycans and glycoconjugates,
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78 including N- glycans (Chapters 4 and 5), O- mannosyl glycans (Chapter 6),
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9/ glycopeptides and glycoproteins (Chapter 7), glycosaminoglycans (Chap-
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1 ters 8 and 9), glycosphingolipids (Chapter 10), and human milk oligo-
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oi:1 saccharides (Chapter 11). Chapter 12 describes the synthesis of marine
g | d polysaccharides/oligosaccharides and their derivatives. The next four chap-
or ters present some of the most advanced methodologies in preparing gly-
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s cans other than traditional chemical and enzymatic synthesis, including
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n cially available complex carbohydrates (Chapter 17) and glycan microarrays
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19 (Chapter 19), as well as the application of glycan microarrays in unmasking
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April 2 glyWcaen w fouunlcdt iloiknes t(oC hsainpcteerre 1ly8 )t.hank all authors who contributed to individ-
08 ual chapters. Without their significant efforts, the book would not have been
on possible. We also acknowledge all chapter reviewers, and all staff members
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Wanyi Guan
Lei Li
Peng George Wang
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5- Contents
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0.1 Chapter 1 Introduction: Glycome and the Glyco- toolbox 1
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d on of Carbohydrates 15
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2.1 Introduction 15
2.2 Before Glycosylation 16
2.2.1 Protecting Groups 16
2.2.2 De Novo Syntheses of
Carbohydrates 19
2.3 Amidst Glycosylation 21
2.3.1 Reactivity 21
2.3.2 Stereochemistry 25

Chemical Biology No. 11
Synthetic Glycomes
Edited by Wanyi Guan, Lei Li and Peng George Wang
© The Royal Society of Chemistry 2019
Published by the Royal Society of Chemistry, www.rsc.org
vii
View Online
viii Contents
2.4 Applications Beyond Glycosylation 33
2.4.1 Oligosaccharides and Polysaccharides 33
2.4.2 Glycoconjugates 34
2.4.3 Natural Products 38
2.5 Conclusion 41
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57 Chapter 3 Synthetically Useful Glycosyltransferases for the
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3.4.1 Direct GT- catalyzed Reactions 65
3.4.2 GT- catalyzed Reaction with Sugar
Nucleotide In Situ Regeneration 67
3.4.3 One- pot Multienzyme (OPME) Syntheses
and Enzymatic Modular Assembly (EMA) 68
3.4.4 Whole- cell Catalysis 69
3.4.5 Living Cell Factory 70
3.5 Prospective 72
References 72
Chapter 4 Chemical Synthesis of N- Glycans 83
Yu- Hsuan Lih, Sachin S. Shivatare and Chung- Yi Wu
4.1 Introduction 83
4.2 Chemical Synthesis of N- Glycans 84
4.2.1 Chemical Synthesis of Core Trisaccharide
in N- Glycans 85
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Contents ix
4.2.2 Chemical Synthesis of High- mannose
Type N- Glycans 86
4.2.3 Chemical Synthesis of Hybrid Type
N- Glycans 88
4.2.4 Chemical Synthesis of Complex Type
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5.2.6 Glycosynthases 114
5.3 Enzymatic Preparation of N- Glycans 115
5.4 Chemoenzymatic Preparation of N- Glycan
Libraries 116
5.4.1 A General Strategy for Chemoenzymatic
Synthesis of Asymmetric Complex Type
N- Glycans 116
5.4.2 Core Synthesis/Enzymatic Extension (CSEE)
Strategy for the Synthesis of Hybrid and
Complex Type N- Glycans 118
5.4.3 Enzymatic Synthesis of Complex Type
N- Glycans from One Chemically Prepared
Precursor 119
5.5 Modular Synthesis of All Types of
N- Glycans 120
5.6 Summary 122
References 122
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x Contents
Chapter 6 Chemoenzymatic Synthesis of α- Dystroglycan
O- Mannose Glycans 125
Caicai Meng, Chang- Cheng Liu and Hongzhi Cao
6.1 Introduction 125
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57 6.2.1 Biosynthesis Pathway of O- Mannosyl
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g | d 6.2.5 O- Mannosylated Substrates Beyond
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08 Abbreviations 146
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Glycoproteins 151
Nikesh Narang, Rohit K. Sharma and Hironobu Hojo
7.1 Introduction 151
7.2 Synthesis of Glycopeptide 152
7.2.1 Synthesis of Polypeptide Chain 152
7.2.2 Synthesis of PSGL- 1 153
7.2.3 Synthesis of CD52 155
7.3 Ligation Method 157
7.3.1 Basic Strategies 157
7.3.2 Glycopeptide Thioester Synthesis 158
7.4 Synthesis of O- linked Glycoproteins 160
7.4.1 Synthesis of Antifreeze Glycoprotein 160
7.4.2 Synthesis of MUC2 Model 162
7.4.3 Synthesis of Interleukin- 2 163
7.5 Synthesis of N- linked Glycoprotein 164
7.5.1 Strategies for N- linked Glycoprotein Synthesis 164
7.5.2 Synthesis of Human Interferon- β 165