Domino and Intramolecular Rearrangement Reactions as Advanced Synthetic Methods in Glycoscience

Zbigniew J. Witczak obtained his Ph.D. from Medical University of Lodz, Faculty of Pharmacy (Poland). After postdoctoral work at Purdue University, he worked in industry (A. E.Staley), then joined the faculty of the School of Pharmacy at University of Connecticut. He moved to Wilkes University, Nesbitt School of Pharmacy in 2000, where he is Full Professor. He has published over ninety research papers and holds six patents in the fields of carbohydrate medicinal and biological chemistry. In 2000 he was awarded the Melville L. Wolfrom Award of the ACS Division of Carbohydrate Chemistry. His research interests are in the area of carbohydrate Synthons including Levoglucosenone and L-Arabinose as template for carbohydrate based therapeutics.Roman Bielski obtained his Ph.D. at the Institute of Organic Chemistry, Polish Academy of Sciences. He is currently a Senior Scientist in Value Recovery, Inc., a partner in Cheminnolab, LLC, and adjunct professor at Wilkes University. Recently he (with M. Tencer) developed a method of enantiomers' resolution requiring no use of chiral compounds. His research interests are origin of homochirality, modification of carbohydrates, solutions to environmental issues and sustainability. He published over three dozen papers and co-authored 18 patents.

• Foreword xiiiPreface xvAcknowledgments xixList of Contributors xxiAbbreviations xxv1 Introduction to Asymmetric Domino Reactions 1Hélène Pellissier1.1 Introduction, 11.2 Asymmetric Domino Reactions using Chiral Carbohydrate Derivatives, 31.2.1 Stereocontrolled Domino Reactions of Chiral Carbohydrate Derivatives, 31.2.2 Enantioselective Domino Reactions Catalyzed by Chiral Carbohydrate Derivatives, 81.3 Conclusions, 12References, 132 Organocatalyzed Cascade Reaction in Carbohydrate Chemistry 16Benjamin Voigt and Rainer Mahrwald2.1 Introduction, 162.2 C-Glycosides, 172.3 Amine-Catalyzed Knoevenagel-Additions, 202.4 Multicomponent Reactions, 322.5 Amine-Catalyzed Cascade Reactions of Ketoses with 1,3-Dicarbonyl Compounds, 402.6 Conclusions, 44References, 443 Reductive Ring-Opening in Domino Reactions of Carbohydrates 49Raquel G. Soengas, Sara M. Tomé, and Artur M. S. Silva3.1 Introduction, 493.2 Bernet–Vasella Reaction, 503.2.1 Domino Reductive Fragmentation/Reductive Amination, 513.2.2 Domino Reductive Fragmentation/Barbier-Type Allylation, 523.2.3 Domino Reductive Fragmentation/Barbier-Type Propargylation, 573.2.4 Domino Reductive Fragmentation/Vinylation, 593.2.5 Domino Reductive Fragmentation/Alkylation, 603.2.6 Domino Reductive Fragmentation/Olefination, 613.2.7 Domino Reductive Fragmentation/Nitromethylation, 623.3 Reductive Ring Contraction, 643.3.1 Ring Opening/Ketyl-Olefin Annulation, 653.3.2 Ring Opening/Intramolecular Carbonyl Alkylation, 693.4 Conclusions, 73References, 734 Domino Reactions Toward Carbohydrate Frameworks for Applications Across Biology and Medicine 76Vasco Cachatra and Amélia P. Rauter4.1 Introduction, 764.2 Domino Reactions Toward Butenolides Fused to Six-Membered Ring Sugars and Thio Sugars, 774.3 Exploratory Chemistry for Amino Sugars’ Domino Reactions, 804.4 Domino Reactions Toward Sugar Ring Contraction, 844.4.1 Pyrano–Furano Ring Contraction, 844.4.2 Ring Contraction of Furans to Oxetanes, 874.5 Macrocyclic Bislactone Synthesis via Domino Reaction, 914.6 Sugar Deoxygenation by Domino Reaction, 924.7 Conclusions, 94References, 945 Multistep Transformations of BIS-Thioenol Ether-Containing Chiral Building Blocks: New Avenues in Glycochemistry 97Daniele D’Alonzo, Giovanni Palumbo, and Annalisa Guaragna5.1 Introduction, 975.2 (5,6-Dihydro-1,4-dithiin-2-yl)Methanol: Not Simply a Homologating Agent, 985.3 Sulfur-Assisted Multistep Processes and Their Use in the De Novo Synthesis of Glycostructures, 1015.3.1 Three Steps in One Process: Double Approach to 4-Deoxy l-(and d-)-Hexoses, 1015.3.2 Five Steps in One Process: The Domino Way to l-Hexoses (and Their Derivatives), 1025.3.3 Up to Six Steps in One Process: 4′-Substituted Nucleoside Synthesis, 1055.3.4 Eight Steps in One Process: Beyond Achmatowicz Rearrangement, 1095.4 Concluding Remarks, 1115.5 Acknowledgments, 111References, 1116 Thio-Click and Domino Approach to Carbohydrate Heterocycles 114Zbigniew J. Witczak and Roman Bielski6.1 Introduction, 1146.2 Classification and Reaction Mechanism, 1146.3 Conclusions, 119References, 1207 Convertible Isocyanides: Application in Small Molecule Synthesis, Carbohydrate Synthesis, and Drug Discovery 121Soumava Santra, Tonja Andreana, Jean-Paul Bourgault, and Peter R. Andreana7.1 Introduction, 1217.2 Convertible Isocyanides, 1257.2.1 CIC Employed in the Ugi Reaction, 1257.2.2 Resin-Bound CICs, 1677.2.3 CIC Employed in the Ugi–Smile Reaction, 1727.2.4 CIC Employed in the Joulli´e–Ugi Reaction, 1727.2.5 CIC Employed in the Passerini Reaction, 1757.2.6 CIC Employed in the Groebke–Blackburn–Bienaym´e Reaction, 1787.2.7 CIC Employed in the Diels–Alder Reaction, 1827.2.8 Monosaccharide Isocyanides Employed in the Ugi and Passerini Reaction, 1837.2.9 Methyl isocyanide in the Preparation of the Hydroxy DKP Thaxtomin A, 1867.3 Conclusions, 187References, 1878 Adding Additional Rings to the Carbohydrate Core: Access via (SPIRO) Annulation Domino Processes 195Daniel B. Werz8.1 Introduction, 1958.2 Spiroketals via a Domino Oxidation/Rearrangement Sequence, 1968.3 Chromans and Isochromans via Domino Carbopalladation/Carbopalladation/Cyclization Sequence, 200References, 2089 Introduction to Rearrangement Reactions in Carbohydrate Chemistry 209Zbigniew J. Witczak and Roman Bielski9.1 Introduction, 2099.2 Classification, 2109.3 Chapman Rearrangement, 2119.4 Hofmann Rearrangement, 2119.5 Cope Rearrangement, 2119.6 Ferrier Rearrangement, 2129.7 Claisen Rearrangement, 2139.8 Overman Rearrangement, 2149.9 Baeyer–Villiger Rearrangement, 2159.10 Ring Contraction, 2159.11 Conclusions, 216References, 21710 Rearrangement of a Carbohydrate Backbone Discovered “En Route” to Higher-Carbon Sugars 219S³awomir Jarosz, Anna Osuch-Kwiatkowska, Agnieszka Gajewska, and Maciej Cieplak10.1 Introduction, 21910.2 Rearrangements Without Changing the Sugar Skeleton, 22010.3 Rearrangements Connected with the Change of Sugar Unit(s), 22110.4 Rearrangements Changing the Structure of a Sugar Skeleton, 22410.5 Rearrangement of the Sugar Skeleton Discovered En Route to Higher-Carbon Sugars, 22610.5.1 Synthesis of Higher-Carbon Sugars by the Wittig-Type Methodology, 22610.5.2 The Acetylene/Vinyltin Methodology in the Synthesis of HCS, 22710.5.3 The Allyltin Methodology in the Synthesis of HCS, 22710.5.4 Rearrangement of the Structure of HCS, 23010.5.5 Synthesis of Polyhydroxylated Carbocyclic Derivatives with Large Rings, 23510.6 Conclusions, 237Acknowledgments, 237References, 23711 Novel Levoglucosenone Derivatives 240Roman Bielski and Zbigniew J. Witczak11.1 Introduction, 24011.2 Additions to the Double Bond of the Enone System Leading to the Formation of New Rings, 24111.3 Reductions of the Carbonyl Group Followed by Various Reactions of the Formed Alcohol, 24111.4 Functionalization of the Carbonyl Group by Forming Carbon-Nitrogen Double Bonds (Oximes, Enamines, Hydrazines), 24211.5 Additions (But Not Cycloadditions) (Particularly Michael Additions) to the Double Bond of the Enone, 24311.6 Enzymatic Reactions of Levoglucosenone, 24411.7 High-Tonnage Products from Levoglucosenone, 24411.7.1 Overman and Allylic Xanthate Rearrangement, 24511.8 Conclusions, 246References, 24712 The Preparation and Reactions of 3,6-Anhydro-d-Glycals 248Vikram Basava, Emi Hanawa, and Cecilia H. Marzabadi12.1 Introduction, 24812.2 Preparation of 3,6-Anhydro-d-Glucal Under Reductive Conditions, 25012.3 Addition Reactions of 3,6-Anhydro-d-Glucal, 25112.4 Preparation of 6-O-Tosyl-d-Galactal and Reduction with Lithium Aluminum Hydride, 25212.5 Conclusions, 254References, 25413 Ring Expansion Methodologies of Pyranosides to Septanosides and Structures of Septanosides 256Supriya Dey, N. Vijaya Ganesh, and N. Jayaraman13.1 Introduction, 25613.2 Synthesis of Septanosides, 25813.2.1 Synthesis of Septanosides via Hemiacetal Formation, 25813.2.2 Knoevenagel Condensation, 26013.2.3 Baeyer–Villiger Oxidation of Cyclohexanone Derivatives, 26013.2.4 Electrophile-Induced Cyclization, 26013.2.5 Metal-Catalyzed Cyclization, 26113.2.6 Nicolas–Ferrier Rearrangements, 26213.2.7 Ring Opening of Carbohydrate-Derived Cyclopropanes, 26313.2.8 Ring Opening of Glycal-Derived 1,2-Cyclopropane, 26313.2.9 Ring Opening of Oxyglycal Derived 1,2-Cyclopropane, 26513.2.10 Functionalization of Oxepines, 26813.3 Structure and Conformation of Septanosides, 26913.3.1 Solid-State Structures and Conformations, 27013.3.2 Solution-Phase Conformations, 27313.4 Conclusions, 275Acknowledgments, 276References, 27614 Rearrangements in Carbohydrate Templates to theWay to Peptide-Scaffold Hybrids and Functionalized Heterocycles 279Bernardo Herrad´on, Irene de Miguel, and Enrique Mann14.1 Introduction, 27914.2 Synthesis of the Chiral Building Blocks: Applications of the Claisen–Johnson and Overman Rearrangements, 28014.3 Peptide–Scaffold Hybrids, 28214.4 Sequential Reactions for the Synthesis of Polyannular Heterocycles, 28414.5 The First Total Synthesis of Amphorogynine C, 284Acknowledgments, 293References, 29315 Palladium- and Nickel-Catalyzed Stereoselective Synthesis of Glycosyl Trichloroacetamides and Their Conversion to 𝛂- and 𝛃-Urea Glycosides 297Nathaniel H. Park, Eric T. Sletten, Matthew J. McKay, and Hien M. Nguyen15.1 Introduction, 29715.2 Development of the Palladium(II)-Catalyzed Glycal Trichloroacetimidate Rearrangement, 30015.3 Stereoselective Synthesis of Glycosyl Ureas from Glycal Trichloroacetimidates, 30715.4 Development of the Stereoselective Nickel-Catalyzed Transformation of Glycosyl Trichloroacetimidates to Trichloroacetamides, 31015.5 Transformation of Glycosyl Trichloroacetimidates into α- and β-Urea Glycosides, 31715.6 Mechanistic Studies on the Nickel-Catalyzed Transformation of Glycosyl Trichloracetimidates, 31715.7 Conclusions, 323References, 323Index 325