유기 반응의 이해 II

CHAPTER 01 Reactions of Carbon-Heteroatom pi-Bonds with Heteronucleophiles
1.1 Types and Reactivity Order of Carbonyl Compounds 2
1.2 Addition of Strong Anionic Heteronucleophiles 3
1.3 Addition of Weak Neutral Nucleophiles 6
1.4 Addition of Water to Form Hydrates 8
1.5 Addition of Alcohol to Form Hemiacetals 10
1.6 Acetal Formation from Hemiacetals 12
1.7 Reactions with Thiols to Form Dithioacetals 18
1.8 Formation of Aminals (N,N-Acetals) 21
1.9 Imine Formation with Primary Amines 23
1.10 Enamine Formation with Secondary Amines 26
1.11 Addition of Cyanide to Form Cyanohydrins 29
1.12 Reactivity Order of Carboxyl Derivatives 31
1.13 Catalyzed Acyl Substitution of Carboxyl Derivatives 37
1.14 Formation and Reactions of Esters 43
1.15 Formation and Reactions of Amides and Nitriles 50
1.16 Derivatives of Carbonic Acid 58
1.17 Hydride Reduction of Carbonyl Compounds: Typical Nonreversible Carbonyl Addition 61

CHAPTER 02 Reactions of Carbon-Heteroatom pi-Bonds with Carbonucleophiles
2.1 Organometallics: Important Carbonucleophiles 74
2.2 Formation of Grignard Reagents: Metal Insertion 75
2.3 Lithiation of Organo Halides 79
2.4 Carbonucleophiles by Deprotonation 83
2.5 Addition of Alkylmetals to Aldehydes and Ketones 88
2.6 Addition of Alkylmetals to Carboxyl Derivatives 95
2.7 Addition of Alkylmetals to Imines and Nitriles 100
2.8 Addition of Alkylmetals Carbonic Acid Derivatives 102
2.9 Enols and Enolates: Formation and Trapping 105
2.10 Aldol Reactions via Anionic Enolate 112
2.11 Crossed Aldol and Intramolecular Aldol Reactions 116
2.12 Directed Aldol Reactions 120
2.13 Acid Catalyzed Aldol Reactions via Enol 124
2.14 Mukaiyama Aldol Reactions via TMS Enol Ethers 126
2.15 Knoevenagel Condensation 129
2.16 Mannich Reactions Proceed via Iminium Ions 132
2.17 Reactions of Enolates with Other Carbonyl Derivatives 134
2.18 Claisen Condensation of Esters 136
2.19 Crossed Claisen Condensation 140
2.20 Decarboxylation of β-Keto Acids and Esters 143
2.21 Acylation of Carbonyls under Acidic Conditions 144
2.22 Acylation of Enol Ethers and Enamines 146
2.23 Sulfur-Stabilized Carbanions and Lithiodithianes 147



CHAPTER 03 Nucleophilic Substitutions at Saturated Carbon
3.1 Characteristic Feature of SN2 Reactions and Mechanism 156
3.2 Steric Crowdedness: the Most Crucial Factor for SN2 158
3.3 Soft Nucleophiles are Best for SN2 162
3.4 Good Leaving Group is Essential in SN2 Reactions 165
3.5 Stereospecific SN2 (Inversion of Configuration) 169
3.6 Leaving Group Departs First in SN1 Mechanism 172
3.7 SN1 Reactions Produce Racemates 174
3.8 Carbocations are the Most Unstable Species 176
3.9 Rate of SN1 Depends on Rate of Carbocation Formation 179
3.10 Carbocations Can React with Reluctant Nucleophiles 181
3.11 Too Unstable Carbocations CANNOT be Formed 185
3.12 Concerted SN2 Competes with Cationic SN1 188
3.13 Anchimeric Assistance in SN1 Reactions 190
3.14 Intramolecular Substitution Produces Cyclic Compounds 193
3.15 Reactions of Nucleophiles with Heteroelectrophiles 196
3.16 Substitution by Hydride Nucleophiles (Defunctionalization) 201
3.17 Substitution by Nitrogen Nucleophiles 203
3.18 Substitution by Oxygen Nucleophiles 205
3.19 Substitution by Phosphorous and Sulfur Nucleophiles 209
3.20 Substitution by the Most Important Carbon Nucleophiles 212
3.20.1 ?Alkylmetals as Nucleophiles 213
3.20.2 ?Doubly-Stabilized Carbanions 216
3.20.3 ?Less-Stabilized Enolates 220
3.20.4 ?Nucleophilic Substitution by Enol Ethers and Enamines 227
End of Chapter Problems 231


CHAPTER 04 Elimination Reactions Leading to Alkenes and Alkynes
4.1 Competitive Substitution and Elimination at sp3 Carbon 236
4.2 Regiochemistry of E1: Deprotonation of Carbocation 241
4.3 Rearranged Alkenes from E1 Reactions 244
4.4 Stereospecific anti-Elimination: E2 Mechanism 249
4.5 Regio- and Stereo-isomeric Mixture of Products in E2 255
4.6 Prediction of Competitive E2 and SN2 260
Nucleophilicity and Basicity 260
Structure of Alkyl Halides 262
Other Factors Affecting SN2 and E2 264
4.7 Modification of OH Group for E2 Reactions 265
4.8 Proton Abstraction First for E1cb Reactions 267
4.9 Triple Bond-Forming Elimination 270
4.10 Elimination on Aromatic Rings: Benzyne Mechanism 273
4.11 Thermal syn-Elimination (Ei reaction) 278
4.12 Practical Synthesis of Alkenes I. Wittig Reaction 284
4.13 Practical Synthesis of Alkenes II. Peterson Olefination 288
4.14 Practical Synthesis of Alkenes III. Julia Olefination 293
End of Chapter Problems 295


CHAPTER 05 Nucleophilic Addition to Carbon-Carbon pi-Bonds
5.1 What are Electrophilic Alkenes? 300
5.2 α, β-Unsaturated Carbonyls: Conjugate or Direct Addition? 301
5.3 Conjugate Addition of Heteroatom Nucleophiles 303
5.4 Factors Affecting Conjugate and Direct Addition 309
5.5 Unsaturated Systems Favoring Conjugate Addition 314
5.6 Epoxidation of Enones by Hydroperoxide 315
5.7 Carbonyl Reduction or Conjugate Reduction? 317
5.8 1,4-Addition of Carbonucleophiles: Michael Addition 321
5.9 Addition of Alkylcuprates to Unsaturated Carbonyls 329
5.10 Michael Addition in Acidic Media 335
5.11 Michael Addition via Enamines and Silyl Enol Ethers 336
5.12 Robinson Annulation 343
5.13 Various Ylides React with Carbonyl Compounds 349
5.14 Nucleophilic Vinylic Substitution 352
5.15 Nucleophilic Aromatic Substitution 355
5.16 Nucleophilic Substitution at Allylic Carbon: SN2' Mechanism 362
5.17 Some Alkylmetals Add to Simple Alkenes and Alkynes 364


CHAPTER 06 Electrophilic Addition to Carbon-Carbon pi-Bonds
6.1 Electrophilic Addition to Alkenes: General Features 372
6.2 Hydroboration: Concerted Stereospecific syn-Addition 373
6.3 Synthetic Application of Alkylboranes 378
6.4 Epoxidation of Alkenes 386
6.5 Electrophilic Addition to C=C π-bond through Onium Ions 389
6.6 Diastereoselective anti-Addition of Bromine 389
6.7 Electrophilic Addition of Cl2 Produces an anti-Adduct 396
6.8 Halolactonization 398
6.9 Solvomercuration of Alkenes and Alkynes 401
6.10 Addition of Other Heteroatom Electrophiles 404
6.11 Electrophilic Addition of Hydrogen Halides 405
6.12 Addition of Water and Alcohols to Alkenes 409
6.13 Alkyne Hydration Leads to Ketone Formation 411
6.14 Electrophilic Addition to Conjugate Dienes 413
6.15 Isomerization of Alkenes 416
6.16 Carbocations Add to C=C π-Bonds 418


CHAPTER 07 Electrophilic Substitution of Arenes and Alkenes
7.1 Electrophilic Aromatic Substitution in General 426
7.2 Substituent Effect on Electrophilic Aromatic Substitution 428
7.3 Electrophilic Halogen Substitution on Aromatics 438
7.4 Sulfonation of Aromatic Compounds 442
7.5 Nitration of Aromatic Compounds 444
7.6 Coupling Reactions of Aryldiazonium ions 450
7.7 Friedel-Craft Acylation 451
7.8 Friedel-Craft Alkylation 457
7.9 Electrophilic Substitution on Heteroaromatic Rings 463
7.10 Thermodynamic Products from Aromatic Substitution 470
7.11 ipso-Substitution and Related Reactions 475
7.12 Indirect Introduction of Substituents onto Aromatic Rings 479
7.13 Regio-Control of Substituents 484
More Problems on Aromatic Substitution 488
7.14 Electrophilic Aliphatic Substitution 490
7.15 Reactions of Allylsilanes and Vinylsilanes 493