Advanced Organic Chemistry

by Carey, Francis A.; Sundberg, Richard J.

• ISBN13: 9780387448978
• ISBN10: 0387448977
• Edition: 5th
• Format: Hardcover
• Copyright: 2007-05-01
• Publisher: Springer Verlag

Summary

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.

Table of Contents

Preface	p. v
Acknowledgment and Personal Statement	p. vii
Introduction	p. ix
Chemical Bonding and Molecular Structure	p. 1
Introduction	p. 1
Description of Molecular Structure Using Valence Bond Concepts	p. 2
Hybridization	p. 4
The Origin of Electron-Electron Repulsion	p. 7
Electronegativity and Polarity	p. 8
Electronegativity Equalization	p. 11
Differential Electronegativity of Carbon Atoms	p. 12
Polarizability, Hardness, and Softness	p. 14
Resonance and Conjugation	p. 18
Hyperconjugation	p. 22
Covalent and van der Waals Radii of Atoms	p. 24
Molecular Orbital Theory and Methods	p. 26
The Huckel MO Method	p. 27
Semiempirical MO Methods	p. 32
Ab Initio Methods	p. 32
Pictorial Representation of MOs for Molecules	p. 35
Qualitative Application of MO Theory to Reactivity: Perturbational MO Theory and Frontier Orbitals	p. 41
Numerical Application of MO Theory	p. 50
Electron Density Functionals	p. 54
Representation of Electron Density Distribution	p. 57
Mulliken Population Analysis	p. 60
Natural Bond Orbitals and Natural Population Analysis	p. 61
Atoms in Molecules	p. 63
Comparison and Interpretation of Atomic Charge Calculations	p. 70
Electrostatic Potential Surfaces	p. 73
Relationships between Electron Density and Bond Order	p. 76
The Origin of the Rotational (Torsional) Barrier in Ethane and Other Small Molecules	p. 78
Heteroatom Hyperconjugation (Anomeric Effect) in Acyclic Molecules	p. 81
Bonding in Cyclopropane and Other Small Ring Compounds	p. 85
Representation of Electron Density by the Laplacian Function	p. 92
Application of Density Functional Theory to Chemical Properties and Reactivity	p. 94
DFT Formulation of Chemical Potential, Electronegativity, Hardness and Softness, and Covalent and van der Waal Radii	p. 95
DFT Formulation of Reactivity-The Fukui Function	p. 97
DFT Concepts of Substituent Groups Effects	p. 100
General References	p. 106
Problems	p. 106
Stereochemistry, Conformation, and Stereoselectivity	p. 119
Introduction	p. 119
Configuration	p. 119
Configuration at Double Bonds	p. 119
Configuration of Cyclic Compounds	p. 121
Configuration at Tetrahedral Atoms	p. 122
Molecules with Multiple Stereogenic Centers	p. 126
Other Types of Stereogenic Centers	p. 128
The Relationship between Chirality and Symmetry	p. 131
Configuration at Prochiral Centers	p. 133
Resolution-The Separation of Enantiomers	p. 136
Conformation	p. 142
Conformation of Acyclic Compounds	p. 142
Conformations of Cyclohexane Derivatives	p. 152
Conformations of Carbocyclic Rings of Other Sizes	p. 161
Molecular Mechanics	p. 167
Stereoselective and Stereospecific Reactions	p. 169
Examples of Stereoselective Reactions	p. 170
Examples of Stereospecific Reactions	p. 182
Enantioselective Reactions	p. 189
Enantioselective Hydrogenation	p. 189
Enantioselective Reduction of Ketones	p. 193
Enantioselective Epoxidation of Allylic Alcohols	p. 196
Enantioselective Dihydroxylation of Alkenes	p. 200
Double Stereodifferentiation: Reinforcing and Competing Stereoselectivity	p. 204
Analysis and Separation of Enantiomeric Mixtures	p. 208
Chiral Shift Reagents and Chiral Solvating Agents	p. 208
Separation of Enantiomers	p. 211
Enzymatic Resolution and Desymmetrization	p. 215
Lipases and Esterases	p. 216
Proteases and Acylases	p. 222
Epoxide Hydrolases	p. 224
The Anomeric Effect in Cyclic Compounds	p. 227
Polar Substituent Effects in Reduction of Carbonyl Compounds	p. 234
General References	p. 239
Problems	p. 240
Structural Effects on Stability and Reactivity	p. 253
Introduction	p. 253
Thermodynamic Stability	p. 254
Relationship between Structure and Thermodynamic Stability for Hydrocarbons	p. 256
Calculation of Enthalpy of Formation and Enthalpy of Reaction	p. 257
Chemical Kinetics	p. 270
Fundamental Principles of Chemical Kinetics	p. 270
Representation of Potential Energy Changes in Reactions	p. 273
Reaction Rate Expressions	p. 280
Examples of Rate Expressions	p. 283
General Relationships between Thermodynamic Stability and Reaction Rates	p. 285
Kinetic versus Thermodynamic Control of Product Composition	p. 285
Correlations between Thermodynamic and Kinetic Aspects of Reactions	p. 287
Curtin-Hammett Principle	p. 296
Electronic Substituent Effects on Reaction Intermediates	p. 297
Carbocations	p. 300
Carbanions	p. 307
Radical Intermediates	p. 311
Carbonyl Addition Intermediates	p. 319
Kinetic Isotope Effects	p. 332
Linear Free-Energy Relationships for Substituent Effects	p. 335
Numerical Expression of Linear Free-Energy Relationships	p. 335
Application of Linear Free-Energy Relationships to Characterization of Reaction Mechanisms	p. 342
Catalysis	p. 345
Catalysis by Acids and Bases	p. 345
Lewis Acid Catalysis	p. 354
Solvent Effects	p. 359
Bulk Solvent Effects	p. 359
Examples of Specific Solvent Effects	p. 362
Acidity of Hydrocarbons	p. 368
General References	p. 376
Problems	p. 376
Nucleophilic Substitution	p. 389
Introduction	p. 389
Mechanisms for Nucleophilic Substitution	p. 389
Substitution by the Ionization (S[subscript N]1) Mechanism	p. 391
Substitution by the Direct Displacement (S[subscript N]2) Mechanism	p. 393
Detailed Mechanistic Description and Borderline Mechanisms	p. 395
Relationship between Stereochemistry and Mechanism of Substitution	p. 402
Substitution Reactions of Alkyldiazonium Ions	p. 405
Structural and Solvation Effects on Reactivity	p. 407
Characteristics of Nucleophilicity	p. 407
Effect of Solvation on Nucleophilicity	p. 411
Leaving-Group Effects	p. 413
Steric and Strain Effects on Substitution and Ionization Rates	p. 415
Effects of Conjugation on Reactivity	p. 417
Neighboring-Group Participation	p. 419
Structure and Reactions of Carbocation Intermediates	p. 425
Structure and Stability of Carbocations	p. 425
Direct Observation of Carbocations	p. 436
Competing Reactions of Carbocations	p. 438
Mechanisms of Rearrangement of Carbocations	p. 440
Bridged (Nonclassical) Carbocations	p. 447
The Role Carbocations and Carbonium Ions in Petroleum Processing	p. 454
General References	p. 459
Problems	p. 459
Polar Addition and Elimination Reactions	p. 473
Introduction	p. 475
Addition of Hydrogen Halides to Alkenes	p. 476
Acid-Catalyzed Hydration and Related Addition Reactions	p. 482
Addition of Halogens	p. 485
Sulfenylation and Selenenylation	p. 497
Sulfenylation	p. 498
Selenenylation	p. 500
Addition Reactions Involving Epoxides	p. 503
Epoxides from Alkenes and Peroxidic Reagents	p. 503
Subsequent Transformations of Epoxides	p. 511
Electrophilic Additions Involving Metal Ions	p. 515
Solvomercuration	p. 515
Argentation-the Formation of Silver Complexes	p. 520
Synthesis and Reactions of Alkylboranes	p. 521
Hydroboration	p. 522
Reactions of Organoboranes	p. 526
Enantioselective Hydroboration	p. 529
Comparison of Electrophilic Addition Reactions	p. 531
Additions to Alkynes and Allenes	p. 536
Hydrohalogenation and Hydration of Alkynes	p. 538
Halogenation of Alkynes	p. 540
Mercuration of Alkynes	p. 544
Overview of Alkyne Additions	p. 544
Additions to Allenes	p. 545
Elimination Reactions	p. 546
The E2, E1 and E1cb Mechanisms	p. 548
Regiochemistry of Elimination Reactions	p. 554
Stereochemistry of E2 Elimination Reactions	p. 558
Dehydration of Alcohols	p. 563
Eliminations Reactions Not Involving C-H Bonds	p. 564
General References	p. 569
Problems	p. 569
Carbanions and Other Carbon Nucleophiles	p. 579
Introduction	p. 559
Acidity of Hydrocarbons	p. 579
Carbanion Character of Organometallic Compounds	p. 588
Carbanions Stabilized by Functional Groups	p. 591
Enols and Enamines	p. 601
Carbanions as Nucleophiles in S[subscript N]2 Reactions	p. 609
Substitution Reactions of Organometallic Reagents	p. 609
Substitution Reactions of Enolates	p. 611
General References	p. 619
Problems	p. 619
Addition, Condensation and Substitution Reactions of Carbonyl Compounds	p. 629
Introduction	p. 629
Reactivity of Carbonyl Compounds toward Addition	p. 632
Hydration and Addition of Alcohols to Aldehydes and Ketones	p. 638
Condensation Reactions of Aldehydes and Ketones with Nitrogen Nucleophiles	p. 645
Substitution Reactions of Carboxylic Acid Derivatives	p. 654
Ester Hydrolysis and Exchange	p. 654
Aminolysis of Esters	p. 659
Amide Hydrolysis	p. 662
Acylation of Nucleophilic Oxygen and Nitrogen Groups	p. 664
Intramolecular Catalysis of Carbonyl Substitution Reactions	p. 668
Addition of Organometallic Reagents to Carbonyl Groups	p. 676
Kinetics of Qrganometallic Addition Reactions	p. 677
Stereoselectivity of Organometallic Addition Reactions	p. 680
Addition of Enolates and Enols to Carbonyl Compounds: The Aldol Addition and Condensation Reactions	p. 682
The General Mechanisms	p. 682
Mixed Aldol Condensations with Aromatic Aldehydes	p. 685
Control of Regiochemistry and Stereochemistry of Aldol Reactions of Ketones	p. 687
Aldol Reactions of Other Carbonyl Compounds	p. 692
General References	p. 698
Problems	p. 698
Aromaticity	p. 713
Introduction	p. 713
Criteria of Aromaticity	p. 715
The Energy Criterion for Aromaticity	p. 715
Structural Criteria for Aromaticity	p. 718
Electronic Criteria for Aromaticity	p. 720
Relationship among the Energetic, Structural, and Electronic Criteria of Aromaticity	p. 724
The Annulenes	p. 725
Cyclobutadiene	p. 725
Benzene	p. 727
1,3,5,7-Cyclooctatetraene	p. 727
[10]Annulenes-1,3,5,7,9-Cyclodecapentaene Isomers	p. 728
[12], [14], and [16]Annulenes	p. 730
[18]Annulene and Larger Annulenes	p. 733
Other Related Structures	p. 735
Aromaticity in Charged Rings	p. 738
Homoaromaticity	p. 743
Fused-Ring Systems	p. 745
Heteroaromatic Systems	p. 758
General References	p. 760
Problems	p. 760
Aromatic Substitution	p. 771
Introduction	p. 771
Electrophilic Aromatic Substitution Reactions	p. 771
Structure-Reactivity Relationships for Substituted Benzenes	p. 779
Substituent Effects on Reactivity	p. 779
Mechanistic Interpretation of the Relationship between Reactivity and Selectivity	p. 787
Reactivity of Polycyclic and Heteroaromatic Compounds	p. 791
Specific Electrophilic Substitution Reactions	p. 796
Nitration	p. 796
Halogenation	p. 800
Protonation and Hydrogen Exchange	p. 804
Friedel-Crafts Alkylation and Related Reactions	p. 805
Friedel-Crafts Acylation and Related Reactions	p. 809
Aromatic Substitution by Diazonium Ions	p. 813
Substitution of Groups Other than Hydrogen	p. 814
Nucleophilic Aromatic Substitution	p. 816
Nucleophilic Aromatic Substitution by the Addition-Elimination Mechanism	p. 817
Nucleophilic Aromatic Substitution by the Elimination-Addition Mechanism	p. 821
General References	p. 824
Problems	p. 824
Concerted Pericyclic Reactions	p. 833
Introduction	p. 833
Cycloaddition Reactions	p. 834
The Diels-Alder Reaction	p. 839
Stereochemistry of the Diels-Alder Reaction	p. 839
Substituent Effects on Reactivity, Regioselectivity and Stereochemistry	p. 843
Catalysis of Diels-Alder Reactions by Lewis Acids	p. 848
Computational Characterization of Diels-Alder Transition Structures	p. 851
Scope and Synthetic Applications of the Diels-Alder Reaction	p. 860
Enantioselective Diels-Alder Reactions	p. 865
Intramolecular Diels-Alder Reactions	p. 868
1,3-Dipolar Cycloaddition Reactions	p. 873
Relative Reactivity, Regioselectivity, Stereoselectivity, and Transition Structures	p. 874
Scope and Applications of 1,3-Dipolar Cycloadditions	p. 884
Catalysis of 1,3-Dipolar Cycloaddition Reactions	p. 886
[2 + 2] Cycloaddition Reactions	p. 888
Electrocyclic Reactions	p. 892
Overview of Electrocyclic Reactions	p. 892
Orbital Symmetry Basis for the Stereospecificity of Electrocyclic Reactions	p. 894
Examples of Electrocyclic Reactions	p. 903
Electrocyclic Reactions of Charged Species	p. 906
Electrocyclization of Heteroatomic Trienes	p. 910
Sigmatropic Rearrangements	p. 911
Overview of Sigmatropic Rearrangements	p. 911
[1,3]-, [1,5]-, and [1,7]-Sigmatropic Shifts of Hydrogen and Alkyl Groups	p. 912
Overview of [3,3]-Sigmatropic Rearrangements	p. 919
[2,3]-Sigmatropic Rearrangements	p. 939
Application of DFT Concepts to Reactivity and Regiochemistry of Cycloaddition Reactions	p. 945
Problems	p. 951
Free Radical Reactions	p. 965
Introduction	p. 965
Generation and Characterization of Free Radicals	p. 967
Background	p. 967
Long-Lived Free Radicals	p. 968
Direct Detection of Radical Intermediates	p. 970
Generation of Free Radicals	p. 976
Structural and Stereochemical Properties of Free Radicals	p. 980
Substituent Effects on Radical Stability	p. 986
Charged Radicals	p. 988
Characteristics of Reactions Involving Radical Intermediates	p. 992
Kinetic Characteristics of Chain Reactions	p. 992
Determination of Reaction Rates	p. 995
Structure-Reactivity Relationships	p. 1000
Free Radical Substitution Reactions	p. 1018
Halogenation	p. 1018
Oxygenation	p. 1024
Free Radical Addition Reactions	p. 1026
Addition of Hydrogen Halides	p. 1026
Addition of Halomethanes	p. 1029
Addition of Other Carbon Radicals	p. 1031
Addition of Thiols and Thiocarboxylic Acids	p. 1033
Examples of Radical Addition Reactions	p. 1033
Other Types of Free Radical Reactions	p. 1037
Halogen, Sulfur, and Selenium Group Transfer Reactions	p. 1037
Intramolecular Hydrogen Atom Transfer Reactions	p. 1040
Rearrangement Reactions of Free Radicals	p. 1041
S[subscript RN]1 Substitution Processes	p. 1044
S[subscript RN]1 Substitution Reactions of Alkyl Nitro Compounds	p. 1045
S[subscript RN]1 Substitution Reactions of Aryl and Alkyl Halides	p. 1048
Relationships between Bond and Radical Stabilization Energies	p. 1052
Structure-Reactivity Relationships in Hydrogen Abstraction Reactions	p. 1056
General References	p. 1062
Problems	p. 1063
Photochemistry	p. 1073
Introduction	p. 1073
General Principles	p. 1073
Photochemistry of Alkenes, Dienes, and Polyenes	p. 1081
Cis-trans Isomerization	p. 1081
Photoreactions of Other Alkenes	p. 1091
Photoisomerization of 1,3-Butadiene	p. 1096
Orbital Symmetry Considerations for Photochemical Reactions of Alkenes and Dienes	p. 1097
Photochemical Electrocyclic Reactions	p. 1100
Photochemical Cycloaddition Reactions	p. 1109
Photochemical Rearrangements Reactions of 1,4-Dienes	p. 1112
Photochemistry of Carbonyl Compounds	p. 1116
Hydrogen Abstraction and Fragmentation Reactions	p. 1118
Cycloaddition and Rearrangement Reactions of Cyclic Unsaturated Ketones	p. 1125
Cycloaddition of Carbonyl Compounds and Alkenes	p. 1132
Photochemistry of Aromatic Compounds	p. 1134
Computational Interpretation of Diene and Polyene Photochemistry	p. 1137
General References	p. 1145
Problems	p. 1146
References to Problems	p. 1155
Index	p. 1171
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