Carbohydrate Chemistry ─ Proven Synthetic Methods

Long gone are the days when synthetic publications included parallel preparative experiments to document reproducibility of the experimental protocols and when journals required such documentation. The new Proven Synthetic Methods Series addresses concerns to chemists regarding irreproducibility of synthetic protocols, lack of characterization data for new compounds, and inflated yields reported in many chemical communications—trends that have recently become a serious problem.

Volume One of Carbohydrate Chemistry: Proven Synthetic Methods includes more detailed versions of protocols previously published for the synthesis of oligosaccharides, C-glycosyl compounds, sugar nucleotides, click chemistry, thioglycosides, and thioimidates, among others. The compilation of protocols covers both common and less frequently used synthetic methods as well as examples of syntheses of selected carbohydrate intermediates with general utility. The major focus of this book is devoted to the proper practice of state-of-the-art preparative procedures, including:



References to the starting materials used, reaction setup, work-up and isolation of products, followed by identification and proof of purity of the final material
General information regarding convenience of operation and comments on safety issues
Versatile and practically useful methods that have not received deserved, long-lasting recognition or that are difficult to access from their primary sources
Copies of 1D NMR spectra of compounds prepared, showing purity of materials readers can expect


Exploring carbohydrate chemistry from the academic points of view, the Carbohydrate Chemistry: Proven Synthetic Methods Series provides a compendium of preparatively useful procedures checked by chemists from independent research groups.

Series editor Pavol Kovác, Ph.D., Dr. h.c., with more than 40 years of experience in carbohydrate chemistry and more than 270 papers published in refereed scientific journals or books, is a strong promoter of good laboratory practices and a vocal critic of the publication of experimental chemistry lacking data that allows reproducibility. He obtained an MSc in Chemistry at Slovak Technical University in Bratislava (Slovakia) and a PhD in Organic Chemistry at the Institute of Chemistry, Slovak Academy of Sciences, Bratislava. After postdoctoral training at the Department of Biochemistry, Purdue University, Lafayette, Indiana (R. L. Whistler, advisor), he returned to the Institute of Chemistry and formed a group of synthetic carbohydrate chemists, active mainly in oligosaccharide chemistry, which put the Institute on the map for quality synthetic carbohydrate chemistry.
After relocating to the United States in 1981, he first worked at Bachem, Inc., Torrance, California, where he established a laboratory for production of oligonucleotides for the automated synthesis of DNA. In 1983 he joined the National Institutes of Health, where he is currently one of the Principal Investigators and Chief of the Section on Carbohydrates (NIDDK, Laboratory of Bioorganic Chemistry), the world’s oldest research group continuously working on chemistry, biochemistry, and immunology of carbohydrates, originally established by America’s greatest carbohydrate chemist, Claude S. Hudson. Dr. Kovác’s main interest is in development of conjugate vaccines for bacterial diseases from synthetic carbohydrate antigens.

Synthetic MethodsAcetolysis of 6-Deoxysugars Controlled by Armed–Disarmed EffectEmiliano Bedini, Luigi Cirillo, Ian Cumpstey, and Michelangelo ParrilliNaH/Im2SO2-Mediated Preparation of Hex-2- and Hex-3-Enopyranoside Enol EthersEmanuele Attolino, Giorgio Catelani, Felicia D. Andrea, Lorenzo Guazzelli, and Marie-Christine ScherrmannEnhancement of the Rate of Purdie Methylation by Me2S CatalysisShujie Hou, Thomas Ziegler, and Pavol Kováč Synthesis of Oligosaccharides by Preactivation-Based Chemoselective Glycosylation of Thioglycosyl Donors Zhen Wang, Gilbert Wasonga, Benjamin M. Swarts, and Xuefei HuangThe Use of Hypophosphorous Acid in Radical Chain Deoxygenation of CarbohydratesKarsten Krohn, Ivan Shuklov, Ishtiaq Ahmed, and Alice VossDiphenylsulfoxide-Trifluoromethanesulfonic Anhydride: A Potent Activator for ThioglycosidesJeroen D.C. Codee, Thomas J. Boltje, and Gijsbert A. van der MarelPreparation of Glycosyl Chlorides from Glycopyranoses/Glycofuranoses under Mild ConditionsChih-Wei Chang, Chin-Sheng Chao, Chang-Ching Lin, and Kwok-Kong T. MongC-Glycosylation Starting from Unprotected O-GlycosidesBarbara La Ferla, Laura Cipolla, Wouter Hogendorf, and Francesco NicotraPalladium-Catalyzed Sonogashira Coupling on p-Lodophenyl α-D-Mannopyranoside Tze Chieh Shiao, Jacques Rodrigue, and Mohamed TouaibiaSynthesis by "Click Chemistry" of an α-D-Mannopyranoside Having a 1,4-Disubstituted Triazole as AglyconeTze Chieh Shiao, Denis Giguere, and Mohamed TouaibiaSynthesis of Methyl Glycuronates by Chemo- and Regioselective TEMPO/BAIB-OxidationMarthe T.C. Walvoort, Deepak Sail, Gijsbert A. van der Marel, and Jeroen D.C. CodéeSynthesis of Sugar Nucleotides: A Phosphoramidite ApproachHenrik Gold, Karine Descroix, Jeroen D.C. Codée, and Gijsbert A. van der MarelConversion of N-2,2,2-Trichloroethoxycarbonyl-Protected 2-Aminoglycosides into N-Alkylated 2,3-N,O-Carbonyl GlycosidesThomas Honer, Siegfried Förster, and Thomas ZieglerTIBAL-Induced Rearrangement: Synthesis of gem-DifluorocarbagalactoseJoão Sardinha, Amélia Pilar Rauter, Matthieu Sollogoub, and Yves BleriotPyranose-Fused Butenolides: An Expedient Preparation from Furanose SynthonsNuno M. Xavier, Sebastian Kopitzki, and Amélia Pilar RauterGlycal Dimerization with High DiastereoselectivityAndreas H. Franz, Paul H. Gross, and Katja MichaelRegioselective Debenzylation of C-GlycosylpropeneLaura Cipolla, Barbara La Ferla, Amélia Pilar Rauter, and Francesco NicotraSynthesis of Azido-Functionalized Carbohydrates for the Design of GlycoconjugatesSamy Cecioni, Mehdi Almant, Jean-Pierre Praly, and Sébastien VidalSynthesis of Thioglycosides and Thioimidates from Glycosyl HalidesArchana R. Parameswar, Daniel Mueller, Lin Liu, Cristina De Meo, and Alexei V. DemchenkoSynthesis of Thioglycosides and Thioimidates from PeracetatesArchana R. Parameswar, Akihiro Imamura, and Alexei V. DemchenkoSynthetic Intermediates2-Acetamido-4,6-O-Benzylidene-2-Deoxy-D-GlucopyranoseSergey S. Pertel, Sergey A. Gunchak, Elena S. Kakayan, Vasily Ya. Chirva, and Sébastien VidalSynthesis of 1,3,4,6-Tetra-O-Acetyl-2-Azido-2-Deoxy-α,β-D-Glucopyranose and 2-Azido-4,6-O-Benzylidene-2-Deoxy-α,β-D-Glucopyranose Rafael Ojeda, José Luis de Paz, Ricardo Lucas, Niels Reichardt, Lin Liu, and Manuel Martín-LomasAn Easy Access to 2,3,4,6-Tetra-O-Benzyl-D-Galactopyranose and 2,3,6-Tri-O-Benzyl-D-GlucopyranoseIan Cumpstey, Riccardo Cribiu, and Lorenzo GuazzelliBenzyl 2,3,6,2′,3′,6′-Hexa-O-Benzyl-β-Cellobioside Deepak Sail, Paula Correia da Silva, and Pavol Kováč One-Step Syntheses of 1,2,3,5,6-Penta-O-Benzoyl-α,β-D-Galactofuranose and 1,2,3,5-Tetra-O-Benzoyl-α,β-D-Arabinofuranose Carla Marino, Lucía Gandolfi-Donadío, Carola Gallo Rodriguez, Yu Bai, and Rosa M. de LederkremerStereoselective Synthesis of α-C-Sialyl CompoundsJin-Hwan Kim, Fei Huang, Sayaka Masuko, Deepak Sail, and Robert J. LinhardtSynthesis of O-Acetylated N-Acetylneuraminic Acid GlycalNadezhda Y. Kulikova, Anna M. Shpirt, Alexander Chinarev, and Leonid O. KononovSubstituted Benzyl Glycosides of N-Acetylneuraminic AcidAlexander Chinarev, A.B. Tuzikov, A.I. Zinin, and N.V. BovinSynthesis of 1,5-Di-C-Alkyl 1,5-Iminoxylitols Related to 1-DeoxynojirimycinVincent Chagnault, Philippe Compain, Olivier R. Martin, and Jean-Bernard BehrSynthesis of 1,6-Anhydro-2,3,5-Tri-O-Benzoyl-α-D-Galactofuranose Sujit K. Sarkar, Ambar K. Choudhury, Ján Hirsch, and Nirmolendu RoySynthesis of Prop-2-Ynyl 2,3,4,6-Tetra-O-Acetyl-α-D-MannopyranosideYoann M. Chabre, Tze Chieh Shiao, Sébastien Vidal, and René RoySynthesis of 3-C-(2,3,4,6-Tetra-O-Acetyl-β-D-Galactopyranosyl)prop-1-Ene Subhash Rauthu, Tze Chieh Shiao, Dominique Lafont,and René RoySynthesis of (E)-Methyl 4-(2,3,4,6-Tetra-O-Acetyl-β-D-Galactopyranosyl)but-2-Enoate by Cross-Metathesis Reaction Denis Giguère, Jacques Rodrigue, David Goyard, and René RoyPreparation of O-β-D-GalactopyranosylhydroxylamineTze Chieh Shiao, Alex Papadopoulos, Olivier Renaudet, and René RoySynthesis of 2,3,4,6-Tetra-O-Acetyl-1,5-Anhydro-D-Lyxo-Hex-1-Enitol and Its Conversion into a Hex-3-Enopyranosid-2-Ulose Analogue of LevoglucosenoneVerónica E. Manzano, Evangelina Repetto, María Laura Uhrig, Marek Baráth, and Oscar VarelaEfficient Synthesis of Methyl(Allyl 4-O-Acyl-2,3-Di-O-Benzyl-β-D-Galactopyranosid)uronates from d-Galacturonic AcidAlice Voss, Navid Nemati, Hmayak Poghosyan, Hans-Ulrich Endress, Andreas Krause, and Christian VogelMethyl(Ethyl 2,3,5-Tri-O-Benzoyl-1-Thio-α,β-D-Galactofuranosid)uronateAmbar K. Choudhury, Dirk Michalik, Andreas Gottwald, and Nirmolendu Royp-Tolyl 2,3,5-Tri-O-Benzoyl-1-Thio-α-D-Arabinofuranoside: A Useful Thioglycoside Building Block in the Synthesis of OligoarabinofuranosidesMaju Joe, Yu Bai, Lucía Gandolfi-Donadío, and Todd L. LowaryEthylene Dithioacetals of Common HexosesRui C. Pinto, Marta M. Andrade, Cécile Ouairy, and Maria Teresa BarrosPreparation of 2,6-Anhydro-Aldose TosylhydrazonesMarietta Tóth, László Somsák, and David GoyardPreparation of Exo-Glycals from (C-Glycopyranosyl) formaldehyde TosylhydrazoneMarietta Tóth, Sándor Kun, László Somsak, and David GoyardSynthesis of O-(6-Deoxy-α- and β-l-Galactopyranosyl) Hydroxylamines (α- and β-l-Fucopyranosylhydroxylamines) Isabelle Bossu, Barbara Richichi, Pascal Dumy, and Olivier RenaudetFunctionalization of Terminal Positions of Sucrose—Part I: Synthesis of 2,3,3′,4,4′-Penta-O-Benzylsucrose and Differentiation of the Terminal Positions (1,6,6′) Mateusz Mach, A. Zawisza, B. Lewandowski, and S. JaroszFunctionalization of Terminal Positions of Sucrose—Part II: Preparation of 1′,2,3,3′,4,4′-Hexa-O-Benzylsucrose and 6,6′-Bis-O-(2-Hydroxyethyl)-1′,2,3,3′,4,4′-Hexa-O-BenzylsucroseB. Lewandowski, A. Listkowski, K. Petrova, and S. JaroszIndex