Rhodium Catalysis in Organic Synthesis: Methods and Reactions

An essential reference to the highly effective reactions applied to modern organic synthesis Rhodium complexes are one of the most important transition metals for organic synthesis due to their ability to catalyze a variety of useful transformations. Rhodium Catalysis in Organic Synthesis explores the most recent progress and new developments in the field of catalytic cyclization reactions using rhodium(I) complexes and catalytic carbon-hydrogen bond activation reactions using rhodium(II) and rhodium(III) complexes. Edited by a noted expert in the field with contributions from a panel of leading international scientists, Rhodium Catalysis in Organic Synthesis presents the essential information in one comprehensive volume. Designed to be an accessible resource, the book is arranged by different reaction types. All the chapters provide insight into each transformation and include information on the history, selectivity, scope, mechanism, and application. In addition, the chapters offer a summary and outlook of each transformation. This important resource: -Offers a comprehensive review of how rhodium complexes catalyze a variety of highly useful reactions for organic synthesis (e.g. coupling reactions, CH-bond functionalization, hydroformylation, cyclization reactions and others) -Includes information on the most recent developments that contain a range of new, efficient, elegant, reliable and useful reactions -Presents a volume edited by one of the international leading scientists working in the field today -Contains the information that can be applied by researchers in academia and also professionals in pharmaceutical, agrochemical and fine chemical companies Written for academics and synthetic chemists working with organometallics, Rhodium Catalysis in Organic Synthesis contains the most recent information available on the developments and applications in the field of catalytic cyclization reactions using rhodium complexes.

Table of Contents:
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