1st Edition

Carbohydrate Chemistry Proven Synthetic Methods, Volume 2

Edited By Gijsbert van der Marel, Jeroen Codee Copyright 2014
    333 Pages
    by CRC Press

    334 Pages 215 B/W Illustrations
    by CRC Press

    The second volume in the series Carbohydrate Chemistry: Proven Synthetic Methods, Volume 2 offers a collection of synthetic procedures valuable to the practice of synthetic carbohydrate chemistry. The series takes an important and unique approach in that all described procedures have been independently verified as reliable and reproducible. With editors and contributors who are highly respected scientists in the field, this book provides a widely useful reference for both researchers and students, exploring carbohydrate chemistry from both academic and industrial points of view.

    The book begins with an introductory section that offers tricks and tips collected by the series editor from many years of experience working in carbohydrate laboratories. The subsequent chapters present detailed protocols on both specific synthetic transformations and the preparation of common synthetic intermediates, with figures to aid in comprehension. Procedures are described for regioselective benzylidene ring opening reactions, oxidation reactions to provide uronic acids, stereoselective alpha-glucosylation reactions, and more. Protocols for synthetic intermediates of general utility include 3,4,6-tri-O-acetyl-d-galactal, phenyl 4,6-O-benzylidene-1-thio-α-d-mannopyranoside, 1,2-anhydro-3,4,6-tri-O-benzyl-β-d-mannopyranoside, and methyl N-acetylneuraminic acid, among many others.

    Each chapter presents in-depth experimental descriptions for the reported procedures, including reaction setup, reaction conditions, work-up procedures, and purification protocols. The chapters also provide detailed characterization of all products and intermediates as well as copies of the 1H NMR and 13C NMR of the described products and intermediates to indicate the purity of the obtained materials and to serve as a valuable reference for future practitioners.

    This book provides an important starting point to reliably access synthetic carbohydrate materials and as such offers a valuable resource for the synthetic organic chemistry community. Through the streamlined access of well-defined products it provides a thrust to the rapidly growing field of chemical glycobiology.

    Section I: Synthetic Methods

    Highly Stereoselective 1,2-cis-Glycosylations Employing C-2 (S)-(Phenylthiomethyl)benzyl Ether as a Chiral Auxiliary
    Thomas J. Boltje, Randy Benedict, and Geert-Jan Boons

    Regioselective Reductive Openings of 4,6-O-Benzylidene-Type Acetals Using LiAlH4-AlCl3
    Mihály Herczeg, László Lázár, Markus Ohlin, and Anikó Borbás

    A Facile Method for Oxidation of Primary Alcohols to Carboxylic Acids in Carbohydrate Synthesis
    Zhaojun Yin, Steven Dulaney, Gopinath Tiruchinapally, Bo Yang, Guitao Wang and Xuefei Huang

    Ultrasonic Energy Promoted Allylation to Generate 1-C-(2,3,4,6-Tetra-O-benzyl-α-d-glucopyranosyl)prop-2-ene
    Mark Farrell, Ciaran O’Reilly, Dilip V. Jarikote, Paul V. Murphy, and Jani Rahkila

    Synthesis of a Multivalent Glycocyclopeptide Using Oxime Ligation
    Isabelle Bossu, Baptiste Thomas, René Roy, Pascal Dumy, and Olivier Renaudet

    Reductive Amination Methodology for Synthesis of Primary Amines from Unprotected Synthons
    Emma M. Dangerfield, Zhimeng Wu, Mattie S. M. Timmer, and Bridget L. Stocker

    General Preparation of Imidazole-1-sulfonate Esters
    Travis Coyle, Mark B. Richardson, Mitchell Hattie, and Keith A. Stubbs

    Regioselective Monoacylation and Monoalkylation of Carbohydrates Catalyzed by a Diarylborinic Ester
    Doris Lee, Christopher J. Moore, Lina Chan, and Mark S. Taylor

    The Synthesis of Carbamates from Alkenylamines
    Emma M. Dangerfield, Shivali A. Gulab, Bridget L. Stocker, and Mattie S. M. Timmer

    Hydrolysis of Thioglycosides Using Anhydrous N-Iodosuccinimide (NIS) and Trifluoroacetic Acid (TFA)
    Ana R. de Jong, Bas Hagen, Kevin Sheerin, Jeroen D.C. Codée, and Gijsbert A. van der Marel

    Highly Diastereoselective Construction of l-Heptosides by a Sequential Grignard Addition/Fleming-Tamao Oxidation
    Maxime Durka, Kevin Buffet, Tianlei Li, Abdellatif Tikad, Bas Hagen, and Stéphane P. Vincent

    Synthesis of Fluorinated Exo-glycals Mediated by Selectfluor
    Guillaume Eppe, Audrey Caravano, Jérôme Désiré and Stéphane P. Vincent

    A Direct and Stereospecific Approach to the Synthesis of α-Glycosyl Thiols
    Roger A. Ashmus, Lei Zhang, and Xiangming Zhu

    Efficient Microwave-Assisted Synthesis of 1′,2,3,3′,4,4′,6-Hepta-O-benzyl-sucrose and 1′,2,3,3′,4,4′-Hexa-O-benzylsucrose
    M. Teresa Barros, Krasimira T. Petrova, Paula Correia-da-Silva, and Ana-Paula Esteves

    Section II: Synthetic Intermediates

    Oligosaccharide-Salicylaldehyde Derivatives as Precursors of Water-Soluble, Biocompatible Anion Receptors
    Emiliano Bedini, Gianpiero Forte, Ivone Carvalho, Michelangelo Parrilli, and Antonella Dalla Cort

    Allyl 3,4,6-Tri-O-Benzyl-α-d-Mannopyranoside
    Chakree Wattanasiri, Somsak Ruchirawat, Mélanie Platon, and Siwarutt Boonyarattanakalin

    Synthesis of a Spacer-Armed 6′-Sialyl-N-Acetyllactosamine
    G. V. Pazynina, A. A. Chinarev, A. B. Tuzikov, V. V. Nasonov, N. N. Malysheva, and N. V. Bovin

    Synthesis of β-(1→3)-mannobiose
    Sebastien Picard, Mikael Thomas, Anne Geert Volbeda, Xavier Guinchard, and David Crich

    Phenyl 4,6-O-Benzylidene-1-thio-α-d-mannopyranoside
    Min Huang, Huu-Anh Tran, Luis Bohé, and David Crich

    Synthesis of 1,3,4,6-Tetra-O-acetyl-α-d-glucopyranose Revisited
    Swati S. Nigudkar, Scott J. Hasty, Monica Varese,Papapida Pornsuriyasak, and Alexei V. Demchenko

    Synthesis of 4,6-O-Benzylidene Acetals of Methyl α-d-Glucopyranoside, Ethyl 1-Thio-β-d-gluco- and Galactopyranoside
    Papapida Pornsuriyasak, Jagodige P. Yasomanee, Edward I. Balmond, Cristina De Meo, and Alexei V. Demchenko

    Synthesis of α-N-Acetylneuraminic Acid Methyl Glycoside
    Leonid O. Kononov, Alexander Chinarev,Alexander I. Zinin, and Chase Gobble

    Synthesis of Ammonium 3-Deoxy-d-manno-oct-2-ulopyranosylonate (Ammonium Kdo)
    Hannes Mikula, Markus Blaukopf, Georg Sixta, Christian Stanetty, and Paul Kosma

    Synthesis and Characterization of Tetra-O-propargyl Pentaerythritol
    Peng Xu, Riccardo Castelli, and Pavol Kováč

    Improved Synthesis of Ethyl (2,3,4,6-Tetra-O-acetyl-β-dgalactopyranosyl)-(1→3)-4,6-O-benzylidene-2-deoxy-1-thio-2-trichloroacetamido-β-d-glucopyranoside
    Sameh E. Soliman, Zoeisha Chinoy, and Pavol Kováč

    Synthesis of α-d-Galactofuranosyl Phosphate
    Carla Marino, Cecilia Attorresi, Silvia Miranda, and Rosa M. de Lederkremer

    Synthesis of 1,2 4,5-Di-O-(3,3-pentylidene)arabitol via Kinetic Acetal Formation
    Konrad Hohlfeld, Solen Josse, Sylvain Picon, and Bruno Linclau

    Shino Manabe, Qingju Zhang, and Yukishige Ito

    Synthesis of Glucosyl C-1 Dihalides from Tetra-O-acetyl-β-d-glucopyranosyl Chloride
    Jean-Pierre Praly and Tze Chieh Shiao

    Synthesis of 3,4,6-Tri-O-acetyl-d-galactal
    Tze Chieh Shiao, Jacques Rodrigue, Olivier Renaudet, and René Roy

    Efficient Synthesis of Hepta-O-acetyl-β-lactosyl Azide via Phase Transfer Catalysis
    Tze Chieh Shiao, Denis Giguère,Nicolas Galanos, and René Roy

    Synthesis of 2,3,4,6-Tetra-O-acetyl-α-d-mannopyranosyl Azide
    Tze Chieh Shiao, Yoann M. Chabre, Myriam Roy, and René Roy

    Synthesis of Phenyl 2,3,4,6-Tetra-O-acetyl-1-thio-β-d-galactopyranoside
    Tze Chieh Shiao, Denis Giguère, Patrick Wisse, and René Roy

    An Alternative, Large-Scale Synthesis of 1,2 5,6-Di-Oisopropylidene-α-d-ribo-hex-3-ulofuranose
    Pāvels Ostrovskis, Jevgeņija Mackeviča, Viktors Kumpiņš, Óscar López, and Māris Turks


    Series Editor:

    Pavol Kováč, Ph.D., Dr. h.c., obtained his Ph.D. in organic chemistry at the Institute of Chemistry, Slovak Academy of Sciences, Bratislava. Dr. Kováč is a strong promoter of good laboratory practices and a vocal critic of the publication of experimental chemistry lacking data that allow reproducibility. He has more than 40 years of experience in carbohydrate chemistry and over 280 papers published in refereed scientific journals, several patents, and book chapters. He joined the National Institutes of Health (NIH) (Bethesda, Maryland) in 1983 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, it was originally established by the American carbohydrate chemist Claude S. Hudson. Kováč’s main interest is the development of conjugate vaccines for bacterial diseases from synthetic carbohydrate antigens.

    Volume Two Editors:

    Jeroen Codée
    obtained his Ph.D. from Leiden University, the Netherlands, under the guidance of Jacques van Boom and Stan van Boeckel in 2004. Codée then moved to the Eidgenossische Technische Hochschule (ETH) Zurich, Switzerland, for a two-year post-doctoral stay with Peter Seeberger. He subsequently returned to Leiden University, where he is now an associate professor in bio-organic chemistry. His research focuses on glycochemistry and glycobiology, ranging from fundamental organic synthesis to vaccine/drug development and the development of glycobiology tools. He has authored or co-authored more than 70 publications and seven book chapters.

    Gijs van der Marel conducted his Ph.D. studies on DNA chemistry with Jacques van Boom and received his Ph.D. degree in 1981 from Leiden University, the Netherlands. He has remained associated with this university, where he is now a full professor in synthetic organic chemistry. He has supervised more than 70 Ph.D. students and authored or co-authored over 700 papers. His research focuses on all synthetic aspects of biopolymers, including nucleic acids, peptides, and carbohydrates, and hybrids and analogues thereof.

    '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.