Carbohydrates: Tools for Stereoselective Synthesis

Closing a gap in the literature, this comprehensive book presents the utility of carbohydrate derivatives as chiral auxiliaries, reagents, complex ligands and organocatalysts, together with details of their preparation, as well as their successful application in stereo–selective synthesis.  Divided into four parts: Carbohydrate Auxiliaries Carbohydrate Reagents Carbohydrate Ligands Carbohydrate Organocatalysts  It is an indispensable source for every organic chemist.  Contains a Foreword by Professor Horst Kunz, Johannes–Gutenberg–University of Mainz, Germany  

Foreword XI Preface XIII List of Contributors XV Part I Carbohydrate Auxiliaries 1 1 Reactions of Nucleophiles with Electrophiles Bound to Carbohydrate Auxiliaries 3 Zhiwei Miao 1.1 Introduction 3 1.2 Strecker Reactions 3 1.3 Ugi Reactions 8 1.4 Allylations 13 1.5 Mannich–Type Reactions 15 1.6 Addition of Phosphites 19 1.7 Dynamic Kinetic Resolution of α–Chloro Carboxylic Esters 22 References 24 2 1,4–Addition of Nucleophiles to α , β –Unsaturated Carbonyl Compounds 27 Kiichiro Totani and Kin–ichi Tadano 2.1 Introduction 27 References 45 3 Reaction of Enolates 47 Noureddine Khiar, Inmaculada Fernández, Ana Alcudia, Maria Victoria García and Rocío Recio 3.1 Introduction 47 3.2 Aldol Alkylation 48 3.3 Aldol Addition 56 3.4 Concluding Remarks 60 References 62 4 Cycloadditions 65 Mike M.K. Boysen 4.1 Diels–Alder Reactions 65 4.2 1,3–Diploar Cycloadditions 93 4.3 [2 + 2] Cycloadditions 101 References 104 5 Cyclopropanation 107 Noureddine Khiar, Inmaculada Fernández, Ana Alcudia, Maria Victoria García and Rocío Recio 5.1 Introduction 107 5.2 Epoxidation 113 5.3 Construction of Chiral Sulfur and Phosphorus Centers 117 5.4 Chiral Phosphorus Compounds 120 5.5 Concluding Remarks 122 References 123 Part II Carbohydrate Reagents 125 6 Hydride Reductions and 1,2–Additions of Nucleophiles to Carbonyl Compounds Using Carbohydrate–Based Reagents and Additives 127 Omar Boutureira and Benjamin G. Davis 6.1 Introduction 127 6.2 Hydride Reductions 127 6.3 1,2–Additions of Nucleophiles to Carbonyl Compounds 135 References 140 7 Aldol–Type Reactions 143 Inmaculada Fernández, Noureddine Khiar, Ana Alcudia, Maria Victoria García and Rocío Recio 7.1 Introduction 143 7.2 Titanium Lewis Acids for Enolate Formation 143 7.3 1,2–Additions of Nucleophiles to Carbonyl Compounds Using Stoichiometric Reagents 149 References 153 Part III Carbohydrate Ligands 155 8 Hydrogenation Reactions 157 Carmen Claver, Sergio Castillón, Montserrat Diéguez and Oscar Pàmies 8.1 Introduction 157 8.2 Hydrogenation of C=C and C=N Bonds 158 8.3 P–Donor Ligands 159 8.4 P–N Donors 177 8.5 P–S Donors 178 Acknowledgments 180 References 180 9 Hydroformylations, Hydrovinylations, and Hydrocyanations 183 Mike M.K. Boysen 9.1 Hydroformylation Reactions 183 9.2 Hydrovinylation Reactions 202 9.3 Hydrocyanation Reactions 206 9.4 Hydrosilylation Reactions 211 9.5 Conclusion 214 References 215 10 Carbohydrate–Derived Ligands in Asymmetric Tsuji–Trost Reactions 217 Montserrat Diéguez and Oscar Pàmies 10.1 Introduction 217 10.2 Ligands 220 10.3 Conclusions 242 Acknowledgments 242 References 242 11 Carbohydrate–Derived Ligands in Asymmetric Heck Reactions 245 Montserrat Diéguez and Oscar Pàmies 11.1 Introduction 245 11.2 Ligands 247 11.3 Conclusions 250 Acknowledgments 251 References 251 12 1,4–Addition of Nucleophiles to α , β –Unsaturated Carbonyl Compounds 253 Yolanda Díaz, M. Isabel Matheu, David Benito and Sergio Castillón 12.1 Copper–Catalyzed Reactions – Introduction 253 12.2 Copper–Catalyzed Reactions – Ligands 257 12.3 Enantioselective Copper–Catalyzed 1,4–Addition of Organometallics to α,β–Unsaturated Carbonyl Compounds 266 12.4 Rhodium–Catalyzed Reactions 286 12.5 Conclusions 287 References 288 13 1,2–Addition of Nucleophiles to Carbonyl Compounds 293 M. Isabel Matheu, Yolanda Díaz, Patricia Marcé and Sergio Castillón 13.1 Introduction 293 13.2 Addition of Organometallic Reagents to Aldehydes 294 13.3 Addition of Trimethylsilyl Cyanide to Ketones. P=O,O Ligands 308 13.4 Conclusion 311 References 312 14 Cyclopropanation 313 Mike M.K. Boysen References 318 Part IV Carbohydrate Organocatalysts 319 15 Oxidations 321 O. Andrea Wong, Brian Nettles and Yian Shi 15.1 Oxidations 321 15.2 Conclusion 346 References 347 16 Enantioselective Addition Reactions Catalyzed by Carbohydrate–Derived Organocatalysts 351 Jun–An Ma and Guang–Wu Zhang 16.1 Introduction 351 16.2 Strecker, Mannich, and Nitro–Mannich Reactions 351 16.3 Michael Additions 358 16.4 Miscellaneous Reactions 364 16.5 Outlook 367 Acknowledgment 368 References 368 Index 371

Mike Boysen is Junior Professor at the Leibniz University, Hannover, Germany. He obtained his Ph.D. degree under the guidance of Thisbe K. Lindhorst at th University Kiel. After a postdoctoral fellowship with Stefan Oscarson at Göteborg University he joined the faculty at Hannover University. His research interests include synthetic carbohydrate chemistry, monosaccharide transformation, enantioselective synthesis and development of novel chiral ligands for metal catalysis based on carbohydrates.