Intended for students of intermediate organic chemistry, this text shows how to write a reasonable mechanism for an organic chemical transformation. The discussion is organized by types of mechanisms and the conditions under which the reaction is executed, rather than by the overall reaction. Worked problems are included with each mechanism, and "common error alerts" are strategically placed throughout the text. Each chapter is capped by a large problem set. The author draws on both his own research and the current literature to cover topics across the range of modern organic chemistry. The text includes a chapter on reactions mediated or catalyzed by transition metals, and covers emerging topics without short-changing more traditional material. Assuming a basic knowledge of organic chemistry, the text can be used in a formal course or by students working independently, and will be particularly useful as a study aid for qualifying examinations.
Autorentext
Robert B. Grossman earned his A.B. degree at Princeton University and his Ph.D. at MIT. He then moved from Cambridge, Massachusetts to Cambridge, England for his postdoctoral work. In 1994, he moved from the United Kingdom (UK) to the University of Kentucky (UK), where he has been ever since. At UK, Dr. Grossman maintains an active research program focused on synthetic methodology, target-directed synthesis, and biosynthesis. He is also the creator of ACE Organic, a Web-based organic chemistry homework program. Dr. Grossman has also served two terms as one of the two faculty representatives on the UK Board of Trustees.
Inhalt
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; Hybridizationo Aromaticity
2. Bronsted Acidity and Basicity
o pKa Values
o Tautomerism
3. Kinetics and Thermodynamics
4. Getting Started at Drawing a Mechanism5. 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 Mechanismso Predicting Substitution vs. Elimination
2. Addition of Nucleophiles to Electrophilic p Bonds
o Addition to Carbonyl Compounds
o Conjugate Addition; The Michael Reaction3. 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 Bondso 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 Exchangeo a-Elimination; Generation and Reactions of Carbenes
5. Base-Promoted Rearrangements
o Migrations from C to C
o Migrations from C to Oo Migrations from B to C or O
6. Two Multistep Reactions
o The Swern Oxidation
o The Mitsunobu Reaction7. Summary
8. End of Chapter Problems
Chapter 3. Polar Reactions under Acidic Conditions.
1. Carbocations
o Carbocation Stabilityo 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 Mechanismo Predicting Substitution vs. Elimination
3. Electrophilic Addition to Nucleophilic C=C p Bonds
4. Substitution at Nucleophilic C=C p Bonds
o Electrophilic Aromatic Substitutiono Aromatic Substitution of Anilines via Diazonium Salts
o Electrophilic Aliphatic Substitution
5. Nucleophilic Addition to and Substitution at Electrophilic p Bonds.
o Heteroatom Nucleophileso 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 Reactionso Typical Reactions
o Stereospecificity
o Stereoselectivity
3. Cycloadditionso Typical Reactions
§ The Diels-Alder Reaction
§ Other Cycloadditions
o Regioselectivityo Stereospecificity
o Stereoselectivity
4. Sigmatropic Rearrangements
o Typical Reactionso Stereospecificity
o Stereoselectivity
5. Ene Reactions.
6. SummaryChapter 5. Free Radical Reactions.
1. Free Radicals
o Stability
o Generation from Closed-Shell Species
o Typical Reactionso Chain vs. Nonchain Mechanisms
2. Chain Free-Radical Reactions
o Substitution Reactions
o Addition and Fragmentation Reactions3. 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. SummaryChapter 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. Addition Reactionso Late-Metal-Catalyzed Hydrogenation and Hydrometallation (Pd, Pt, Rh)
o Hydroformylation (Co, Rh)
o Hydrozirconation (Zr)
o Alkene Polymerization (Ti, Zr, Sc, and others)o Cyclopropanation, Epoxidation, and Aziridination of Alkenes (Cu, Rh, Mn, Ti)
o Dihydroxylation and Aminohydroxylation of Alkenes (Os)
o Nucleophilic Addition to Alkenes and Alkynes (Hg, Pd)
o Conjugate Addition Reactions (Cu)o Reductive Coupling Reactions (Ti, Zr)
o Pauson-Khand Reaction (Co)
o Dötz Reaction (Cr)
o Metal-Catalyzed Cycloaddition and Cyclotrimerization (Co, Ni, Rh)3. Substitution Reactions
o Hydrogenolysis (Pd)
o Carbonylation of Alkyl Halides (Pd, Rh)
o Heck Reaction (Pd)
o Metal-Caatalyzed Nucleophilic Substitution Reactions: Kumada, Stille, Suzuki, Negishi, Buchwald-Hartwig, Sonogashira, and Ullmann Reactions (Ni, Pd, Cu)
o Allyli…