Stereoselective Multiple Bond-Forming Transformations in Organic Synthesis

List of Contributors xiii Foreword xvii Preface xix 1 Definitions and Classifications of MBFTs 1 Damien Bonne and Jean Rodriguez 1.1 Introduction 1 1.2 Definitions 4 1.3 Conclusion and Outlook 6 References 7 PART I STEREOSELECTIVE SYNTHESIS OF HETEROCYCLES 9 2 Five-Membered Heterocycles 11 Hanmin Huang and Pan Xie 2.1 Introduction 11 2.2 Monocyclic Targets 12 2.2.1 1,3-Dipolar Cycloaddition 12 2.2.2 Michael Addition-Initiated Domino Process 20 2.2.3 Multicomponent Reactions 23 2.2.4 Carbohalogenation Reactions 26 2.2.5 Radical Processes 26 2.3 Fused Polycyclic Targets 28 2.3.1 Cycloaddition Reactions 28 2.3.2 Domino Cyclization Reactions 32 2.4 Bridged Polycyclic Targets 34 2.5 Conclusion and Outlook 36 References 37 3 Six-Membered Heterocycles 45 Giammarco Tenti, M. Teresa Ramos, and J. Carlos Menéndez 3.1 Introduction 45 3.2 Monocyclic Targets 47 3.2.1 Nitrogen-Only Heterocycles 47 3.2.2 Oxygen-Containing Heterocycles 58 3.3 Fused Polycyclic Targets 62 3.3.1 Nitrogen-Only Fused Polycyclic Targets 62 3.3.2 Oxygen-Containing Fused Polycyclic Targets 70 3.3.3 Sulfur-Containing Fused Polycyclic Targets 74 3.4 Bridged Polycyclic Targets 74 3.4.1 General Procedure for the Preparation of 2,6-DABCO-Derived Compounds 138 76 3.5 Polycyclic Spiro Targets 77 3.6 Summary and Outlook 79 References 79 4 Other Heterocycles 87 Qian Wang and Jieping Zhu 4.1 Introduction 87 4.2 Synthesis of Medium-Sized Monocyclic, Fused and Bridged Polycyclic Heterocycles 88 4.2.1 Ring Synthesis by Ring Transformation via Rearrangements/Ring Expansions 88 4.2.2 Ring Synthesis by Annulation 99 4.3 Summary and Outlook 109 References 109 PART II STEREOSELECTIVE SYNTHESIS OF CARBOCYCLES 115 5 Three- and Four-Membered Carbocycles 117 Renata Marcia de Figueiredo, Gilles Niel, and Jean-Marc Campagne 5.1 Introduction 117 5.2 Cyclopropane Derivatives 118 5.2.1 Organocatalysis and Related Reactions [Michael-Initiated Ring-Closure (MIRC) Reactions] 118 5.2.2 Organometallics and Metal Catalysis 123 5.2.3 Lewis Acid-Promoted Sequences 133 5.2.4 Pericyclic Domino Strategies 134 5.2.5 Radical Domino Strategies 135 5.3 Cyclobutane Derivatives 136 5.3.1 Organocatalyzed Cyclobutanations 136 5.3.2 Organometallics and Metal Catalysis 137 5.3.3 Acid- or Base-Promoted Transformations 143 5.3.4 Multicomponent Reactions (MCRs) 145 5.4 Summary and Outlook 146 References 146 6 Five-Membered Carbocycles 157 Vijay Nair and Rony Rajan Paul 6.1 Introduction 157 6.2 Monocyclic Targets 158 6.2.1 Metal-Catalyzed Reactions 158 6.2.2 Organocatalytic Reactions 158 6.2.3 Miscellaneous Reactions 167 6.3 Fused Polycyclic Targets 169 6.3.1 Metal-Catalyzed Reactions 169 6.3.2 Organocatalytic Reactions 170 6.3.3 Lewis Acid-Catalyzed Reactions 172 6.3.4 Miscellaneous Reactions 173 6.4 Bridged Polycyclic Targets 176 6.5 Conclusion and Outlook 178 References 179 7 Stereoselective Synthesis of Six-Membered Carbocycles 185 Muriel Amatore, Corinne Aubert, Marion Barbazanges, Marine Desage-El Murr, and Cyril Ollivier 7.1 Introduction 185 7.2 Metal-Catalyzed Stereoselective Multiple Bond-Forming Transformations 186 7.2.1 Introduction 186 7.2.2 Cycloadditions 186 7.2.3 Metal-Catalyzed Cascades as Formal [2+2+2] Cycloadditions 191 7.2.4 Metal-Catalyzed Cycloisomerization Cascades 192 7.3 Enantioselective Organocatalyzed Synthesis of Six-Membered Rings 195 7.3.1 Organocatalyzed Miscellaneous Reactions 195 7.3.2 Organocatalyzed Cascade and Multicomponent Reactions 197 7.3.3 Polycyclization Cascade Reactions 201 7.4 Stereoselective Multiple Bond-Forming Radical Transformations 202 7.4.1 Intermolecular Cascade Reactions 202 7.4.2 Intramolecular Cascade Reactions 203 7.5 Conclusions 204 References 205 8 Seven- and Eight-Membered Carbocycles 211 Gérard Buono, Hervé Clavier, Laurent Giordano, and Alphonse Tenaglia 8.1 Introduction 211 8.2 Cycloheptenes 212 8.3 Cycloheptadienes 219 8.4 Cycloheptatrienes 221 8.5 Cyclooctenes 222 8.6 Cyclooctadienes 225 8.7 Cyclooctatrienes 229 8.8 Cyclooctatetraenes 234 8.9 Concluding Remarks 235 References 235 PARTIII STEREOSELECTIVE SYNTHESIS OF SPIROCYCLIC COMPOUNDS 241 9 Metal-Assisted Methodologies 243 Gaëlle Chouraqui, Laurent Commeiras, and Jean-Luc Parrain 9.1 Introduction 243 9.2 Quaternary Spirocenter 244 9.2.1 Copper-Assisted Methodologies 245 9.2.2 Gold-Assisted Methodologies 247 9.2.3 Palladium-Assisted Methodologies 247 9.2.4 Rhodium-Assisted Methodologies 251 9.2.5 Platinum-Assisted Methodologies 252 9.3 alpha-Heteroatom-Substituted Spirocenter 252 9.3.1 Zinc-, Magnesium-, and Copper-Assisted Methodologies 253 9.3.2 Titanium-Assisted Methodologies 254 9.3.3 Gold- and Platinum-Assisted Methodologies 255 9.3.4 Palladium-Assisted Methodologies 258 9.3.5 Rhodium-Assisted Methodologies 259 9.4 alpha,alpha'-Diheteroatom-Substituted Spirocenter 261 9.5 Conclusion and Outlook 264 References 265 10 Organocatalyzed Methodologies 271 Ramon Rios 10.1 Introduction 271 10.2 Enantioselective Synthesis of All-Carbon Spirocenters 275 10.2.1 Organocatalytic Enantioselective Methodologies for the Synthesis of Spirooxindoles 275 10.2.2 Other Spirocycles 292 10.3 Enantioselective Synthesis Spirocenters with at Least One Heteroatom 299 10.3.1 Synthesis of Spirooxindoles 299 10.3.2 Synthesis of Other Spirocycles 301 10.4 Conclusion and Outlook 301 References 302 PARTIV STEREOSELECTIVE SYNTHESIS OF ACYCLIC COMPOUNDS 307 11 Metal-Catalyzed Methodologies 309 Gabriela Guillena and Diego J. Ramón 11.1 Introduction 309 11.2 Anion Relay Approach 310 11.3 Mannich Reaction 312 11.3.1 Diastereoselective Approach 312 11.3.2 Enantioselective Approach 312 11.4 Reactions Involving Isonitriles 314 11.4.1 Diastereoselective Passerini Reaction 314 11.4.2 Enantioselective Passerini Reaction 315 11.4.3 Diastereoselective Ugi Reaction 316 11.5 1,2-Addition-Type Processes 317 11.5.1 Diastereoselective Approach 317 11.5.2 Enantioselective Approach 320 11.6 Michael-Type Processes 324 11.6.1 Diastereoselective Approach 324 11.6.2 Enantioselective Approach 327 11.7 Summary and Outlook 331 References 332 12 Organocatalyzed Methodologies 339 Vincent Coeffard, Christine Greck, Xavier Moreau, and Christine Thomassigny 12.1 Introduction 339 12.2 Aminocatalysis 340 12.2.1 Enamine-Enamine Activation 340 12.2.2 Iminium-Enamine Activation 343 12.3 N-Heterocyclic Carbene (NHC) Activation 353 12.4 H-Bonding Activation 357 12.5 Phase-Transfer Catalysis 358 12.6 Summary and Outlook 359 References 359 PART V MULTIPLE BOND-FORMING TRANSFORMATIONS: SYNTHETIC APPLICATIONS 363 13 MBFTs for the Total Synthesis of Natural Products 365 Yanxing Jia 13.1 Introduction 365 13.2 Anionic-Initiated MBFTs 366 13.3 Cationic-Initiated MBFTs 371 13.4 Radical-Mediated MBFTs 375 13.5 Pericyclic MBFTs 379 13.6 Transition-Metal-Catalyzed MBFTs 385 13.7 Summary and Outlook 388 References 390 14 Synthesis of Biologically Relevant Molecules 393 Matthijs J. van Lint, Eelco Ruijter, and Romano V.A. Orru 14.1 Introduction 393 14.2 Organocatalyzed MBFTs for BRMs 394 14.3 Multicomponent MBFTs for BRMs 404 14.4 Palladium-Catalyzed MBFTs for BRMs 413 14.5 Conclusion and Outlook 418 References 419 15 Industrial Applications of Multiple Bond-Forming Transformations (MBFTs) 423 Tryfon Zarganes-Tzitzikas, Ahmad Yazbak, Alexander Dömling 15.1 Introduction 423 15.2 Applications of MBFTs 424 15.2.1 Xylocaine 424 15.2.2 Almorexant 424 15.2.3 (.)-Oseltamivir (Tamiflu(r)) 427 15.2.4 Telaprevir (Incivek(r)) 429 15.2.5 Ezetimibe (Zetia(r)) 431 15.2.6 Crixivan (Indinavir(r)) 433 15.2.7 Oxytocine Antagonists: Retosiban and Epelsiban 436 15.2.8 Praziquantel (Biltricide(r)) 439 15.3 Summary and Outlook 442 References 442 Index 447