Rhodium Catalysis in Organic Synthesis

Ken Tanaka is 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 xvPart I Rhodium(I) Catalysis 11 Rhodium(I)-Catalyzed Asymmetric Hydrogenation 3Tsuneo Imamoto1.1 Introduction 31.2 Chiral Phosphorus Ligands 31.2.1 P-Chirogenic Bisphosphine Ligands 41.2.1.1 Electron-Rich C2 Symmetric Ligands 41.2.1.2 Three-Hindered Quadrant Ligands 51.2.1.3 Ligands Bearing Two or Three Aryl Groups at the Phosphorus Atom 51.2.2 DuPhos, BPE, and Analogous Ligands 61.2.3 Ferrocene-Based Bisphosphine Ligands 71.2.4 C2 Symmetric Triaryl- or Diarylphosphine Ligands with Axial Chirality 91.2.5 Phosphine–Phosphite and Phosphine–Phosphoramide Ligands 91.2.6 Other Bidentate Ligands 91.2.7 Monodentate Phosphorus Ligands 111.3 Application of Chiral Phosphorus Ligands in Rhodium-Catalyzed Asymmetric Hydrogenation 121.3.1 Hydrogenation of Alkenes 121.3.1.1 Hydrogenation of Enamides 121.3.1.2 Hydrogenation of Enol Esters 181.3.1.3 Hydrogenation of α,β-Unsaturated Acids, Esters, and Related Substrates 191.3.1.4 Hydrogenation of Other Functionalized Alkenes 211.3.1.5 Hydrogenation of Unfunctionalized Alkenes 241.3.1.6 Hydrogenation of Heteroarenes 241.3.2 Hydrogenation of Ketones 251.3.3 Hydrogenation of Imines, Oximes, and Hydrazones 261.4 EnantioselectionMechanism of Rhodium-Catalyzed Asymmetric Hydrogenation 271.5 Conclusion 28References 292 Rhodium(I)-Catalyzed Hydroboration and Diboration 39Kohei Endo2.1 Introduction 392.2 Hydroboration of Alkenes 392.2.1 Development of Catalyst Systems 392.2.2 Enantioselective Reactions 412.2.3 Hydroboration of FunctionalizedMolecules 442.3 Diboration 452.3.1 1,1-Diboration Reactions 452.3.2 1,2-Diboration Reactions 452.4 Conclusion 46References 473 Rhodium(I)-Catalyzed Hydroformylation and Hydroamination 49Zhiwei Chen and VyM. Dong3.1 Introduction 493.2 Rhodium(I)-Catalyzed Hydroformylation 493.2.1 Asymmetric Hydroformylation of Challenging Substrates 493.2.2 Transfer Hydroformylation 503.3 Rhodium(I)-Catalyzed Hydroamination 543.3.1 Asymmetric Rhodium(I)-Catalyzed Hydroamination 543.3.2 Anti-Markovnikov Rhodium(I)-Catalyzed Hydroamination 563.4 Conclusion 59References 614 Rhodium(I)-Catalyzed Hydroacylation 63Maitane Fernández andMichael C.Willis4.1 Introduction 634.2 Rhodium(I)-Catalyzed Intramolecular Hydroacylation 634.2.1 Small Ring Synthesis: Five-Membered Rings 634.2.2 Larger Ring Synthesis: Six-, Seven-, and Eight-Membered Rings 664.3 Rhodium(I)-Catalyzed Intermolecular Hydroacylation 684.3.1 N-Based Chelation Control 694.3.2 O-Based Chelation Control 704.3.3 S-Based Chelation Control 734.3.4 C=O as a Directing Group for Hydroacylation 794.4 Conclusion 81References 815 Rhodium(I)-Catalyzed Asymmetric Addition of Organometallic Reagents to Unsaturated Compounds 85Hsyueh-LiangWu and Ping-YuWu5.1 Introduction 855.2 α,β-Unsaturated Ketones 855.2.1 Chiral Phosphorus Ligands 855.2.2 Chiral Diene Ligands 895.2.3 Chiral Bis-sulfoxide Ligands 925.2.4 Chiral Hybrid Ligands 925.3 α,β-Unsaturated Aldehydes 955.4 α,β-Unsaturated Esters 985.5 α,β-Unsaturated Amides 1025.6 α,β-Unsaturated Phosphonates 1055.7 α,β-Unsaturated Sulfonyl Compounds 1055.8 Nitroolefin Compounds 1075.9 Alkenylheteroarene and Alkenylarene Compounds 1115.10 Conclusion 111References 1126 Rhodium(I)-Catalyzed Allylation with Alkynes and Allenes 117Adrian B. Pritzius and Bernhard Breit6.1 Introduction 1176.2 Rh(I)-Catalyzed Addition of O-Nucleophiles 1176.3 Rh(I)-Catalyzed Addition of S-Nucleophiles 1236.4 Rh(I)-Catalyzed Addition of N-Nucleophiles 1246.5 Rh(I)-Catalyzed Addition of C-Nucleophiles 1276.6 Application of Rhodium-Catalyzed Addition in Total Synthesis 1276.7 Conclusion 129References 1307 Rhodium(I)-Catalyzed Reductive Carbon–Carbon Bond Formation 133Adam D. J. Calow and John F. Bower7.1 Introduction 1337.2 Hydroformylation 1337.2.1 Directed Rh-Catalyzed Hydroformylation 1347.2.2 Reversibly Bound Directing Groups in Rh-Catalyzed Hydroformylation 1357.3 Reductive C—C Bond Formation Between Electron-Deficient Alkenes and Carbonyls or Imines 1377.3.1 Reductive Aldol Reactions 1377.3.2 Reductive Mannich Reactions 1427.4 Reductive C—C Bond Formation Between Less Polarized Carbon-Based π-Unsaturated Systems and Carbonyls, Imines, or Anhydrides 1447.4.1 Reductive C—C Bond Formations Between Alkenes and Carbonyls,Imines, or Anhydrides 1447.4.2 Reductive C—C Bond Formations Between Alkynes and Carbonyls or Imines 1467.4.3 Miscellaneous Processes 1507.5 Reductive C—C Bond Formation Between Carbon-Based π-Unsaturated Systems 1517.5.1 C—C Bond-Forming Reactions Between Alkenes and Alkynes 1517.5.2 C—C Bond-Forming Reactions Between Alkynes and Alkynes 1547.6 Conclusions 156References 1568 Rhodium(I)-Catalyzed [2+2+1] and [4+1] Cycloadditions 161TsumoruMorimoto8.1 Introduction 1618.2 [2+2+1] Cycloaddition 1618.2.1 [2+2+1] Cycloaddition of an Alkyne, an Alkene, and CO (Pauson–Khand-Type Reaction) 1618.2.1.1 Pauson–Khand-Type Reaction Using Aldehydes as a C1 Component 1628.2.1.2 Pauson–Khand-Type Reaction Using Formates as a C1 Component 1718.2.1.3 Pauson–Khand-Type Reaction Using Oxalic Acid as a C1 Component 1718.2.1.4 Pauson–Khand-Type Reaction Using Supported Carbon Monoxide 1728.2.2 [2+2+1] Cycloaddition of Two Alkynes and CO 1728.2.3 Carbonylative [2+2+1] Cycloaddition Including hetero-Multiple Bonds 1748.3 [4+1] Cycloaddition 1768.3.1 Cycloaddition of All Carbon 4π-Conjugated Systems with CO 1768.3.2 Cycloaddition of 4π-Conjugated Systems Including Nitrogen Atom 1788.4 Conclusion 179References 1799 Rhodium(I)-Catalyzed [2+2+2] and [4+2] Cycloadditions 183Yu Shibata and Ken Tanaka9.1 Introduction 1839.2 [2+2+2] Cycloaddition 1839.2.1 [2+2+2] Cycloaddition of Alkynes 1849.2.2 [2+2+2] Cycloaddition of Alkynes with Nitriles 1999.2.3 [2+2+2] Cycloaddition of Alkynes with Heterocumulenes 2009.2.4 [2+2+2] Cycloaddition of Alkynes with Alkenes 2079.2.5 [2+2+2] Cycloaddition of Alkynes with Carbonyl Compounds and Imines 2119.3 [4+2] Cycloaddition 2149.3.1 [4+2] Cycloaddition of Alkynes with 1,3-Dienes 2159.3.2 [4+2] Cycloaddition via C—H Bond Cleavage 2189.4 Conclusion 222References 22510 Rhodium(I)-Catalyzed Cycloadditions Involving Vinylcyclopropanes and Their Derivatives 229Xing Fan, Cheng-Hang Liu, and Zhi-Xiang Yu10.1 Introduction 22910.2 VCP Isomerization Catalyzed by Rh(I) 23010.3 Cycloaddition Reactions Using VCPs 5C Synthon 23110.3.1 [5+1] cycloadditions of VCPs and CO 23110.3.2 [5+1] Cycloaddition Reactions of VCP Derivatives and CO 23310.3.3 Intermolecular [5+2] Cycloaddition Reactions 23710.3.4 Intramolecular [5+2] Cycloaddition Reactions 23910.3.5 [5+2] Cycloaddition Reactions of VCP Derivatives with 2π Components 24510.3.6 [5+2+1] and [5+1+2+1] Cycloaddition Reactions 25110.4 Cycloaddition Reactions Using VCPs 3C Synthon 25510.4.1 [3+2] Cycloaddition Reactions of VCPs 25510.4.2 [3+2] Cycloaddition Reactions of VCP Derivatives and 2π-Components 26110.4.3 [3+2+1] Cycloaddition Reactions 26210.4.4 [3+4] and [3+3] Cycloaddition Reactions of Vinylaziridines 26410.5 Miscellaneous Cycloaddition 26610.5.1 [7+1] Cycloaddition of Buta-1,3-dienylcyclopropanes 26610.5.2 Intramolecular Reactions of ACPs and 2π-Synthon 26610.5.3 Intramolecular Hydroacylation of VCPs 26810.6 Conclusion 270Acknowledgments 270References 27111 Rhodium(I)-Catalyzed Reactions via Carbon–Hydrogen Bond Cleavage 277Takanori Shibata11.1 Introduction 27711.2 C–H Arylation 27711.3 C–H Alkylation 27911.3.1 Directed C–H Alkylation by Alkenes 27911.3.2 Undirected C–H Alkylation by Alkene 28111.4 C–H Alkenylation 28311.5 Tandem Reaction Initiated by C–H Activation 28511.6 C–H Borylation 28711.7 Undirected Dehydrogenative C–H/Si–H Coupling 29011.8 Conclusion 295References 29512 Rhodium(I)-Catalyzed Reactions via Carbon–Carbon Bond Cleavage 299Masahiro Murakami and Naoki Ishida12.1 Introduction 29912.2 Reactions of Cyclopropanes and Cyclobutanes 29912.3 Reactions via Cleavage of C(Carbonyl)—C Bonds 31012.4 Reactions via Directing Group-Assisted C—C Bond Cleavage 31512.5 Reactions of Alcohols via C—C Bond Cleavage 32312.6 Reactions via Cleavage of C—CN Bond 33012.7 Reactions via Decarbonylation of Aldehydes and Carboxylic Acid  Derivatives 33212.8 Conclusion 333References 334Part II Rhodium(II) Catalysis 34113 Rhodium(II) Tetracarboxylate-Catalyzed Enantioselective C–H Functionalization Reactions 343Sidney M.Wilkerson-Hill and Huw M. L. Davies13.1 Introduction 34313.2 Mechanistic Insights and General Considerations 34413.3 Development of Rh2(S-DOSP)4 as a Chiral Catalyst for C–H Functionalization 34713.4 Combined C–H Functionalization/Cope Rearrangement 35013.5 Phthalimido Amino Acid-Derived Catalysts for Intramolecular C–H Functionalization 35313.6 Development of Triarylcyclopropane Carboxylate Rh(II) Complexes for Catalyst-Controlled Site-Selective C–H Functionalization 35913.7 Emerging Chiral Dirhodium Catalyst for Enantioselective C–H Functionalization 36413.8 New Paradigms in the Logic of Chemical Synthesis 36513.9 Conclusion 368Acknowledgments 369References 36914 Rhodium(II)-Catalyzed Nitrogen-Atom Transfer for Oxidation of Aliphatic C—H Bonds 373TomG. Driver14.1 Introduction 37314.2 Mechanism-Inspired Development of New Rh2(II) Catalysts 37414.2.1 Mechanism of Intramolecular Rh2(II)-Catalyzed C—H Bond Amination 37414.2.2 Tetradentate Carboxylate Ligands for Bimetallic Rhodium(II) Complexes 37514.2.3 Design, Synthesis, and Performance of Rh2 II,III Complexes 38114.3 The Development of New Intramolecular Rh2(II)-Catalyzed sp3-C—H Bond Amination 38314.3.1 C—H Bond Amination of Ethereal Bonds 38314.3.2 The Use of Rh2(II)-Catalyzed C—H Bond Amination to Create Glycans and Glycosides 38514.3.3 C—H Bond Amination of MIDA Boronates 38614.3.4 Formation of Medium-Ring N-HeterocyclesThrough C—H Bond Amination 38714.3.5 Synthesis of Spiroaminal Scaffolds 38714.3.6 Expanding the Scope of C—H Bond Amination with New NH2-Based N-Atom Precursors 38914.3.7 N-Tosylcarbamate N-Atom Precursors in Rh2(II)-Catalyzed C—H Bond Amination Reactions 39414.3.8 Aryl Azide N-Atom Precursors in Rh2(II)-Catalyzed sp3-C—H Bond Amination Reactions 39814.4 Intermolecular Rh2(II)-Catalyzed sp3-C—H Bond Amination Using an Iodine(III) Oxidant to Generate the Nitrene 40014.4.1 Intermolecular C—H Bond Amination of Activated C—H Bonds 40014.5 Non-Oxidatively Generated Nitrenes in Intermolecular Rh2(II)-Catalyzed sp3-C—H Bond Amination 41114.5.1 N-Tosylcarbamates as the Nitrogen-Atom Precursor in Intermolecular sp3-C—H Bond Amination Processes 41114.5.2 Azides as the Nitrogen-Atom Precursor in Intermolecular sp3-C—H Bond Amination Reactions 41414.6 Diastereoselective Rh2(II)-Catalyzed sp3-C—H Bond Amination Using Chiral, Non-racemic Nitrogen-Atom Precursors 41614.6.1 Intermolecular Diastereoselective C—H Bond Amination Using Sulfonimidamides 41614.6.2 Intermolecular Diastereoselective C—H Bond Amination Using N-Tosylcarbamates 42214.7 Enantioselective Rh2(II)-Catalyzed sp3-C—H Bond Amination 42214.7.1 Intramolecular Asymmetric C—H Bond Amination 42214.8 Conclusion 429References 43015 Rhodium(II)-Catalyzed Cyclopropanation 433Vincent N.G. Lindsay15.1 Introduction 43315.1.1 Mechanistic Considerations 43415.2 Intermolecular Cyclopropanation of Alkenes 43615.2.1 Via Rhodium(II) Carbenes Bearing One Electron-Withdrawing Group (Acceptor Carbenes) 43815.2.2 Via Rhodium(II) Carbenes Bearing One Electron-Withdrawing Group and One Electron-Donating Group (Donor–Acceptor Carbenes) 44015.2.3 Via Rhodium(II) Carbenes Bearing Two Electron-Withdrawing Groups (Acceptor–Acceptor Carbenes) 44115.3 Intramolecular Cyclopropanation of Alkenes 44315.4 Cyclopropanation of Poorly Nucleophilic 𝜋-Systems: Alkynes, Arenes, and Allenes as Substrates 44415.5 Conclusion 445References 44516 Reactions of 𝛂-Imino Rhodium(II) Carbene Complexes Generated fromN-Sulfonyl-1,2,3-Triazoles 449TomoyaMiura and Masahiro Murakami16.1 Introduction 44916.2 Synthesis of N-Sulfonyl-1,2,3-Triazoles 45116.3 Reactions of Carbon Nucleophiles with α-Imino Rhodium(II) Carbene Complexes 45116.4 Reactions of Oxygen and Sulfur Nucleophiles with α-Imino Rhodium(II) Carbene Complexes 45816.5 Reactions of Nitrogen Nucleophiles with α-Imino Rhodium(II) Carbene Complexes 46416.6 Conclusion 466References 46717 Rhodium(II)-Catalyzed 1,3- and 1,5-Dipolar Cycloaddition 471Nirupam De, Donguk Ko, and Eun Jeong Yoo17.1 Introduction 47117.2 1,3-Dipolar Cycloadditions of Carbonyl Ylides 47117.2.1 [3+2] Cycloadditions of Carbonyl Ylides and Dipolarophiles 47117.2.2 Chemoselective [3+2] Cycloadditions of Carbonyl Ylides 47517.2.3 Applications to Natural Product Synthesis 47617.3 1,3-Dipolar Cycloadditions of Azomethine Ylides 47817.4 1,3-Dipolar Cycloadditions of Enoldiazo Compounds 47917.5 1,5-Dipolar Cycloadditions of Pyridinium Zwitterions 48217.6 Conclusion 484References 484Part III Rhodium(III) Catalysis 48718 Rhodium(III)-Catalyzed Annulative Carbon–Hydrogen Bond Functionalization 489Tetsuya Satoh andMasahiroMiura18.1 Introduction 48918.2 Type A Annulation 49018.2.1 Annulation Utilizing Oxygen-containing Directing Group 49018.2.2 Annulation Utilizing Nitrogen-containing Directing Group 49218.2.3 Annulation Utilizing Sulfur-containing Directing Group 50418.2.4 Annulation Utilizing Phosphorus-containing Directing Group 50618.3 Type B Annulation 50818.4 Type C Annulation 51018.5 Type D Cyclization 51518.6 Conclusion 516References 51719 Rhodium(III)-Catalyzed Non-annulative Carbon–Hydrogen Bond Functionalization 521Fang Xie and Xingwei Li19.1 Introduction 52119.2 Alkenylation and Arylation 52219.2.1 Rh(III)-Catalyzed Non-annulative C—H Alkenylation 52219.2.1.1 Oxidative Dehydrogenative Alkenylation Reactions 52219.2.1.2 Redox-Neutral Alkenylation with Internal Oxidizing Ability 52319.2.1.3 Alkenylations from Alkynes 52519.2.2 Rh(III)-Catalyzed Non-annulative C—H Arylation 52919.2.2.1 Non-annulative Oxidative Dehydrogenative Arylation 52919.2.2.2 Other Types of C–H Arylation 53319.3 Alkynylation 54019.3.1 Rh(III)-Catalyzed Non-annulative C—H Alkynylation 54019.4 Alkylation 54119.4.1 Rh(III)-Catalyzed Non-annulative C—H Couplings with Diazo Compounds 54119.4.2 Rh(III)-Catalyzed Non-annulative Allylations 54319.4.3 Rh(III)-Catalyzed Non-annulative Alkylations Through Addition of C—H Bond to C=X (X =C, O, N) Bonds 55219.4.3.1 Addition of C—H Bond to C=C Bond 55219.4.3.2 Addition of C—H Bond to C=O Bond 55519.4.3.3 Addition of C—H Bond to C=N Bond 55819.4.4 Rh(III)-Catalyzed Non-annulative Alkylations Through Opening Strained Rings 56019.4.5 Rh(III)-Catalyzed Non-annulative Alkylations Through Transmetalation 56319.5 C—N Bond Formation 56419.5.1 Rh(III)-Catalyzed Non-annulative Aminations 56419.5.2 Rh(III)-Catalyzed Non-annulative Amidations 56919.6 Introduction of C=O Bond 57719.6.1 Rh(III)-Catalyzed Non-annulative Acylations 57719.6.2 Rh(III)-Catalyzed Non-annulative Amidations 57919.7 Cyanation 57919.8 C—O Bond Formation 58019.9 C—X Bond Formation 58119.9.1 Non-annulative Halogenation of Arenes 58119.9.2 C—H Hyperiodination of Arenes 58319.10 Non-annulative Thiolation of Arenes 58519.11 C—Se Bond Formation 58519.12 Conclusion 586References 58720 Sterically and Electronically Tuned Cp Ligands for Rhodium(III)-Catalyzed Carbon–Hydrogen Bond Functionalization 593Fedor Romanov-Michailidis, Erik J.T. Phipps, and Tomislav Rovis20.1 Introduction 59320.2 QuantitativeModels for Steric and Electronic Parameterization of Cp Ligands on Rhodium(III) 59420.3 Sterically Tuned Cp Ligands 59820.3.1 Earlier Results 59820.3.2 Synthesis of Isoquinolones, Pyridones, and Derivatives 59920.3.3 Synthesis of Pyridines 60720.3.4 Cyclopropanation and Carboamination Reactions 60720.4 Electronically Tuned Cp Ligands 61220.4.1 Synthesis of Pyridines and Derivatives 61220.4.2 Tanaka’s Ethoxycarbonyl-Substituted Cyclopentadienyl Ligand (CpE) 61520.5 Conclusion 626References 62621 Chiral Cp Ligands for Rhodium(III)-Catalyzed Asymmetric Carbon–Hydrogen Bond Functionalization 629Christopher G. Newton and Nicolai Cramer21.1 Introduction 62921.2 SeminalWork 62921.3 The Ligands 63021.3.1 Development 63021.3.2 Established Families 63121.3.3 Complexation Methods 63321.4 Applications 63421.4.1 Introduction 63421.4.2 Hydroxamate Directing Groups 63421.4.3 Pyridyl Directing Groups 63821.4.4 Hydroxy Directing Groups 63921.4.5 Other Directing Groups 64121.5 Conclusion 642References 642Index 645