PREPARATIVE ORGANIC CHEMISTRY
Part I Reactions via Nickelacycles 1 1 Formation of Nickelacycles and Reaction with Carbon Monoxide 3 11 Introduction 3 12 Formation of Hetero-nickelacycles from Nickel(0) 3 13 Stoichiometric Reaction of Hetero-nickelacycles with Carbon Monoxide 4 References 9 2 Transformation of Aldehydes via Nickelacycles 13 21 Introduction and Scope ofThis Chapter 13 22 Catalytic Transformation of Aldehydes ThroughThree-Membered Oxanickelacycle Complexes 14 23 Catalytic Transformation of Aldehydes Through Five-Membered Oxanickelacycle Complexes 18 24 Catalytic Transformation of Aldehydes Through Seven-Membered Oxanickelacycle Complexes 22 25 Conclusion and Outlook 23 References 25 3 Transformation of Imines via Nickelacycles 29 31 Introduction 29 32 [2+2+1] Carbonylative Cycloaddition of an Imine and Either an Alkyne or an Alkene Leading to ?-Lactams 29 33 [2+2+2] Cycloaddition Reaction of an Imine with Two Alkynes: Formation of 1,2-Dihydropyridine Derivatives 31 34 Three-Component Coupling and Cyclocondensation Reactions of an Imine, an Alkyne, and Alkylmetal Reagents 34 References 37 4 Asymmetric C—C Bond Formation Reactions via Nickelacycles 39 41 Introduction 39 42 Enantioselective Reactions Involving Nickelacycles 39 421 Nickel-Catalyzed Asymmetric Coupling of Alkynes and Aldehydes 39 4211 Nickel-Catalyzed Asymmetric Reductive Coupling of Alkynes and Aldehydes 40 4212 Nickel-Catalyzed Asymmetric Alkylative Coupling of Alkynes and Aldehydes 43 422 Nickel-Catalyzed Asymmetric Coupling of Alkynes and Imines 44 423 Nickel-Catalyzed Asymmetric Coupling of 1,3-Enynes and Aldehydes 45 424 Nickel-Catalyzed Asymmetric Coupling of 1,3-Enynes and Ketones 46 425 Nickel-Catalyzed Asymmetric Coupling of 1,3-Dienes and Aldehydes 47 426 Nickel-Catalyzed Asymmetric Coupling of Enones and Alkynes 50 4261 Nickel-Catalyzed Asymmetric Alkylative Coupling of Enones and Alkynes 50 4262 Nickel-Catalyzed Asymmetric Coupling of Enones and Alkynes 51 427 Nickel-Catalyzed Asymmetric Coupling of Arylenoates and Alkynes 55 428 Nickel-Catalyzed Asymmetric Coupling of Diynes with Ketenes 56 429 Nickel-Catalyzed Asymmetric Coupling of Allenes, Aldehydes, and Silanes 57 4210 Nickel-Catalyzed Asymmetric Coupling of Allenes and Isocyanates 58 4211 Nickel-Catalyzed Asymmetric Coupling of Alkenes, Aldehydes, and Silanes 59 4212 Nickel-Catalyzed Asymmetric Coupling of Formamide and Alkene 61 4213 Nickel-Catalyzed Asymmetric Coupling of Alkynes and Cyclopropyl Carboxamide 63 43 Miscellaneous 64 431 Nickel-Catalyzed Asymmetric Annulation of Pyridones via Hydroarylation to Alkenes 64 432 Nickel-Catalyzed Asymmetric Synthesis of Benzoxasilole 65 44 Overview and Future Perspective 66 References 67 Part II Functionalization of Unreactive Bonds 69 5 Recent Advances in Ni-Catalyzed Chelation-Assisted Direct Functionalization of Inert C—HBonds 71 51 Introduction 71 52 Ni-Catalyzed Functionalization of Inert C—H BondsAssisted by Bidentate Directing Groups 71 521 Arylation 72 522 Alkylation 76 523 Alkenylation 83 524 Alkynylation 85 525 Other C—C Bond Formation Reactions Directed by Bidentate Directing Group 88 526 C—N Bond Formation 89 527 C–Chalcogen (Chalcogen = O, S, Se) Bond Formation 89 528 C–Halogen Bond Formation 92 53 Ni-Catalyzed Functionalization of Inert C—H BondsAssisted by Monodentate Directing Groups 94 531 Alkylation 94 532 Alkenylation 95 533 Alkynylation 96 534 C–Calcogen Bond Formation 97 54 Summary 98 References 98 6 C—C Bond Functionalization 103 61 Introduction 103 62 C—C Bond Functionalization ofThree-Membered Rings 103 63 C—C Bond Functionalization of Four- and Five-Membered Rings 110 64 C—C Bond Functionalization of Less Strained Molecules 113 65 C—CN Bond Functionalization 115 66 Summary and Outlook 116 References 117 7 C—OBond Transformations 123 71 Introduction 123 72 C(aryl)—O Bond Cleavage 124 721 Aryl Esters, Carbamates, and Carbonates 124 722 Aryl Ethers 132 723 Arenols 136 73 C(benzyl)—O Bond Cleavage 138 731 Benzyl Esters and Carbamates 138 732 Benzyl Ethers 140 74 C(acyl)—O Bond Cleavage 141 75 Summary and Outlook 144 References 145 Part III Coupling Reactions via Ni(I) and/or Ni(III) 151 8 Photo-Assisted Nickel-Catalyzed Cross-Coupling Processes 153 81 Introduction 153 82 Development of Visible-Light Photoredox/Nickel Dual Catalysis 154 821 For the Formation of Carbon–Carbon Bonds 154 8211 Starting from Organotrifluoroborates 154 8212 Starting from Carboxylates or Keto Acids or fromMethylanilines 157 8213 Starting from Alkylsilicates 160 8214 Starting from 1,4-Dihydropyridines 166 8215 Starting from Alkylsulfinates 168 8216 Starting from Alkyl Bromides 168 8217 Starting from Xanthates 169 8218 Starting from Sp3 CH Bonds 169 822 For the Formation of Carbon–Heteroatom Bonds 170 8221 Formation of C—O Bond 170 8222 Formation of C—P Bond 171 8223 Formation of C—S Bond 171 83 Energy-Transfer-Mediated Nickel Catalysis 173 84 Conclusion 175 References 176 9 Cross-Electrophile Coupling: Principles and New Reactions 183 91 Introduction 183 92 Mechanistic Discussion of Cross-Electrophile Coupling 185 93 C(sp2)—C(sp3) Bond Formation 188 931 Cross-Electrophile Coupling of Aryl-X and Alkyl-X 188 932 Cross-Electrophile Coupling of ArX and Bn-X 195 933 Cross-Electrophile Coupling of ArX and Allyl-X 196 934 Vinyl-X with R-X 197 935 Acyl-X with Alkyl-X 199 94 C(sp2)–C(sp2) Coupling 201 941 Aryl-X/Vinyl-X+Aryl-X/Vinyl-X 201 942 Aryl-X+Acyl-X 202 95 C(sp3)–C(sp3) Coupling 203 96 C(sp)–C(sp3) Coupling 205 97 Multicomponent Reactions 206 98 Future of the Field 208 References 209 10 Organometallic Chemistry of High-Valent Ni(III) and Ni(IV) Complexes 223 101 Introduction 223 102 Organometallic Ni(III) Complexes 223 103 Organometallic Ni(IV) Complexes 234 104 Other High-Valent Ni Complexes 239 1041 Additional NiIII Complexes 239 1042 Additional NiIV Complexes 241 105 Conclusions and Outlook 243 References 244 Part IV Carbon Dioxide Fixation 249 11 Carbon Dioxide Fixation via Nickelacycle 251 111 Introduction: Carbon Dioxide as a C1 Building Block 251 112 Formation, Structure, and Reactivity of Nickelalactone 252 1121 Formation and Characterization of Nickelalactone via Oxidative Cyclization with CO2 252 11211 Reaction with Alkene 252 11212 Reaction with Allene 255 11213 Reaction with Diene 256 11214 Reaction with Alkyne 257 11215 Other Related Reactions 260 11216 Generation of NickelalactoneWithout CO2 261 1122 Reactivity of Nickelalactone 261 11221 Transmetalation with Organometallic Reagent 261 11222 ?-Hydride Elimination 263 11223 Insertion of Another Unsaturated Molecule 264 11224 Retro-cyclization 265 11225 Nucleophilic Attack 265 11226 Oxidation 267 11227 Ligand Exchange 267 113 Catalytic Transformation via Nickelalactone 1: Reactions of Alkynes 268 1131 Synthesis of Pyrone 268 11311 Initial Finding 268 11312 Reaction of Diynes with CO2 268 1132 Synthesis of ?,?-Unsaturated Ester 269 11321 Electrochemical Reactions 269 11322 Reduction with Organometallic Reagents 270 114 Catalytic Transformation via Nickelalactone 2: Reactions of Alkenes and Related Molecules 271 1141 Transformation of Diene, Allene, and Substituted Alkene 271 11411 Coupling of Diene with CO2 271 11412 Electrochemical Process 272 11413 Use of Reductant 272 1142 Synthesis of Acrylic Acid from Ethylene and CO2 274 11421 Before the Dawn 275 11422 Development of Catalytic Reaction 276 115 Concluding Remarks 278 References 279 12 Relevance of Ni(I) in Catalytic Carboxylation Reactions 285 121 Introduction 285 122 Mechanistic Building Blocks 287 1221 Additives 287 1222 Coordination of CO2 287 1223 Insertion/C—C Bond Formation 288 1224 Ligand Effects 289 1225 Oxidative Addition 290 1226 Oxidation State 290 1227 Single Electron Transfer (SET) 290 1228 Conclusion 290 123 Electrocarboxylation 291 1231 Introduction 291 1232 Phosphine Ligands 294 1233 Bipyridine and Related ?-Diimine Ligands 296 1234 Salen Ligands 297 1235 Conclusion 298 124 Non-electrochemical Methods 298 1241 Aryl Halides 300 1242 Benzyl Electrophiles 304 1243 Carboxylation of Unactivated Alkyl Electrophiles 306 1244 Carboxylation of Allyl Electrophiles 312 1245 Unsaturated Systems 315 125 Conclusions 318 References 319