Page 19 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

9.4. Specific Electrophilic Substitution Reactions ............................................. 796 xix
9.4.1. Nitration............................................................................................ 796
Contents
9.4.2. Halogenation..................................................................................... 800
9.4.3. Protonation and Hydrogen Exchange .............................................. 804
9.4.4. Friedel-Crafts Alkylation and Related Reactions............................ 805
9.4.5. Friedel-Crafts Acylation and Related Reactions ............................. 809
9.4.6. Aromatic Substitution by Diazonium Ions...................................... 813
9.4.7. Substitution of Groups Other than Hydrogen ................................. 814
9.5. Nucleophilic Aromatic Substitution............................................................. 816
9.5.1. Nucleophilic Aromatic Substitution by the
Addition-Elimination Mechanism.................................................... 817
9.5.2. Nucleophilic Aromatic Substitution by the
Elimination-Addition Mechanism.................................................... 821
General References ................................................................................................ 824
Problems................................................................................................................. 824

Chapter 10. Concerted Pericyclic Reactions.............................. 833

Introduction ............................................................................................................ 833
10.1. Cycloaddition Reactions .............................................................................. 834
10.2. The Diels-Alder Reaction ............................................................................ 839
10.2.1. Stereochemistry of the Diels-Alder Reaction................................. 839
10.2.2. Substituent Effects on Reactivity, Regioselectivity
and Stereochemistry........................................................................ 843
10.2.3. Catalysis of Diels-Alder Reactions by Lewis Acids...................... 848
10.2.4. Computational Characterization of Diels-Alder Transition
Structures......................................................................................... 851
10.2.5. Scope and Synthetic Applications of the
Diels-Alder Reaction....................................................................... 860
10.2.6. Enantioselective Diels-Alder Reactions ......................................... 865
10.2.7. Intramolecular Diels-Alder Reactions ............................................ 868
10.3. 1,3-Dipolar Cycloaddition Reactions........................................................... 873
10.3.1. Relative Reactivity, Regioselectivity, Stereoselectivity,
and Transition Structures................................................................ 874
10.3.2. Scope and Applications of 1,3-Dipolar Cycloadditions................. 884
10.3.3. Catalysis of 1,3-Dipolar Cycloaddition Reactions......................... 886
10.4. 2+2 Cycloaddition Reactions .................................................................. 888
10.5. Electrocyclic Reactions................................................................................ 892
10.5.1. Overview of Electrocyclic Reactions ............................................. 892
10.5.2. Orbital Symmetry Basis for the Stereospecificity of
Electrocyclic Reactions................................................................... 894
10.5.3. Examples of Electrocyclic Reactions ............................................. 903
10.5.4. Electrocyclic Reactions of Charged Species.................................. 906
10.5.5. Electrocyclization of Heteroatomic Trienes................................... 910
10.6. Sigmatropic Rearrangements ....................................................................... 911
10.6.1. Overview of Sigmatropic Rearrangements..................................... 911
10.6.2. [1,3]-, [1,5]-, and [1,7]-Sigmatropic Shifts of Hydrogen
and Alkyl Groups............................................................................ 912