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 a-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 a,a'-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®) 427

15.2.4 Telaprevir (Incivek®) 429

15.2.5 Ezetimibe (Zetia®) 431

15.2.6 Crixivan (Indinavir®) 433

15.2.7 Oxytocine Antagonists: Retosiban and Epelsiban 436

15.2.8 Praziquantel (Biltricide®) 439

15.3 Summary and Outlook 442

References 442

Index 447