Advanced Organic Chemistry: Part A: Structure and Mechanisms (Advanced Organic Chemistry / Part A: Structure and Mechanisms)

Since its original appearance in 1977, Advanced Organic Chemistry has maintained its place as the premier textbook in the field, offering broad coverage of the structure, reactivity and synthesis of organic compounds. As in the earlier editions, the text contains extensive references to both the primary and review literature and provides examples of data and reactions that illustrate and document the generalizations. While the text assumes completion of an introductory course in organic chemistry, it reviews the fundamental concepts for each topic that is discussed. The two-part fifth edition has been substantially revised and reorganized for greater clarity. Among the changes: Updated material reflecting advances in the field since 2001’s Fourth Edition, especially in computational chemistry; A companion Web site provides digital models for study of structure, reaction and selectivity; Solutions to the exercises provided to instructors online. The material in Part A is organized on the basis of fundamental structural topics such as structure, stereochemistry, conformation and aromaticity and basic mechanistic types, including nucleophilic substitution, addition reactions, carbonyl chemistry, aromatic substitution and free radical reactions. Together with Part B: Reaction and Synthesis, the two volumes are intended to provide the advanced undergraduate or beginning graduate student in chemistry with a sufficient foundation to comprehend and use the research literature in organic chemistry. Preface 5 Acknowledgment and Personal Statement 7 Introduction 9 Table of Contents 13 1. Chemical Bonding and Molecular Structure 22 Introduction 22 1.1. Description of Molecular Structure Using Valence Bond Concepts 23 1.1.1. Hybridization 25 1.1.2. The Origin of Electron-Electron Repulsion 28 1.1.3. Electronegativity and Polarity 29 1.1.4. Electronegativity Equalization 32 1.1.5. Differential Electronegativity of Carbon Atoms 33 1.1.6. Polarizability, Hardness, and Softness 35 1.1.7. Resonance and Conjugation 39 1.1.8. Hyperconjugation 43 1.1.9. Covalent and van der Waals Radii of Atoms 45 1.2. Molecular Orbital Theory and Methods 47 1.2.1. The Huckel MO Method 48 1.2.2. Semiempirical MO Methods 53 1.2.3. Ab Initio Methods 53 1.2.4. Pictorial Representation of MOs for Molecules 56 1.2.5. Qualitative Application of MO Theory to Reactivity: Perturbational MO Theory and Frontier Orbitals 62 1.2.6. Numerical Application of MO Theory 71 1.3. Electron Density Functionals 75 1.4. Representation of Electron Density Distribution 78 1.4.1. Mulliken Population Analysis 81 1.4.2. Natural Bond Orbitals and Natural Population Analysis 82 1.4.3. Atoms in Molecules 84 1.4.4. Comparison and Interpretation of Atomic Charge Calculations 91 1.4.5. Electrostatic Potential Surfaces 94 1.4.6. Relationships between Electron Density and Bond Order 97 Chapter Summary 98 Topic 1.1. The Origin of the Rotational (Torsional) Barrier in Ethane and Other Small Molecules 99 Topic 1.2. Heteroatom Hyperconjugation (Anomeric Effect) in Acyclic Molecules 102 Topic 1.3. Bonding in Cyclopropane and Other Small Ring Compounds 106 Topic 1.4. Representation of Electron Density by the Laplacian Function 113 Topic 1.5. Application of Density Functional Theory to Chemical Properties and Reactivity 115 T.1.5.1. DFT Formulation of Chemical Potential, Electronegativity, Hardness and Softness, and Covalent and van der Waal Radii 116 T.1.5.2. DFT Formulation of Reactivity - The Fukui Function 118 T.1.5.3. DFT Concepts of Substituent Groups Effects 121 General References 127 Problems 127 2. Stereochemistry, Conformation, and Stereoselectivity 139 Introduction 139 2.1. Configuration 139 2.1.1. Configuration at Double Bonds 139 2.1.2. Configuration of Cyclic Compounds 141 2.1.3. Configuration of Tetrahedral Atoms 142 2.1.4. Molecules with Multiple Stereogenic Centers 146 2.1.5. Other Types of Stereogenic Centers 148 2.1.6. The Relationships between Chirality and Symmetry 151 2.1.7. Configuration at Prochiral Centers 153 2.1.8. Resolution - The Seperation of Enantiomers 156 2.2. Conformation 162 2.2.1. Conformation of Acyclic Compounds 162 2.2.2. Conformations of Cyclohexane Derivatives 172 2.2.3. Conformations of Carbocyclic Rings of Other Sizes 181 2.3. Molecular Mechanics 187 2.4. Stereoselective and Stereospecific Reactions 189 2.4.1. Examples of Stereoselective Reactions 190 2.4.1.1. Substituent Directing Effects in Heterogeneous and Homogeneous Hydrogenation 190 2.4.1.2. Hydride Reduction of Cyclic Ketones 196 2.4.1.3. Stereoselective Nucleophilic Additions to Acyclic Carbonyl Groups 198 2.4.2. Examples of Stereospecific Reactions 202 2.4.2.1. Bromination of Alkenes 203 2.4.2.2. Epoxidation and Dihydroxylation of Alkenes 205 2.4.2.3. Hydroboration-Oxidation 206 2.5. Enantioselective Reactions 209 2.5.1. Enantioselective Hydrogenation 209 2.5.2. Enantioselective Reduction of Ketones 213 2.5.3. Enantioselective Epoxidation of Allylic Alcohols 216 2.5.4. Enantioselective Dihydroxylation of Alkenes 220 2.6. Double Stereodifferentiation: Reinforcing and Competing Stereoselectivity 224 Topic 2.1. Analysis and Seperation of Enantiomeric Mixtures 228 T.2.1.1. Chiral Shift Reagents and Chiral Solvating Agents 228 T.2.1.2. Separation of Enantiomers 231 T.2.1.2.1. Separation by Chromatography 231 T.2.1.2.2. Resolution by Capillary Electrophoresis 233 Topic 2.2. Enzymatic Resolution and Desymmetrization 235 T.2.2.1. Lipases and Esterases 236 T.2.2.2. Proteases and Acylases 242 T.2.2.3. Epoxide Hydrolases 244 Topic 2.3. The Anomeric Effect in Cyclic Compounds 247 Topic 2.4. Polar Substituent Effects in Reduction of Carbonyl Compounds 254 General References 259 Problems 260 3. Structural Effects on Stability and Reactivity 272 Introduction 272 3.1. Thermodynamic Stability 273 3.1.1. Relationships between Structure and Thermodynamic Stability for Hydrocarbons 275 3.1.2. Calculation of Enthalpy of Formation and Enthalpy of Reaction 276 3.1.2.1. Calculations of Enthalpy of Reaction Based on Summation of Bond Energies 276 3.1.2.2. Relationships between Bond Energies and Electronegativity and Hardness 278 3.1.2.3. Calculation of Enthalpy of Formation Using Transferable Group Equivalents 280 3.1.2.4. Calculation of Enthalpy of Formation by Molecular Mechanics 282 3.1.2.5. Thermodynamic Data from MO and DFT Computations 283 3.1.2.6. Limitations on Enthalpy Data for Predicting Reactivity 288 3.2. Chemical Kinetics 289 3.2.1. Fundamental Principles of Chemical Kinetics 289 3.2.2. Representation of Potential Energy Changes in Reactions 292 3.2.2.1. Reaction Energy Profiles 292 3.2.2.2. Reaction Energy Diagrams with Two or More Dimensions 295 3.2.2.3. Computation of Reaction Potential Energy Surfaces 297 3.2.3. Reaction Rate Expressions 299 3.2.4. Examples of Rate Expressions 302 3.3. General Relationships between Thermodynamic Stability and Reaction Rates 304 3.3.1. Kinetic versus Thermodynamic Control of Product Composition 304 3.3.2. Correlations between Thermodynamic and Kinetic Aspects of Reactions 306 3.3.2.1. Bells-Evans-Polyani Relationship 307 3.3.2.2. Hammond's Postulate 308 3.3.2.3. The Marcus Equation 312 3.3.3. Curtin-Hammett Principle 315 3.4. Electronic Substituent Effects on Reaction Intermediates 316 3.4.1. Carbocations 319 3.4.2. Carbanions 326 3.4.3. Radical Intermediates 330 3.4.4. Carbonyl Addition Intermediates 338 3.5. Kinetic Isotope Effects 351 3.6. Linear Free-Energy Relationships for Substituent Effects 354 3.6.1. Numerical Expressions of Linear Free-Energy Relationships 354 Example 3.2 358 Example 3.3 358 Example 3.4 359 3.6.2. Application of Linear Free-Energy Relationships to Characterization of Reaction Mechanisms 361 3.7. Catalysis 364 3.7.1. Catalysis by Acids and Bases 364 3.7.1.1. Specific and General Acid/Base Catalysis 365 3.7.1.2. Bronsted Catalysis Law 367 3.7.1.3. Acidity Functions 368 3.7.1.4. pH-Rate Profiles 369 3.7.2. Lewis Acid Catalysis 373 3.8. Solvent Effects 378 3.8.1. Bulk Solvent Effects 378 3.8.2. Examples of Specific Solvent Effects 381 3.8.2.1. Enhanced Nucleophilicity in Polar Aprotic Solvents 382 3.8.2.2. Crown Ether and Phase Transfer Catalysts 382 3.8.2.3. Differential Solvation of Reactants and Transition States 384 3.8.2.4. Oxygen versus Carbon Alkylation in Ambident Enolate Anions 385 Topic 3.1. Acidity of Hydrocarbons 387 General References 395 Problems 395 4. Nucleophilic Substitution 408 Introduction 408 4.1. Mechanisms for Nucelophilic Substitution 408 4.1.1. Substitution by the Ionization (SN1) Mechanism 410 4.1.2. Substitution by the Direct Displacement (SN2) Mechanism 412 4.1.3. Detailed Mechanistic Description and Borderline Mechanisms 414 4.1.4. Relationship between Stereochemistry and Mechanism of Substitution 421 4.1.5. Substitution Reactions of Alkyldiazonium Ions 424 4.2. Structural and Solvation Effects on Reactivity 426 4.2.1. Characteristics of Nucelophilicty 426 4.2.2. Effect of Solvation on Nucleophilicity 430 4.2.3. Leaving-Group Effects 432 4.2.4. Steric and Strain Effects on Substitution and Ionization Rates 434 4.2.5. Effects of Conjugation on Reactivity 436 4.3. Neighboring-Group Participation 438 4.4. Structure and Reactions of Carbocation Intermediates 444 4.4.1. Structure and Stability of Carbocations 444 4.4.2. Direct Observation of Carbocations 455 4.4.3. Competing Reactions of Carbocations 457 4.4.4. Mechanisms of Rearrangement of Carbocations 459 4.4.5. Bridged (Nonclassical Carbocations) 466 Topic 4.1. The Role Carbocations and Caronium Ions in Petroleum Processing 473 General References 478 Problems 478 5. Polar Addition and Elimination Reactions 492 Introduction 492 5.1. Addition of Hydrogen Halides to Alkenes 495 5.2. Acid-Catalyzed Hydration and Related Addition Reactions 501 5.3. Addition of Halogens 504 5.4. Sulfenylation and Selenenylation 516 5.4.1. Sulfenylation 517 5.4.2. Selenenylation 519 5.5. Addition Reactions Involving Epoxides 522 5.5.1. Epoxides from Alkenes and Peroxidic Reagents 522 5.5.2. Subsequent Transformations of Epoxides 530 5.6. Electrophilic Additions Involving Metal Ions 534 5.6.1. Solvomercuration 534 5.6.2. Argentation - the Formation of Silver Complexes 539 5.7. Synthesis and Reactions of Alkylboranes 540 5.7.1. Hydroboration 541 5.7.2. Reactions of Organoboranes 545 5.7.3. Enantioselective Hydroboration 548 5.8. Comparison of Electrophilic Addition Reactions 550 5.9. Additions to Alkynes and Allenes 555 5.9.1. Hydrohalogenation and Hydration of Alkynes 557 5.9.2. Halogenation of Alkynes 559 5.9.3. Mercuration of Alkynes 563 5.9.4. Overview of Alkyne Additions 563 5.9.5. Additions to Allenes 564 5.10. Elimination Reactions 565 5.10.1. The E2, E1 and E1cb Mechanisms 567 5.10.2. Regiochemistry of Elimination Reactions 573 5.10.3. Stereochemistry of E2 Elimination Reactions 577 5.10.4. Dehydration of Alcohols 582 5.10.5. Elimination Reactions Not Involving C-H Bonds 583 General References 588 Problems 588 6. Carbanions and Other Carbon Nucleophiles 597 Introduction 597 6.1. Acidity of Hydrocarbons 597 6.2. Carbanion Character of Organometallic Compounds 606 6.3. Carbanions Stabilized by Functional Groups 609 6.4. Enols and Enamines 619 6.5. Carbanions as Nucleophiles in SN2 Reactions 627 6.5.1. Substitution Reactions of Organometallic Reagents 627 6.5.2. Substitution Reactions of Enolates 629 General References 637 Problems 637 7. Addition, Condensation and Substitution Reactions of Carbonyl Compounds 647 Introduction 647 7.1. Reactivity of Carbonyl Compounds toward Addition 650 7.2. Hydration and Addition of Alcohols to Aldehydes and Ketones 656 7.3. Condensation Reactions of Aldehydes and Ketones with Nitrogen Nucleophiles 663 7.4. Substitution Reactions of Carboxylic Acid Derivatives 672 7.4.1. Ester Hydrolysis and Exchange 672 7.4.2. Aminolysis of Esters 677 7.4.3. Amide Hydrolysis 680 7.4.4. Acylation of Nucleophilic Oxygen and Nitrogen Groups 682 7.5. Intramolecular Catalysis of Carbonyl Substitution Reactions 686 7.6. Addition of Organometallic Reagents to Carbonyl Groups 694 7.6.1. Kinetics of Organometallic Addition Reactions 695 7.6.2. Stereoselectivity of Organometallic Addition Reactions 698 7.7. Addition of Enolates and Enols to Carbonyl Compounds: The Aldol Addition and Condensation Reactions 700 7.7.1. The General Mechanisms 700 7.7.2. Mixed Aldol Condensations with Aromatic Aldehydes 703 7.7.3. Control of Regiochemistry and Stereochemistry of Aldol Reactions of Ketones 705 7.7.4. Aldol Reactions of Other Carbonyl Compounds 710 General References 716 Problems 716 8. Aromaticity 730 Introduction 730 8.1. Criteria of Aromaticity 732 8.1.1. The Energy Criterion for Aromaticity 732 8.1.2. Structural Criteria for Aromaticity 735 8.1.3. Electronic Criteria for Aromaticity 737 8.1.4. Relationship among the Energetic, Structural, and Electronic Criteria of Aromaticity 741 8.2. The Annulenes 742 8.2.1. Cyclobutadiene 742 8.2.2. Benzene 744 8.2.3. 1,3,5,7-Cyclooctatetraene 744 8.2.4. [10]Annulenes - 1,3,5,7,9-Cyclodecapentaene Isomers 745 8.2.5. [12], [14], and [16]Annulenes 747 8.2.6. [18]Annulene and Larger Annulenes 750 8.2.7. Other Related Structures 752 8.3. Aromaticity in Charged Rings 755 8.4. Homoaromaticity 760 8.5. Fused-Ring Systems 762 8.6. Heteroaromatic Systems 775 General References 777 Problems 777 9. Aromatic Substitution 788 Introduction 788 9.1. Electrophilic Aromatic Substitution Reactions 788 9.2. Structure-Reactivity Relationships for Substituted Benzenes 796 9.2.1. Substituent Effects on Reactivity 796 9.2.2. Mechanistic Interpretation of the Relationship between Reactivity and Selectivity 804 9.3. Reactivity of Polycyclic and Heteroaromatic Compounds 808 9.4. Specific Electrophilic Substitution Reactions 813 9.4.1. Nitration 813 9.4.2. Halogenation 817 9.4.3. Protonation and Hydrogen Exchange 821 9.4.4. Friedel-Crafts Alkylation and Related Reactions 822 9.4.5. Friedel-Crafts Acylation and Related Reactions 826 9.4.6. Aromatic Substitution by Diazonium Ions 830 9.4.7. Substitution of Groups Other than Hydrogen 831 9.5. Nucleophilic Aromatic Substitution 833 9.5.1. Nucleophilic Aromatic Substitution by the Addition-Elimination Mechanism 834 9.5.2. Nucleophilic Aromatic Substitution by the Elimination-Addition Mechanism 838 General References 841 Problems 841 10. Concerted Pericyclic Reactions 849 Introduction 849 10.1. Cycloaddition Reactions 850 10.2. The Diels-Adler Reaction 855 10.2.1. Stereochemistry of the Diels-Adler Reaction 855 10.2.2. Substituent Effects on Reactivity, Regioselectivity, and Stereochemistry 859 10.2.3. Catalysis of Diels-Adler Reactions by Lewis Acids 864 10.2.4. Computational Characterization of Diels-Adler Transition Structures 867 10.2.5. Scope and Synthetic Applications of the Diels-Adler Reaction 876 10.2.5.1. Dienophiles 877 10.2.5.2. Dienes 880 10.2.6. Enantioselective Diels-Adler Reactions 881 10.2.6.1. Chiral Auxilaries for Diels-Adler Reactions 881 10.2.6.2. Enantioselective Catalysts for Diels-Adler Reactions 883 10.2.7. Intramolecular Diels-Adler Reactions 884 10.3. 1,3-Dipolar Cycloaddition Reactions 889 10.3.1. Relative Reactivity, Regioselectivity, Stereoselectivity, and Transition Structures 890 10.3.2. Scope and Applications of 1,3-Dipolar Cycloadditions 900 10.3.3. Catalysis of 1,3-Dipolar Cycloaddition Reactions 902 10.4. [2+2] Cycloaddition Reactions 904 10.5. Electrocyclic Reactions 908 10.5.1. Overview of Electrocyclic Reactions 908 10.5.2. Orbital Symmetry Basis for the Stereospecificity of Electrocyclic Reactions 910 10.5.3. Examples of Electrocyclic Reactions 919 10.5.4. Electrocyclic Reactions of Charged Species 922 10.5.5. Electrocyclization of Heteroatomic Trienes 926 10.6. Sigmatropic Rearrangements 927 10.6.1. Overview of Sigmatropic Rearrangements 927 10.6.2. [1,3]-, [1,5]-, and [1,7]-Sigmatropic Shifts of Hydrogen and Alkyl Groups 928 10.6.2.1. Computational Characterization of Transition Structures for [1,3]-, [1,5]-, and [1,7]-Sigmatropic Shifts 931 10.6.2.2. Examples of Sigmatropic Shifts of Hydrogen and Alkyl Groups 932 10.6.3. Overview of [3,3]-Sigmatropic Rearrangements 935 10.6.4. [2,3]-Sigmatropic Rearrangements 955 10.6.4.1. Mechanism of [2,3]-Sigmatropic Rearrangements 955 10.6.4.2. [2,3]-Sigmatropic Rearrangements of Oxides and Ylides 956 10.6.4.3. [2,3]-Sigmatropic Rearrangements of Anions 958 Topic 10.1. Application of DFT Concepts to Reactivity and Regiochemistry of Cycloaddition Reactions 961 Problems 967 11. Free Radical Reactions 981 Introduction 981 11.1. Generation and Characterization of Free Radicals 983 11.1.1. Background 983 11.1.2. Long-Lived Free Radicals 984 11.1.3. Direct Detection of Radical Intermediates 986 11.1.4. Generation of Free Radicals 992 11.1.5. Structural and Stereochemical Properties of Free Radicals 996 11.1.6. Substituent Effects on Radical Stability 1002 11.1.7. Charged Radicals 1004 11.2. Characteristics of Reactions Involving Radical Intermediates 1008 11.2.1. Kinetic Characteristics of Chain Reactions 1008 11.2.2. Determination of Reaction Rates 1011 11.2.3. Structure-Reactivity Relationships 1016 11.2.3.1. Hydrogen Abstraction Reactions 1016 11.2.3.2. Addition Reactions 1020 11.2.3.3. Radical Cyclizations 1024 11.2.3.4. Other Radical Reactions 1029 11.3. Free Radical Substitution Reactions 1034 11.3.1. Halogenation 1034 11.3.2. Oxygenation 1040 11.4. Free Radical Addition Reactions 1042 11.4.1. Addition of Hydrogen Halides 1042 11.4.2. Addition of Halomethanes 1045 11.4.3. Addition of Other Carbon Radicals 1047 11.4.4. Addition of Thiols and Thiocarboxylic Acids 1049 11.4.5. Examples of Radical Addition Reactions 1049 11.5. Other Types of Free Radical Reactions 1053 11.5.1. Halogen, Sulfur, and Selenium Group Transfer Reactions 1053 11.5.2. Intramolecular Hydrogen Atom Transfer Reactions 1056 11.5.3. Rearrangement Reactions of Free Radicals 1057 11.6. SRN1 Substitution Processes 1060 11.6.1. SRN1 Substitution Reactions of Alkyl Nitro Compounds 1061 11.6.2. SRN1 Substitution Reactions of Aryl and Alkyl Halides 1064 Topic 11.1. Relationships between Bond and Radical Stabilization Energies 1068 Topic 11.2. Structure-Reactivity Relationships in Hydrogen Abstraction Reactions 1072 General References 1078 Reactions and Mechanisms 1078 Spectroscopic Methods 1079 Problems 1079 12. Photochemistry 1088 Introduction 1088 12.1. General Principles 1088 12.2. Photochemistry of Alkenes, Dienes, and Polyenes 1096 12.2.1. cis-trans Isomerization 1096 12.2.1.1. Photoisomerization of Ethene and Styrene 1097 12.2.1.2. Photoisomerization of Stilbene 1100 12.2.2. Photoreactions of Other Alkenes 1106 12.2.3. Photoisomerization of 1,3-Butadiene 1111 12.2.4. Orbital Symmetry Considerations for Photochemical Reactions of Alkenes and Dienes 1112 12.2.5. Photochemical Electrocyclic Reactions 1115 12.2.6. Photochemical Cycloaddition Reactions 1124 12.2.7. Photochemical Rearrangements Reactions of 1,4-Dienes 1127 12.3. Photochemistry of Carbonyl Compounds 1131 12.3.1. Hydrogen Abstraction and Fragmentation Reactions 1133 12.3.2. Cycloaddition and Rearrangement Reactions of Cyclic Unsaturated Ketones 1140 12.3.3. Cycloaddition of Carbonyl Compounds and Alkenes 1147 12.4. Photochemistry of Aromatic Compounds 1149 Topic 12.1. Computational Interpretation of Diene and Polyene Photochemistry 1152 General References 1160 Problems 1160 References for Problems 1169 Chapter 1 1169 Chapter 2 1170 Chapter 3 1172 Chapter 4 1173 Chapter 5 1174 Chapter 6 1175 Chapter 7 1176 Chapter 8 1177 Chapter 9 1178 Chapter 10 1179 Chapter 11 1181 Chapter 12 1182 Index 1184 Since its original appearance in 1977, Advanced Organic Chemistry has maintained its place as the premier textbook in the field, offering broad coverage of the structure, reactivity and synthesis of organic compounds. As in the earlier editions, the text contains extensive references to both the primary and review literature and provides examples of data and reactions that illustrate and document the generalizations. While the text assumes completion of an introductory course in organic chemistry, it reviews the fundamental concepts for each topic that is discussed. The two-part fifth edition has been substantially revised and reorganized for greater clarity. Part A begins with the fundamental concepts of structure and stereochemistry, and the thermodynamic and kinetic aspects of reactivity. Major reaction types covered include nucleophilic substitution, addition reactions, carbanion and carbonyl chemistry, aromatic substitution, pericyclic reactions, radical reactions, and photochemistry. Among the changes: Coverage of the importance of computational chemistry in modern organic chemistry, including applications to many specific reactions. Expanded coverage of stereoselectivity and enantioselectivity, including discussion of several examples of enantioselective reagents and catalysts Chapter 10, Concerted Pericyclic Reactions, has been reorganized and now begins with cycloaddition reactions. The treatment of photochemical reactions has been extensively updated to reflect both experimental and computational studies of the transient intermediates involved in photochemical reactions. A companion Web site provides digital models for study of structure, reaction and selectivity. Here students can view and manipulate computational models of reaction paths. These sites also provide exercises based on detailed study of the computational models. Several chapters in Part A conclude with Topics - short excursions into specific topics such as more detailed analysis of polar substituent effects, efforts to formulate substituent effects in terms of density functional theory, or the role of carbocations in petroleum refining Solutions to the chapter problems are provided to instructors online Advanced Organic Chemistry Part A provides a close look at the structural concepts and mechanistic patterns that are fundamental to organic chemistry. It relates those mechanistic patterns, including relative reactivity and stereochemistry, to underlying structural factors. Understanding these concepts and relationships will allow students to recognize the cohesive patterns of reactivity in organic chemistry. Part A: Structure and Mechanism and Part B: Reaction and Synthesis - taken together - are intended to provide the advanced undergraduate or beginning graduate student in chemistry with a foundation to comprehend and use the research literature in organic chemistry Since its original appearance in 1977, Advanced Organic Chemistry has maintained its place as the premier textbook in the field, offering broad coverage of the structure, reactivity and synthesis of organic compounds. As in the earlier editions, the text contains extensive references to both the primary and review literature and provides examples of data and reactions that illustrate and document the generalizations. While the text assumes completion of an introductory course in organic chemistry, it reviews the fundamental concepts for each topic that is discussed. The two-part fifth edition has been substantially revised and reorganized for greater clarity. Among the changes: Updated material reflecting advances in the field since 2001's Fourth Edition, especially in computational chemistry; A companion Web site provides digital models for study of structure, reaction and selectivity; Solutions to the exercises provided to instructors online. The control of reactivity to achieve specific syntheses is one of the overarching goals of organic chemistry. Part B describes the most general and useful synthetic reactions, organized on the basis of reaction type. Together with Part A: Structure and Mechanisms, the two volumes are intended to provide the advanced undergraduate or beginning graduate student in chemistry with a sufficient foundation to comprehend and use the research literature in organic chemistry

The two-part, fifth edition of Advanced Organic Chemistry has been substantially revised and reorganized for greater clarity. The material has been updated to reflect advances in the field since the previous edition, especially in computational chemistry. Part A covers fundamental structural topics and basic mechanistic types. It can stand-alone; together, with Part B: Reaction and Synthesis, the two volumes provide a comprehensive foundation for the study in organic chemistry. Companion websites provide digital models for study of structure, reaction and selectivity for students and exercise solutions for instructors.