Title Details

Ken Tanakais a Professor of Applied Chemistry in the Department of Chemical Science and Engineering at the Tokyo Institute of Technology. Since the start of his academic career in 2003, he has published over 190 scientific papers and one book. His research focuses on organometallic chemistry directed toward organic synthesis.

Preface xv

Part I Rhodium(I) Catalysis 1

1 Rhodium(I)-Catalyzed Asymmetric Hydrogenation 3
Tsuneo Imamoto

1.1 Introduction 3

1.2 Chiral Phosphorus Ligands 3

1.2.1 P-Chirogenic Bisphosphine Ligands 4

1.2.1.1 Electron-Rich C2 Symmetric Ligands 4

1.2.1.2 Three-Hindered Quadrant Ligands 5

1.2.1.3 Ligands Bearing Two or Three Aryl Groups at the Phosphorus Atom 5

1.2.2 DuPhos, BPE, and Analogous Ligands 6

1.2.3 Ferrocene-Based Bisphosphine Ligands 7

1.2.4 C2 Symmetric Triaryl- or Diarylphosphine Ligands with Axial Chirality 9

1.2.5 Phosphine–Phosphite and Phosphine–Phosphoramide Ligands 9

1.2.6 Other Bidentate Ligands 9

1.2.7 Monodentate Phosphorus Ligands 11

1.3 Application of Chiral Phosphorus Ligands in Rhodium-Catalyzed Asymmetric Hydrogenation 12

1.3.1 Hydrogenation of Alkenes 12

1.3.1.1 Hydrogenation of Enamides 12

1.3.1.2 Hydrogenation of Enol Esters 18

1.3.1.3 Hydrogenation of α,β-Unsaturated Acids, Esters, and Related Substrates 19

1.3.1.4 Hydrogenation of Other Functionalized Alkenes 21

1.3.1.5 Hydrogenation of Unfunctionalized Alkenes 24

1.3.1.6 Hydrogenation of Heteroarenes 24

1.3.2 Hydrogenation of Ketones 25

1.3.3 Hydrogenation of Imines, Oximes, and Hydrazones 26

1.4 EnantioselectionMechanism of Rhodium-Catalyzed Asymmetric Hydrogenation 27

1.5 Conclusion 28

References 29

2 Rhodium(I)-Catalyzed Hydroboration and Diboration 39
Kohei Endo

2.1 Introduction 39

2.2 Hydroboration of Alkenes 39

2.2.1 Development of Catalyst Systems 39

2.2.2 Enantioselective Reactions 41

2.2.3 Hydroboration of FunctionalizedMolecules 44

2.3 Diboration 45

2.3.1 1,1-Diboration Reactions 45

2.3.2 1,2-Diboration Reactions 45

2.4 Conclusion 46

References 47

3 Rhodium(I)-Catalyzed Hydroformylation and Hydroamination 49
Zhiwei Chen and VyM. Dong

3.1 Introduction 49

3.2 Rhodium(I)-Catalyzed Hydroformylation 49

3.2.1 Asymmetric Hydroformylation of Challenging Substrates 49

3.2.2 Transfer Hydroformylation 50

3.3 Rhodium(I)-Catalyzed Hydroamination 54

3.3.1 Asymmetric Rhodium(I)-Catalyzed Hydroamination 54

3.3.2 Anti-Markovnikov Rhodium(I)-Catalyzed Hydroamination 56

3.4 Conclusion 59

References 61

4 Rhodium(I)-Catalyzed Hydroacylation 63
Maitane Fernández andMichael C.Willis

4.1 Introduction 63

4.2 Rhodium(I)-Catalyzed Intramolecular Hydroacylation 63

4.2.1 Small Ring Synthesis: Five-Membered Rings 63

4.2.2 Larger Ring Synthesis: Six-, Seven-, and Eight-Membered Rings 66

4.3 Rhodium(I)-Catalyzed Intermolecular Hydroacylation 68

4.3.1 N-Based Chelation Control 69

4.3.2 O-Based Chelation Control 70

4.3.3 S-Based Chelation Control 73

4.3.4 C=O as a Directing Group for Hydroacylation 79

4.4 Conclusion 81

References 81

5 Rhodium(I)-Catalyzed Asymmetric Addition of Organometallic Reagents to Unsaturated Compounds 85
Hsyueh-LiangWu and Ping-YuWu

5.1 Introduction 85

5.2 α,β-Unsaturated Ketones 85

5.2.1 Chiral Phosphorus Ligands 85

5.2.2 Chiral Diene Ligands 89

5.2.3 Chiral Bis-sulfoxide Ligands 92

5.2.4 Chiral Hybrid Ligands 92

5.3 α,β-Unsaturated Aldehydes 95

5.4 α,β-Unsaturated Esters 98

5.5 α,β-Unsaturated Amides 102

5.6 α,β-Unsaturated Phosphonates 105

5.7 α,β-Unsaturated Sulfonyl Compounds 105

5.8 Nitroolefin Compounds 107

5.9 Alkenylheteroarene and Alkenylarene Compounds 111

5.10 Conclusion 111

References 112

6 Rhodium(I)-Catalyzed Allylation with Alkynes and Allenes 117
Adrian B. Pritzius and Bernhard Breit

6.1 Introduction 117

6.2 Rh(I)-Catalyzed Addition of O-Nucleophiles 117

6.3 Rh(I)-Catalyzed Addition of S-Nucleophiles 123

6.4 Rh(I)-Catalyzed Addition of N-Nucleophiles 124

6.5 Rh(I)-Catalyzed Addition of C-Nucleophiles 127

6.6 Application of Rhodium-Catalyzed Addition in Total Synthesis 127

6.7 Conclusion 129

References 130

7 Rhodium(I)-Catalyzed Reductive Carbon–Carbon Bond Formation 133
Adam D. J. Calow and John F. Bower

7.1 Introduction 133

7.2 Hydroformylation 133

7.2.1 Directed Rh-Catalyzed Hydroformylation 134

7.2.2 Reversibly Bound Directing Groups in Rh-Catalyzed Hydroformylation 135

7.3 Reductive C—C Bond Formation Between Electron-Deficient Alkenes and Carbonyls or Imines 137

7.3.1 Reductive Aldol Reactions 137

7.3.2 Reductive Mannich Reactions 142

7.4 Reductive C—C Bond Formation Between Less Polarized Carbon-Based π-Unsaturated Systems and Carbonyls, Imines, or Anhydrides 144

7.4.1 Reductive C—C Bond Formations Between Alkenes and Carbonyls,Imines, or Anhydrides 144

7.4.2 Reductive C—C Bond Formations Between Alkynes and Carbonyls or Imines 146

7.4.3 Miscellaneous Processes 150

7.5 Reductive C—C Bond Formation Between Carbon-Based π-Unsaturated Systems 151

7.5.1 C—C Bond-Forming Reactions Between Alkenes and Alkynes 151

7.5.2 C—C Bond-Forming Reactions Between Alkynes and Alkynes 154

7.6 Conclusions 156

References 156

8 Rhodium(I)-Catalyzed [2+2+1] and [4+1] Cycloadditions 161
TsumoruMorimoto

8.1 Introduction 161

8.2 [2+2+1] Cycloaddition 161

8.2.1 [2+2+1] Cycloaddition of an Alkyne, an Alkene, and CO (Pauson–Khand-Type Reaction) 161

8.2.1.1 Pauson–Khand-Type Reaction Using Aldehydes as a C1 Component 162

8.2.1.2 Pauson–Khand-Type Reaction Using Formates as a C1 Component 171

8.2.1.3 Pauson–Khand-Type Reaction Using Oxalic Acid as a C1 Component 171

8.2.1.4 Pauson–Khand-Type Reaction Using Supported Carbon Monoxide 172

8.2.2 [2+2+1] Cycloaddition of Two Alkynes and CO 172

8.2.3 Carbonylative [2+2+1] Cycloaddition Including hetero-Multiple Bonds 174

8.3 [4+1] Cycloaddition 176

8.3.1 Cycloaddition of All Carbon 4π-Conjugated Systems with CO 176

8.3.2 Cycloaddition of 4π-Conjugated Systems Including Nitrogen Atom 178

8.4 Conclusion 179

References 179

9 Rhodium(I)-Catalyzed [2+2+2] and [4+2] Cycloadditions 183
Yu Shibata and Ken Tanaka

9.1 Introduction 183

9.2 [2+2+2] Cycloaddition 183

9.2.1 [2+2+2] Cycloaddition of Alkynes 184

9.2.2 [2+2+2] Cycloaddition of Alkynes with Nitriles 199

9.2.3 [2+2+2] Cycloaddition of Alkynes with Heterocumulenes 200

9.2.4 [2+2+2] Cycloaddition of Alkynes with Alkenes 207

9.2.5 [2+2+2] Cycloaddition of Alkynes with Carbonyl Compounds and Imines 211

9.3 [4+2] Cycloaddition 214

9.3.1 [4+2] Cycloaddition of Alkynes with 1,3-Dienes 215

9.3.2 [4+2] Cycloaddition via C—H Bond Cleavage 218

9.4 Conclusion 222

References 225

10 Rhodium(I)-Catalyzed Cycloadditions Involving Vinylcyclopropanes and Their Derivatives 229
Xing Fan, Cheng-Hang Liu, and Zhi-Xiang Yu

10.1 Introduction 229

10.2 VCP Isomerization Catalyzed by Rh(I) 230

10.3 Cycloaddition Reactions Using VCPs 5C Synthon 231

10.3.1 [5+1] cycloadditions of VCPs and CO 231

10.3.2 [5+1] Cycloaddition Reactions of VCP Derivatives and CO 233

10.3.3 Intermolecular [5+2] Cycloaddition Reactions 237

10.3.4 Intramolecular [5+2] Cycloaddition Reactions 239

10.3.5 [5+2] Cycloaddition Reactions of VCP Derivatives with 2π Components 245

10.3.6 [5+2+1] and [5+1+2+1] Cycloaddition Reactions 251

10.4 Cycloaddition Reactions Using VCPs 3C Synthon 255

10.4.1 [3+2] Cycloaddition Reactions of VCPs 255

10.4.2 [3+2] Cycloaddition Reactions of VCP Derivatives and 2π-Components 261

10.4.3 [3+2+1] Cycloaddition Reactions 262

10.4.4 [3+4] and [3+3] Cycloaddition Reactions of Vinylaziridines 264

10.5 Miscellaneous Cycloaddition 266

10.5.1 [7+1] Cycloaddition of Buta-1,3-dienylcyclopropanes 266

10.5.2 Intramolecular Reactions of ACPs and 2π-Synthon 266

10.5.3 Intramolecular Hydroacylation of VCPs 268

10.6 Conclusion 270

Acknowledgments 270

References 271

11 Rhodium(I)-Catalyzed Reactions via Carbon–Hydrogen Bond Cleavage 277
Takanori Shibata

11.1 Introduction 277

11.2 C–H Arylation 277

11.3 C–H Alkylation 279

11.3.1 Directed C–H Alkylation by Alkenes 279

11.3.2 Undirected C–H Alkylation by Alkene 281

11.4 C–H Alkenylation 283

11.5 Tandem Reaction Initiated by C–H Activation 285

11.6 C–H Borylation 287

11.7 Undirected Dehydrogenative C–H/Si–H Coupling 290

11.8 Conclusion 295

References 295

12 Rhodium(I)-Catalyzed Reactions via Carbon–Carbon Bond Cleavage 299
Masahiro Murakami and Naoki Ishida

12.1 Introduction 299

12.2 Reactions of Cyclopropanes and Cyclobutanes 299

12.3 Reactions via Cleavage of C(Carbonyl)—C Bonds 310

12.4 Reactions via Directing Group-Assisted C—C Bond Cleavage 315

12.5 Reactions of Alcohols via C—C Bond Cleavage 323

12.6 Reactions via Cleavage of C—CN Bond 330

12.7 Reactions via Decarbonylation of Aldehydes and Carboxylic Acid  Derivatives 332

12.8 Conclusion 333

References 334

Part II Rhodium(II) Catalysis 341

13 Rhodium(II) Tetracarboxylate-Catalyzed Enantioselective C–H Functionalization Reactions 343
Sidney M.Wilkerson-Hill and Huw M. L. Davies

13.1 Introduction 343

13.2 Mechanistic Insights and General Considerations 344

13.3 Development of Rh2(S-DOSP)4 as a Chiral Catalyst for C–H Functionalization 347

13.4 Combined C–H Functionalization/Cope Rearrangement 350

13.5 Phthalimido Amino Acid-Derived Catalysts for Intramolecular C–H Functionalization 353

13.6 Development of Triarylcyclopropane Carboxylate Rh(II) Complexes for Catalyst-Controlled Site-Selective C–H Functionalization 359

13.7 Emerging Chiral Dirhodium Catalyst for Enantioselective C–H Functionalization 364

13.8 New Paradigms in the Logic of Chemical Synthesis 365

13.9 Conclusion 368

Acknowledgments 369

References 369

14 Rhodium(II)-Catalyzed Nitrogen-Atom Transfer for Oxidation of Aliphatic C—H Bonds 373
TomG. Driver

14.1 Introduction 373

14.2 Mechanism-Inspired Development of New Rh2(II) Catalysts 374

14.2.1 Mechanism of Intramolecular Rh2(II)-Catalyzed C—H Bond Amination 374

14.2.2 Tetradentate Carboxylate Ligands for Bimetallic Rhodium(II) Complexes 375

14.2.3 Design, Synthesis, and Performance of Rh2 II,III Complexes 381

14.3 The Development of New Intramolecular Rh2(II)-Catalyzed sp3-C—H Bond Amination 383

14.3.1 C—H Bond Amination of Ethereal Bonds 383

14.3.2 The Use of Rh2(II)-Catalyzed C—H Bond Amination to Create Glycans and Glycosides 385

14.3.3 C—H Bond Amination of MIDA Boronates 386

14.3.4 Formation of Medium-Ring N-HeterocyclesThrough C—H Bond Amination 387

14.3.5 Synthesis of Spiroaminal Scaffolds 387

14.3.6 Expanding the Scope of C—H Bond Amination with New NH2-Based N-Atom Precursors 389

14.3.7 N-Tosylcarbamate N-Atom Precursors in Rh2(II)-Catalyzed C—H Bond Amination Reactions 394

14.3.8 Aryl Azide N-Atom Precursors in Rh2(II)-Catalyzed sp3-C—H Bond Amination Reactions 398

14.4 Intermolecular Rh2(II)-Catalyzed sp3-C—H Bond Amination Using an Iodine(III) Oxidant to Generate the Nitrene 400

14.4.1 Intermolecular C—H Bond Amination of Activated C—H Bonds 400

14.5 Non-Oxidatively Generated Nitrenes in Intermolecular Rh2(II)-Catalyzed sp3-C—H Bond Amination 411

14.5.1 N-Tosylcarbamates as the Nitrogen-Atom Precursor in Intermolecular sp3-C—H Bond Amination Processes 411

14.5.2 Azides as the Nitrogen-Atom Precursor in Intermolecular sp3-C—H Bond Amination Reactions 414

14.6 Diastereoselective Rh2(II)-Catalyzed sp3-C—H Bond Amination Using Chiral, Non-racemic Nitrogen-Atom Precursors 416

14.6.1 Intermolecular Diastereoselective C—H Bond Amination Using Sulfonimidamides 416

14.6.2 Intermolecular Diastereoselective C—H Bond Amination Using N-Tosylcarbamates 422

14.7 Enantioselective Rh2(II)-Catalyzed sp3-C—H Bond Amination 422

14.7.1 Intramolecular Asymmetric C—H Bond Amination 422

14.8 Conclusion 429

References 430

15 Rhodium(II)-Catalyzed Cyclopropanation 433
Vincent N.G. Lindsay

15.1 Introduction 433

15.1.1 Mechanistic Considerations 434

15.2 Intermolecular Cyclopropanation of Alkenes 436

15.2.1 Via Rhodium(II) Carbenes Bearing One Electron-Withdrawing Group (Acceptor Carbenes) 438

15.2.2 Via Rhodium(II) Carbenes Bearing One Electron-Withdrawing Group and One Electron-Donating Group (Donor–Acceptor Carbenes) 440

15.2.3 Via Rhodium(II) Carbenes Bearing Two Electron-Withdrawing Groups (Acceptor–Acceptor Carbenes) 441

15.3 Intramolecular Cyclopropanation of Alkenes 443

15.4 Cyclopropanation of Poorly Nucleophilic 𝜋-Systems: Alkynes, Arenes, and Allenes as Substrates 444

15.5 Conclusion 445

References 445

16 Reactions of 𝛂-Imino Rhodium(II) Carbene Complexes Generated fromN-Sulfonyl-1,2,3-Triazoles 449
TomoyaMiura and Masahiro Murakami

16.1 Introduction 449

16.2 Synthesis of N-Sulfonyl-1,2,3-Triazoles 451

16.3 Reactions of Carbon Nucleophiles with α-Imino Rhodium(II) Carbene Complexes 451

16.4 Reactions of Oxygen and Sulfur Nucleophiles with α-Imino Rhodium(II) Carbene Complexes 458

16.5 Reactions of Nitrogen Nucleophiles with α-Imino Rhodium(II) Carbene Complexes 464

16.6 Conclusion 466

References 467

17 Rhodium(II)-Catalyzed 1,3- and 1,5-Dipolar Cycloaddition 471
Nirupam De, Donguk Ko, and Eun Jeong Yoo

17.1 Introduction 471

17.2 1,3-Dipolar Cycloadditions of Carbonyl Ylides 471

17.2.1 [3+2] Cycloadditions of Carbonyl Ylides and Dipolarophiles 471

17.2.2 Chemoselective [3+2] Cycloadditions of Carbonyl Ylides 475

17.2.3 Applications to Natural Product Synthesis 476

17.3 1,3-Dipolar Cycloadditions of Azomethine Ylides 478

17.4 1,3-Dipolar Cycloadditions of Enoldiazo Compounds 479

17.5 1,5-Dipolar Cycloadditions of Pyridinium Zwitterions 482

17.6 Conclusion 484

References 484

Part III Rhodium(III) Catalysis 487

18 Rhodium(III)-Catalyzed Annulative Carbon–Hydrogen Bond Functionalization 489
Tetsuya Satoh andMasahiroMiura

18.1 Introduction 489

18.2 Type A Annulation 490

18.2.1 Annulation Utilizing Oxygen-containing Directing Group 490

18.2.2 Annulation Utilizing Nitrogen-containing Directing Group 492

18.2.3 Annulation Utilizing Sulfur-containing Directing Group 504

18.2.4 Annulation Utilizing Phosphorus-containing Directing Group 506

18.3 Type B Annulation 508

18.4 Type C Annulation 510

18.5 Type D Cyclization 515

18.6 Conclusion 516

References 517

19 Rhodium(III)-Catalyzed Non-annulative Carbon–Hydrogen Bond Functionalization 521
Fang Xie and Xingwei Li

19.1 Introduction 521

19.2 Alkenylation and Arylation 522

19.2.1 Rh(III)-Catalyzed Non-annulative C—H Alkenylation 522

19.2.1.1 Oxidative Dehydrogenative Alkenylation Reactions 522

19.2.1.2 Redox-Neutral Alkenylation with Internal Oxidizing Ability 523

19.2.1.3 Alkenylations from Alkynes 525

19.2.2 Rh(III)-Catalyzed Non-annulative C—H Arylation 529

19.2.2.1 Non-annulative Oxidative Dehydrogenative Arylation 529

19.2.2.2 Other Types of C–H Arylation 533

19.3 Alkynylation 540

19.3.1 Rh(III)-Catalyzed Non-annulative C—H Alkynylation 540

19.4 Alkylation 541

19.4.1 Rh(III)-Catalyzed Non-annulative C—H Couplings with Diazo Compounds 541

19.4.2 Rh(III)-Catalyzed Non-annulative Allylations 543

19.4.3 Rh(III)-Catalyzed Non-annulative Alkylations Through Addition of C—H Bond to C=X (X =C, O, N) Bonds 552

19.4.3.1 Addition of C—H Bond to C=C Bond 552

19.4.3.2 Addition of C—H Bond to C=O Bond 555

19.4.3.3 Addition of C—H Bond to C=N Bond 558

19.4.4 Rh(III)-Catalyzed Non-annulative Alkylations Through Opening Strained Rings 560

19.4.5 Rh(III)-Catalyzed Non-annulative Alkylations Through Transmetalation 563

19.5 C—N Bond Formation 564

19.5.1 Rh(III)-Catalyzed Non-annulative Aminations 564

19.5.2 Rh(III)-Catalyzed Non-annulative Amidations 569

19.6 Introduction of C=O Bond 577

19.6.1 Rh(III)-Catalyzed Non-annulative Acylations 577

19.6.2 Rh(III)-Catalyzed Non-annulative Amidations 579

19.7 Cyanation 579

19.8 C—O Bond Formation 580

19.9 C—X Bond Formation 581

19.9.1 Non-annulative Halogenation of Arenes 581

19.9.2 C—H Hyperiodination of Arenes 583

19.10 Non-annulative Thiolation of Arenes 585

19.11 C—Se Bond Formation 585

19.12 Conclusion 586

References 587

20 Sterically and Electronically Tuned Cp Ligands for Rhodium(III)-Catalyzed Carbon–Hydrogen Bond Functionalization 593
Fedor Romanov-Michailidis, Erik J.T. Phipps, and Tomislav Rovis

20.1 Introduction 593

20.2 QuantitativeModels for Steric and Electronic Parameterization of Cp Ligands on Rhodium(III) 594

20.3 Sterically Tuned Cp Ligands 598

20.3.1 Earlier Results 598

20.3.2 Synthesis of Isoquinolones, Pyridones, and Derivatives 599

20.3.3 Synthesis of Pyridines 607

20.3.4 Cyclopropanation and Carboamination Reactions 607

20.4 Electronically Tuned Cp Ligands 612

20.4.1 Synthesis of Pyridines and Derivatives 612

20.4.2 Tanaka’s Ethoxycarbonyl-Substituted Cyclopentadienyl Ligand (CpE) 615

20.5 Conclusion 626

References 626

21 Chiral Cp Ligands for Rhodium(III)-Catalyzed Asymmetric Carbon–Hydrogen Bond Functionalization 629
Christopher G. Newton and Nicolai Cramer

21.1 Introduction 629

21.2 SeminalWork 629

21.3 The Ligands 630

21.3.1 Development 630

21.3.2 Established Families 631

21.3.3 Complexation Methods 633

21.4 Applications 634

21.4.1 Introduction 634

21.4.2 Hydroxamate Directing Groups 634

21.4.3 Pyridyl Directing Groups 638

21.4.4 Hydroxy Directing Groups 639

21.4.5 Other Directing Groups 641

21.5 Conclusion 642

References 642

Index 645