Pergamon Tetrahedron 54 (1998) 9913-9959 Tetrahedron report number 462 TETRAHEDRON RECENT ADVANCES IN STEREOSELECTIVE C-GLYCOSIDE SYNTHESIS Yuguo Du and Robert J. Linhardt Division of Medicinal and Natural Products Chemistry and Department of Chemical and Biochemical Engineering, University of Iowa, PHAR $328, Iowa City, Iowa, 52242, USA Iontcho R. Vlahov Baker-Norton Pharamceuticals, Inc. 4400 Biscayne Blvd., Miami, Florida 33137, USA Received 10 February 1998 Contents 1. Introduction 2. Electrophilic C-Glycoside Donors 2.1. Glycosyi hahdes 2.2. C-I Lactones 2.3. Glycals 2.4. ! ,2-Anhydrosugars 2.5. C-I Acetylated carbohydrates 2.6. Anomeric trichloroacetimidates 3. C-Glycosylation Through Anomeric Anionic Intermediates 3.1. Reductive lithiation-dianion method • 3.2. Lithiated 1-alkoxyvinyl anions 3.2.1. Aikoxyvinyl deprotonation 3.2.2. Tin-lithium transmetallation 4. Intermolecular Free Radical Approaches 4.1. Radical C-glycosylation using glycosyl bromide 4.2. Radical C-glycosylation with exomethylenic carbohydrates 5. Samarium Iodide Mediated C-Glycosylation 5.1. Single electron transfer reactions 5.2. Sequential single electron transfer reactions 6. Transition Metal M&liated C-Giycosylation 6.1. Palladium mediated C-glycosylation 6.1.1. Heck type couplings 6. 1.2. ~-Allyl-complexes 6.1.3. Palladium-efitalyzed vinylic substitution 6.1.4. Palladium-catalyzed Suzuki coupling 6.2. Other transition metal complexes ~ ,. 7. C-Glycosylation Through Intramolecular Aglycon LJenvery 7.1. Through a temporary C-O connection 7. I. 1. Radicalinduced cyclization 7.1.2. Ionic cyclization 7.2. Silicon tether method 7.3. O-C-glycoside rearrangements 8. C-Glycoside Synthesis Through Intramolecular Cyclization 9. C-Ohgosacchaiide Synthesis 9.1. C-Disaccharides 9.2. C-Oligosaccharides 10. Conclusions 9914 9915 9915 9917 9918 9919 9920 9922 9923 9923 9924 9924 9925 9925 9926 9927 9928 9928 9928 9932 9932 9932 9934 9934 9936 9937 9937 9938 9938 9938 9939 9941 9944 9947 9947 9951 9953 *E-mail: mbert-linhardt~uiowa.edu; FAX: +i 319-335-6634 0040-4020/98/$ - see front matter © 1998 Elsevier Science Ltd. All rights reserved. PII: S0040-4020(98)00405-0