유기 반응의 이해 III

CHAPTER 01 Anchimeric Assistance, Rearrangement and Fragmentation
1.1 Neighboring Group Participation by Lone Pairs 2
1.2 Neighboring Group Participation by pi and sigma-Bonds 10
1.3 Participation and Migration of Neighboring Groups 14
1.4 Carbocation Rearrangement 20
1.5 Rearrangements of Pinacols and Related Compounds 34
1.6 Rearrangements Involving Diazonium Ions 40
1.7 Rearrangements in Borane Chemistry 44
1.8 Migration to Electron-Deficient Oxygen and Nitrogen 55
1.9 Carbonyl Related Migration under Basic Conditions 68
1.10 Rearrangements through Carbenes and Nitrenes 77
1.11 Electron Pair Push-Pull Fragmentation 84

CHAPTER 02 Chemistry of Heteroaromatic Compounds
2.1 Structure of Representative Heteroaromatic Compounds 101
2.2 Reactions of Pyridine Using Lone Pair Electrons 103
2.3 Electrophilic Substitution of Pyridine 105
2.4 Reactions of Pyridine with Nucleophiles 114
2.5 Nucleophilic Substitution of Hydride in Pyridines 116
2.6 Tautomers of Hydroxypyridines and Pyridones 118
2.7 Substitution via Ring Opening and Ring Closure of Pyridine 121
2.8 Reactions of Five-Membered Heteroaromatics with Acid 124
2.9 Reactions of Five-Membered Heteroaromatic Compounds with Heteroatom Electrophiles 126
2.10 Reactions of Five-Membered Heteroaromatic Compounds with Carbon Electrophiles 130
2.11 Reactions of Metallated Heteroaromatic Compounds 136
2.12 Ring Opening of Five-Membered Heteroaromatics 140
2.13 Synthesis of Five-Membered Heteroaromatics 142
2.14 Reactions of Pyridine with Nucleophiles 146
2.15 Synthesis of Pyridines and Derivatives 149
2.16 Synthesis of Quinolines and Isoquinolines 153
2.17 Synthesis of Heteroaromatic Compounds with More than Two Heteroatoms 155

CHAPTER 03 Radicals in Organic Reactions
3.1 How Free Radicals Are Generated? 160
3.2 How Unstable Are Free Radicals? 162
3.3 Major Reaction Types of Radicals 168
3.4 Free Radical Halogenation of Alkanes 171
3.5 Autoxidation 177
3.6 Free Radical Substitution by Heteroatom Abstraction 180
3.7 Free Radical Reduction of Organomercury Compounds 185
3.8 Free Radical Addition of X-Y Type 187
3.9 Radical Hydrostannation and Hydrosilylation 190
3.10 Carbon-Carbon Formation by Addition of Alkyl Radicals 191
3.11 Electrophilic Radicals and Nucleophilic Radicals 193
3.12 Carbon-Carbon Formation Using Organomercurials 197
3.13 Radical Reactions of Aryl Diazonium Salts 200
3.14 Ring-Closing Free Radical Reactions 203
3.15 Do Radicals Rearrange? 209
3.16 Nonchain Free Radical Reactions: Photochemical Reaction 216
3.17 Radical Anions via Single Electron Transfer 221
3.18 Radical Coupling: Pinacol Formation and McMurry Reaction 224
3.19 Birch Reduction 230
3.20 Nucleophilic Substitution via Single Electron Transfer 234

CHAPTER 04 Pericyclic Reactions
4.1 Diels-Alder Reaction: [4+2] Cycloaddition 240
4.1.1 What are Diels-Alder Reactions? 241
4.1.2 Diels-Alder Reactions are Orbital-Controlled 243
4.2 Diels-Alder Reactions are Stereospecific 248
4.2.1 Woodward-Hoffmann Rule and Diels-Alder Reaction 248
4.2.2 Stereospecificity of Diels-Alder Reactions 251
4.3 Regioselectivity of Diels-Alder Reactions 252
4.4 Diels-Alder Reactions are Stereospecific 256
4.4.1 ‘out-endo-cis’ Rule 256
4.4.2 Drawing Stereochemical Structure of Diels-Alder Adducts 260
4.4.3 Anything Different for Intramolecular Diels-Alder Reactions? 262
4.5 1,3-Dipolar Cycloaddition 264
4.5.1 1,3-Dipolar Cycloaddition: Another Type of [4+2] CA 264
4.5.2 Regio- and Stereochemistry of 1,3-Dipolar Cycloaddition 272
4.6 [2+2] Cycloaddition 274
4.6.1 Photochemical [2+2] Cycloaddition 274
4.6.2 Stereo- and Regiochemistry in [2+2] Cycloaddition 276
4.6.3 Thermal [2+2] Cycloaddition: Cycloaddition of Cumulenes 278
4.7 Electrocyclization 287
4.7.1 Types and Energetics of Electrocyclization 287
4.7.2 Stereospecificity in Electrocyclization (FMO View) 288
4.7.3 Woodward-Hoffmann Rule and Stereospecificity 291
4.7.4 Stereoselectivity in Electrocyclization 294
4.7.5 Electrocyclization of Cations and Anions 296
4.8 Sigmatropic Rearrangement and Woodward-Hoffmann Rule 303
4.9 Claisen and Cope Rearrangements 306
4.9.1 Are Sigmatropic Rearrangements Stereospecific? 308
4.9.2 Stereoselectivity in Sigmatropic Rearrangement 310
4.9.3 Variation of [3,3] Sigmatropic Rearrangement 314
4.10 Other Sigmatropic Rearrangements 317
4.10.1 ?[2,3] Sigmatropic Rearrangement 317
4.10.2 ?[1,5] Sigmatropic Rearrangement 319
4.10.3 ?[1,2] Sigmatropic Rearrangement 322
4.10.4 ?[1,3] and [1,7] Sigmatropic Rearrangement 323
4.11 Ene Reactions 328
4.12 Concluding Remark 335

CHAPTER 05 Transition Metal Catalyzed Organic Reactions
5.1 Basic Knowledge of Transition Metal Complexes 338
5.1.1 Recognizing Types of Ligands 339
5.1.2 Total Electron Count 342
5.1.3 Oxidation State: Counting Oxidation Number 345
5.1.4 d Electron Count 345
5.1.5 Summary of Counting Electrons and Oxidation Number 347
5.2 Fundamental Reactions of Transition Metal Complexes 348
5.2.1 Ligand Dissociation, Ligand Substitution, Ligand Addition 348
5.2.2 Oxidative Addition and Reductive Elimination 350
5.2.3 Ligand Insertion and β-Elimination 354
5.2.4 Reactions of Ligands with Nucleophiles 357
5.2.5 Reactions of Ligand with Electrophiles 359
5.2.6 Sigma-Bond Metathesis and Transmetallation 360
5.3 Hydrogen-Related Reactions and Hydrometallation 364
5.3.1 Transition Metal-Catalyzed Hydrogenation 364
5.3.2 Dehydrogenation by Transition Metals and Complex 366
5.3.3 Isomerization of Alkenes 368
5.3.4 Hydrogenolysis 370
5.3.5 Catalyzed Hydroboration, Hydrosilylation, and Hydrocyanation 372
5.4 Carbon Monoxide-Related Reactions 375
5.4.1 Water Gas Shift Reaction 375
5.4.2 Hydroformylation 377
5.4.3 Carbonylation of Alkyl Halides (Pd, Rh) 379
5.4.4 Carbonylation of Alkenes, Alkynes and Allylic Halides 381
5.4.5 Decarbonylation of Aldehydes and Acyl Halides 382
5.4.6 Pauson-Khand Reaction 384
5.5 Ligand Coupling Reactions 387
5.5.1 Heck Reaction (Pd) 388
5.5.2 Kumada Coupling 392
5.5.3 Various Pd(0)-Catalyzed Coupling Reactions 395
5.5.4 Stille Coupling 396
5.5.5 Suzuki Coupling 400
5.5.6 Negishi Coupling 402
5.5.7 Sonogashira Coupling 404
5.5.8 Hiyama Coupling 406
5.5.9 Coupling Reactions Using Copper (Ullmann Reaction) 408
5.6 Reactions Related with Metal Alkylidene 410
5.6.1 Cyclopropanation by Metal Alkylidene 410
5.6.2 Tebbe Reaction (Ti) 411
5.6.3 D?tz Reaction 414
5.6.4 Alkene and Alkyne Metathesis (Ru, W, Mo, Ti) 416
5.7 Reactions with Nucleophiles 421
5.7.1 Coupling Reactions of Aryl, Vinyl with Heteroatom 421
5.7.2 Allylic Substitution 424
5.7.3 Palladium-Catalyzed Nucleophilic Substitution of Alkenes 428
5.7.4 Wacker Oxidation 430
5.7.5 Conjugate Addition of Alkylcuprates to Enones 433
5.8 Addition Reactions of Alkenes 434
5.8.1 Polymerization of Alkenes (Ti, Zr) 434
5.8.2 Metal-Catalyzed Cycloaddition and Cyclotrimerization 436

CHAPTER 06 Stereoselective Organic Reactions
6.1 Review of Representative Stereospecific Reactions 446
6.2 What are Stereoselective Reactions? 451
6.3 Stereoselectivity in Reactions of Cyclic Compounds 455
6.4 Asymmetric Hydroboration Using Chiral Boranes 460
6.5 Stereoselective Addition to Alkenes 462
6.6 Enantioselective Diels-Alder Reactions 467
6.7 Stereoselective Nucleophilic Addition to Chiral Carbonyls 472
6.8 Addition of Chiral Nucleophiles to Carbonyl Compounds 478
6.9 Addition of Chiral Allylmetals to Carbonyl Compounds 479
6.10 Stereochemistry in Enolate Formation 483
6.11 α-Substitution of Enolates with Chiral Center and Auxiliary 486
6.12 Stereochemistry of Aldol Reactions-Diastereoselectivity 490
6.13 Enantioselective Aldol Reactions 495
6.14 Enantioselective Hydride Reduction of Prochiral Ketones 502
6.15 Enantioselective Catalytic Hydrogenation 507
6.16 Enantioselective Epoxidation 512
6.17 Enantioselective Dihydroxylation 516