£44.99
Publication Date:
23 Nov 2019
Publisher:
Springer Nature
For delivery:
Download available
Description
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 inits 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.
Contents
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 -Elimination by the E2 and E1cb Mechanisms o Predicting Substitution vs. Elimination 2. Addition of Nucleophiles to Electrophilic 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 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 -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 -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 Bonds 4. Substitution at Nucleophilic C=C 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 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 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. 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 Doetz 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 Allylic Substitution (Pd) o Pd-Catalyzed Nucleophilic Substitution of Alkenes; Wacker Oxidation o C-H Activation (Pd, Ru, Rh) o Tebbe Reaction (Ti) o Propargyl Substitution in Co-Alkyne Complexes 4. Rearrangement Reactions o Alkene Isomerization (Rh) o Olefin and Alkyne Metathesis (Ru, W, Mo, Ti) 5. Elimination Reactions o Oxidation of Alcohols (Cr, Ru) o Decarbonylation of Aldehydes (Rh) 6. Summary 7. End of Chapter Problems Chapter 7. Mixed Mechanism Problems.
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