Page 17 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

5.6. Electrophilic Additions Involving Metal Ions............................................. 515 xvii
5.6.1. Solvomercuration.............................................................................. 515
Contents
5.6.2. Argentation—the Formation of Silver Complexes.......................... 520
5.7. Synthesis and Reactions of Alkylboranes ................................................... 521
5.7.1. Hydroboration................................................................................... 522
5.7.2. Reactions of Organoboranes ............................................................ 526
5.7.3. Enantioselective Hydroboration ....................................................... 529
5.8. Comparison of Electrophilic Addition Reactions ....................................... 531
5.9. Additions to Alkynes and Allenes............................................................... 536
5.9.1. Hydrohalogenation and Hydration of Alkynes................................ 538
5.9.2. Halogenation of Alkynes.................................................................. 540
5.9.3. Mercuration of Alkynes.................................................................... 544
5.9.4. Overview of Alkyne Additions ........................................................ 544
5.9.5. Additions to Allenes......................................................................... 545
5.10. Elimination Reactions.................................................................................. 546
5.10.1. The E2, E1 and E1cb Mechanisms................................................ 548
5.10.2. Regiochemistry of Elimination Reactions ..................................... 554
5.10.3. Stereochemistry of E2 Elimination Reactions ............................... 558
5.10.4. Dehydration of Alcohols ................................................................ 563
5.10.5. Eliminations Reactions Not Involving C−H Bonds...................... 564
General References ................................................................................................ 569
Problems................................................................................................................. 569

Chapter 6. Carbanions and Other Carbon Nucleophiles................. 579

Introduction ............................................................................................................ 559
6.1. Acidity of Hydrocarbons ............................................................................... 579
6.2. Carbanion Character of Organometallic Compounds ................................... 588
6.3. Carbanions Stabilized by Functional Groups................................................ 591
6.4. Enols and Enamines....................................................................................... 601
6.5. Carbanions as Nucleophiles in S 2 Reactions.............................................. 609
N
6.5.1. Substitution Reactions of Organometallic Reagents.......................... 609
6.5.2. Substitution Reactions of Enolates..................................................... 611
General References................................................................................................. 619
Problems ................................................................................................................. 619

Chapter 7. Addition, Condensation and Substitution Reactions
of Carbonyl Compounds .................................... 629

Introduction............................................................................................................. 629
7.1. Reactivity of Carbonyl Compounds toward Addition .................................. 632
7.2. Hydration and Addition of Alcohols to Aldehydes and Ketones................. 638
7.3. Condensation Reactions of Aldehydes and Ketones with Nitrogen
Nucleophiles................................................................................................... 645
7.4. Substitution Reactions of Carboxylic Acid Derivatives ............................... 654
7.4.1. Ester Hydrolysis and Exchange ......................................................... 654
7.4.2. Aminolysis of Esters .......................................................................... 659
7.4.3. Amide Hydrolysis............................................................................... 662
7.4.4. Acylation of Nucleophilic Oxygen and Nitrogen Groups................. 664