The Art of Writing Reasonable Organic Reaction Mechanisms
Beschreibung
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, ra...Format auswählen
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Beschreibung
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 as is the case in most textbooks. The treatment emphasizes unifying principles, showing how common mechanisms link seemingly disparate reactions.
Each chapter discusses common mechanistic pathways and suggests practical tips for drawing them. Worked problems are included in the discussion of each mechanism, and "common error alerts" are scattered throughout the text to warn readers about pitfalls and misconceptions that bedevil students. Each chapter is capped by a large problem set.
The author has drawn on his own research and the current literature to ensure that appropriate attention is given to topics across the range of modern organic chemistry. The text is unique in its inclusion of a chapter on reactions mediated or catalyzed by transition metals, an area in which mechanistic understanding is now essential. More modern topics such as olefin metathesis and cycloaromatization are covered without giving short shrift to more traditional areas such as carbonyl chemistry. The text assumes a basic knowledge of organic chemistry. It can be used either in a formal course or by students working on their own, and will be particularly useful for graduate students studying for qualifying examinations. It will also be useful to students and researchers in biochemistry, pharmacology, and inorganic chemistry.
The third edition includes greater discussion of the reactions of biological cofactors such as thiamine and pyridoxal, and discussions of modern developments such as metal-catalyzed C-H activation reactions have been added. In terms of stylistic improvements, the author has introduced color into drawings to improve visual clarity and has improved the depictions of radical anions and radical chain reactions.
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.
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
Bronsted Acidity and Basicity
o pKa Values
o Tautomerism
Kinetics and Thermodynamics
- Getting Started at Drawing a Mechanism o Reading and balancing organic reaction equations o Determining which bonds are made and broken in a reaction
Classes of Overall Transformations
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
Summary
End of Chapter Problems
Chapter 2. Polar Reactions under Basic Conditions.
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
Addition of Nucleophiles to Electrophilic p Bonds
o Addition to Carbonyl Compounds o Conjugate Addition; The Michael Reaction
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
- 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
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
Two Multistep Reactions
o The Swern Oxidation o The Mitsunobu Reaction
Summary
End of Chapter Problems
Chapter 3. Polar Reactions under Acidic Conditions.
Carbocations o Carbocation Stability
o Carbocation Generation; The Role of Protonation
o Typical Reactions of Carbocations; Rearrangements
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
Electrophilic Addition to Nucleophilic C=C p Bonds
Substitution at Nucleophilic C=C p Bonds o Electrophilic Aromatic Substitution
o Aromatic Substitution of Anilines via Diazonium Salts
o Electrophilic Aliphatic Substitution
Nucleophilic Addition to and Substitution at Electrophilic p Bonds. o Heteroatom Nucleophiles
o Carbon Nucleophiles
Catalysis Involving Iminium Ions
Summary
End of Chapter Problems
Chapter 4. Pericyclic Reactions.
Introduction
o Classes of Pericyclic Reactions
o Polyene MOs
- Electrocyclic Reactions
o Typical Reactions
o Stereospecificity
o Stereoselectivity
- Cycloadditions
o Typical Reactions
§ The Diels-Alder Reaction
§ Other Cycloadditions o Regioselectivity
o Stereospecificity
o Stereoselectivity
Sigmatropic Rearrangements o Typical Reactions
o Stereospecificity
o Stereoselectivity
Ene Reactions.
- Summary 7. End of Chapter Problems
Chapter 5. Free Radical Reactions.
Free Radicals
o Stability
o Generation from Closed-Shell Species o Typical Reactions
o Chain vs. Nonchain Mechanisms
Chain Free-Radical Reactions
o Substitution Reactions o Addition and Fragmentation Reactions § Carbon-Heteroatom Bond-Forming Reactions § Carbon-Carbon Bond-Forming and -Cleaving Reactions
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
Miscellaneous Radical Reactions
o 1,2-Anionic Rearrangements; Lone-Pair Inversion
o Triplet Carbenes and Nitrenes
- Summary 6. End of Chapter Problems
Chapter 6. Transition-Metal-Mediated and -Catalyzed Reactions.
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
- Addition Reactions
o 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)
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…