The art of writing reasonable organic reaction mechanisms - Grossman, Robert B. 1964- (Springer, 2019)
Chapter 1. The Basics.; 1. Structure and Stability of Organic Compounds; o Conventions of Drawing Structures; Grossman's Rule; o Lewis Structures; Resonance Structures; o Molecular Shape; Hybridization; o Aromaticity; 2. Bronsted Acidity and Basicity; o pKa Values; o Tautomerism; 3. Kinetics and Thermodynamics; 4. Getting Started at Drawing a Mechanism; o Reading and balancing organic reaction equations; o Determining which bonds are made and broken in a reaction; 5. Classes of Overall Transformations; 6. Classes of Mechanisms ; o Polar Mechanisms; § Nucleophiles; § Electrophiles and Leaving Groups; § Acidic and Basic Conditions; The pKa Rule; § A Typical Polar Mechanism; o Free-Radical Mechanisms; o Pericyclic Mechanisms; o Transition-Metal-Catalyzed and -Mediated Mechanisms; 7. Summary; 8. End of Chapter Problems; Chapter 2. Polar Reactions under Basic Conditions.; 1.
- Introduction to Substitution and Elimination; o Substitution by the SN2 Mechanism; o ß-Elimination by the E2 and E1cb Mechanisms; o Predicting Substitution vs. Elimination; 2. Addition of Nucleophiles to Electrophilic p Bonds; o Addition to Carbonyl Compounds; o Conjugate Addition; The Michael Reaction; 3. Substitution at C(sp2)–X s Bonds; o Substitution at Carbonyl C; o Substitution at Alkenyl and Aryl C; o Metal Insertion; Halogen–Metal Exchange; 4. Substitution and Elimination at C(sp3)–X s Bonds; o Substitution by the SRN1 Mechanism; o Substitution by the Elimination–Addition Mechanism; o Substitution by the One-Electron Transfer Mechanism; o Metal Insertion; Halogen–Metal Exchange; o a-Elimination; Generation and Reactions of Carbenes; 5. Base-Promoted Rearrangements; o Migrations from C to C; o Migrations from C to O; o Migrations from C to N; o Migrations from B to C or O; 6.
- Two Multistep Reactions; o The Swern Oxidation; o The Mitsunobu Reaction; 7. Summary; 8. End of Chapter Problems; Chapter 3. Polar Reactions under Acidic Conditions.; 1. Carbocations; o Carbocation Stability; o Carbocation Generation; The Role of Protonation; o Typical Reactions of Carbocations; Rearrangements; 2. Substitution and ß-Elimination Reactions at C(sp3)–X; o Substitution by the SN1 and SN2 Mechanisms; o Elimination by the E1 Mechanism; o Predicting Substitution vs. Elimination; 3. Electrophilic Addition to Nucleophilic C=C p Bonds; 4. Substitution at Nucleophilic C=C p Bonds; o Electrophilic Aromatic Substitution; o Aromatic Substitution of Anilines via Diazonium Salts; o Electrophilic Aliphatic Substitution; 5. Nucleophilic Addition to and Substitution at Electrophilic p Bonds.; o Heteroatom Nucleophiles; o Carbon Nucleophiles; 6. Catalysis Involving Iminium Ions; 7. Summary; 8.
- End of Chapter Problems; Chapter 4. Pericyclic Reactions.; 1. Introduction; o Classes of Pericyclic Reactions; o Polyene MOs; 2. Electrocyclic Reactions; o Typical Reactions; o Stereospecificity; o Stereoselectivity ; 3. Cycloadditions; o Typical Reactions; § The Diels–Alder Reaction; § Other Cycloadditions; o Regioselectivity ; o Stereospecificity; o Stereoselectivity ; 4. Sigmatropic Rearrangements; o Typical Reactions; o Stereospecificity ; o Stereoselectivity; 5. Ene Reactions.; 6. Summary; 7. End of Chapter Problems; Chapter 5. Free Radical Reactions.; 1. Free Radicals; o Stability; o Generation from Closed-Shell Species; o Typical Reactions; o Chain vs. Nonchain Mechanisms; 2. Chain Free-Radical Reactions; o Substitution Reactions; o Addition and Fragmentation Reactions; § Carbon-Heteroatom Bond-Forming Reactions; § Carbon-Carbon Bond-Forming and -Cleaving Reactions; 3.
- Nonchain Free-Radical Reactions; o Photochemical Reactions; o Reductions and Oxidations with Metals; § Addition of H2 across p Bonds ; § Reduction of C-X Bonds. Reductive Coupling; § One-Electron Oxidations; o Cycloaromatizations; 4. Miscellaneous Radical Reactions; o 1,2-Anionic Rearrangements; Lone-Pair Inversion; o Triplet Carbenes and Nitrenes; 5. Summary; 6. End of Chapter Problems; Chapter 6. Transition-Metal-Mediated and -Catalyzed Reactions.; 1. Introduction to the Chemistry of Transition Metals; o Conventions of Drawing Structures; o Counting Electrons; § Typical Ligands; Total Electron Count; § Oxidation State and d Electron Count; o Typical Reactions; o Stoichiometric vs. Catalytic Mechanisms; 2.