1st Edition

Carbohydrate Chemistry Proven Synthetic Methods, Volume 1

Edited By Pavol Kováč Copyright 2012
    468 Pages 463 B/W Illustrations
    by CRC Press

    468 Pages 463 B/W Illustrations
    by CRC Press

    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.

    Synthetic Methods
    Acetolysis of 6-Deoxysugars Controlled by Armed–Disarmed Effect
    Emiliano Bedini, Luigi Cirillo, Ian Cumpstey, and Michelangelo Parrilli
    NaH/Im2SO2-Mediated Preparation of Hex-2- and Hex-3-Enopyranoside Enol Ethers
    Emanuele Attolino, Giorgio Catelani, Felicia D. Andrea, Lorenzo Guazzelli, and Marie-Christine Scherrmann
    Enhancement of the Rate of Purdie Methylation by Me2S Catalysis
    Shujie 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 Huang
    The Use of Hypophosphorous Acid in Radical Chain Deoxygenation of Carbohydrates
    Karsten Krohn, Ivan Shuklov, Ishtiaq Ahmed, and Alice Voss
    Diphenylsulfoxide-Trifluoromethanesulfonic Anhydride: A Potent Activator for Thioglycosides
    Jeroen D.C. Codee, Thomas J. Boltje, and Gijsbert A. van der Marel
    Preparation of Glycosyl Chlorides from Glycopyranoses/Glycofuranoses under Mild Conditions
    Chih-Wei Chang, Chin-Sheng Chao, Chang-Ching Lin, and Kwok-Kong T. Mong
    -Glycosylation Starting from Unprotected O-Glycosides
    Barbara La Ferla, Laura Cipolla, Wouter Hogendorf, and Francesco Nicotra
    Palladium-Catalyzed Sonogashira Coupling on p-Lodophenyl α-D-Mannopyranoside Tze Chieh Shiao, Jacques Rodrigue, and Mohamed Touaibia
    Synthesis by "Click Chemistry" of an α-D-Mannopyranoside Having a 1,4-Disubstituted Triazole as Aglycone
    Tze Chieh Shiao, Denis Giguere, and Mohamed Touaibia
    Synthesis of Methyl Glycuronates by Chemo- and Regioselective TEMPO/BAIB-Oxidation
    Marthe T.C. Walvoort, Deepak Sail, Gijsbert A. van der Marel, and Jeroen D.C. Codée
    Synthesis of Sugar Nucleotides: A Phosphoramidite Approach
    Henrik Gold, Karine Descroix, Jeroen D.C. Codée, and Gijsbert A. van der Marel
    Conversion of N-2,2,2-Trichloroethoxycarbonyl-Protected 2-Aminoglycosides into N-Alkylated 2,3-N,O-Carbonyl Glycosides
    Thomas Honer, Siegfried Förster, and Thomas Ziegler
    TIBAL-Induced Rearrangement: Synthesis of gem-Difluorocarbagalactose
    João Sardinha, Amélia Pilar Rauter, Matthieu Sollogoub, and Yves Bleriot
    Pyranose-Fused Butenolides: An Expedient Preparation from Furanose Synthons
    Nuno M. Xavier, Sebastian Kopitzki, and Amélia Pilar Rauter
    Glycal Dimerization with High Diastereoselectivity
    Andreas H. Franz, Paul H. Gross, and Katja Michael
    Regioselective Debenzylation of C-Glycosylpropene
    Laura Cipolla, Barbara La Ferla, Amélia Pilar Rauter, and Francesco Nicotra
    Synthesis of Azido-Functionalized Carbohydrates for the Design of Glycoconjugates
    Samy Cecioni, Mehdi Almant, Jean-Pierre Praly, and Sébastien Vidal
    Synthesis of Thioglycosides and Thioimidates from Glycosyl Halides
    Archana R. Parameswar, Daniel Mueller, Lin Liu, Cristina De Meo, and Alexei V. Demchenko
    Synthesis of Thioglycosides and Thioimidates from Peracetates
    Archana R. Parameswar, Akihiro Imamura, and Alexei V. Demchenko

    Synthetic Intermediates
    Sergey S. Pertel, Sergey A. Gunchak, Elena S. Kakayan, Vasily Ya. Chirva, and Sébastien Vidal
    Synthesis 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-Lomas
    An Easy Access to 2,3,4,6-Tetra-O-Benzyl-D-Galactopyranose and 2,3,6-Tri-O-Benzyl-D-Glucopyranose
    Ian Cumpstey, Riccardo Cribiu, and Lorenzo Guazzelli
    Benzyl 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 Lederkremer
    Stereoselective Synthesis of α-C-Sialyl Compounds
    Jin-Hwan Kim, Fei Huang, Sayaka Masuko, Deepak Sail, and Robert J. Linhardt
    Synthesis of O-Acetylated N-Acetylneuraminic Acid Glycal
    Nadezhda Y. Kulikova, Anna M. Shpirt, Alexander Chinarev, and Leonid O. Kononov
    Substituted Benzyl Glycosides of N-Acetylneuraminic Acid
    Alexander Chinarev, A.B. Tuzikov, A.I. Zinin, and N.V. Bovin
    Synthesis of 1,5-Di-C-Alkyl 1,5-Iminoxylitols Related to 1-Deoxynojirimycin
    Vincent Chagnault, Philippe Compain, Olivier R. Martin, and Jean-Bernard Behr
    Synthesis of 1,6-Anhydro-2,3,5-Tri-O-Benzoyl-α-D-Galactofuranose Sujit K. Sarkar, Ambar K. Choudhury, Ján Hirsch, and Nirmolendu Roy
    Synthesis of Prop-2-Ynyl 2,3,4,6-Tetra-O-Acetyl-α-D-Mannopyranoside
    Yoann M. Chabre, Tze Chieh Shiao, Sébastien Vidal, and René Roy
    Synthesis 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 Roy
    Synthesis 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 Roy
    Preparation of O-β-D-Galactopyranosylhydroxylamine
    Tze Chieh Shiao, Alex Papadopoulos, Olivier Renaudet, and René Roy
    Synthesis 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 Levoglucosenone
    Verónica E. Manzano, Evangelina Repetto, María Laura Uhrig, Marek Baráth, and Oscar Varela
    Efficient Synthesis of Methyl(Allyl 4-O-Acyl-2,3-Di-O-Benzyl-β-D-Galactopyranosid)uronates from d-Galacturonic Acid
    Alice Voss, Navid Nemati, Hmayak Poghosyan, Hans-Ulrich Endress, Andreas Krause, and Christian Vogel
    Methyl(Ethyl 2,3,5-Tri-O-Benzoyl-1-Thio-α,β-D-Galactofuranosid)uronate
    Ambar K. Choudhury, Dirk Michalik, Andreas Gottwald, and Nirmolendu Roy
    -Tolyl 2,3,5-Tri-O-Benzoyl-1-Thio-α-D-Arabinofuranoside: A Useful Thioglycoside Building Block in the Synthesis of Oligoarabinofuranosides
    Maju Joe, Yu Bai, Lucía Gandolfi-Donadío, and Todd L. Lowary
    Ethylene Dithioacetals of Common Hexoses
    Rui C. Pinto, Marta M. Andrade, Cécile Ouairy, and Maria Teresa Barros
    Preparation of 2,6-Anhydro-Aldose Tosylhydrazones
    Marietta Tóth, László Somsák, and David Goyard
    Preparation of Exo-Glycals from (C-Glycopyranosyl) formaldehyde Tosylhydrazone
    Marietta Tóth, Sándor Kun, László Somsak, and David Goyard
    Synthesis of O-(6-Deoxy-α- and β-l-Galactopyranosyl) Hydroxylamines (α- and β-l-Fucopyranosylhydroxylamines) Isabelle Bossu, Barbara Richichi, Pascal Dumy, and Olivier Renaudet
    Functionalization 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. Jarosz
    Functionalization 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-Benzylsucrose
    B. Lewandowski, A. Listkowski, K. Petrova, and S. Jarosz


    Series editor Pavol Kováč, 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. Kováč’s main interest is in development of conjugate vaccines for bacterial diseases from synthetic carbohydrate antigens.

    'The contributors are the best scientists in the field and the series editor is highly respected. The volumes will ... be of use to undergraduates involved in carbohydrate workshops.'
    Alexei Demchenko, Associate Professor of Chemistry and Biochemistry, Director of Graduate Studies, University of Missouri – St. Louis.

    ‘This essential book series, focused on carbohydrate synthesis, starts with a dedication to Nobel Laureate Sir John W. Cornforth, who is credited with the first public criticism of what he pictured as ‘pouring a large volume of unpurified sewage into the chemical literature.’1 Unfortunately, this issue is not limited to the field of chemistry as many high profile cases of irreproducible experiments have led to alarms being set off even in the popular press.2 This series then serves as the much-needed water treatment plants – places where the reader can be guaranteed a good clean reproducible experiment. … at least now chemists with or without expertise in carbohydrates can count on finding reliable procedures to make sugar-based compounds at one scale – a major achievement. Not only should current practitioners gain back time lost in attempts to properly reconstruct experimental procedures, but these procedures should also allow more creative scientists to contribute to this growing area.

    1. Cornforth JW. Austr. J. Chem. 1993;46:157e70.
    2. For example, see Unreliable research: trouble at the lab. Econ. October 19, 2013.’

    Nicola L.B. Pohl, Indiana University, Department of Chemistry, Bloomington, IN, USA, for Carbohydrate Research, http://dx.doi.org/10.1016/j.carres.2015.04.007.