Carey F.A. Advanced organic chemistry; Pt. A (New York, 2007). - ОГЛАВЛЕНИЕ / CONTENTS
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ОбложкаCarey F.A. Advanced organic chemistry. Pt. A: Structure and mechanisms / F.A.Carey, R.J.Sundberg.- 5th ed. - New York: Springer, 2007. - xxi, 1199 p. - Ref.: p.1155-1169. - Ind.: p.1171-1199. - ISBN 978-0-387-44897-8
 

Оглавление / Contents
 
Preface ......................................................... v
Acknowledgment and Personal Statement ......................... vii
Introduction ................................................... ix

Chapter 1.  Chemical Bonding and Molecular Structure ............ 1

Introduction .................................................... 1

1.1.  Description of Molecular Structure Using Valence Bond
      Concepts .................................................. 2
      1.1.1.  Hybridization ..................................... 4
      1.1.2.  The Origin of Electron-Electron Repulsion ......... 7
      1.1.3.  Electronegativity and Polarity .................... 8
      1.1.4.  Electronegativity Equalization ................... 11
      1.1.5.  Differential Electronegativity of Carbon Atoms ... 12
      1.1.6.  Polarizability, Hardness, and Softness ........... 14
      1.1.7.  Resonance and Conjugation ........................ 18
      1.1.8.  Hyperconjugation ................................. 22
      1.1.9.  Covalent and van der Waals Radii of Atoms ........ 24
1.2.  Molecular Orbital Theory and Methods ..................... 26
      1.2.1.  The Huckel MO Method ............................. 27
      1.2.2.  Semiempirical MO Methods ......................... 32
      1.2.3.  Ab Initio Methods ................................ 32
      1.2.4.  Pictorial Representation of MOs for Molecules .... 35
      1.2.5.  Qualitative Application of MO Theory to
              Reactivity: Perturbational MO Theory and
              Frontier Orbitals ................................ 41
      1.2.6.  Numerical Application of MO Theory ............... 50
1.3.  Electron Density Functionals ............................. 54
1.4.  Representation of Electron Density Distribution .......... 57
      1.4.1.  Mulliken Population Analysis ..................... 60
      1.4.2.  Natural Bond Orbitals and Natural Population
              Analysis ......................................... 61
      1.4.3.  Atoms in Molecules ............................... 63
      1.4.4.  Comparison and Interpretation of Atomic Charge
              Calculations ..................................... 70
      1.4.5.  Electrostatic Potential Surfaces ................. 73
      1.4.6.  Relationships between Electron Density and Bond
              Order ............................................ 76

Topic 1.1.    The Origin of the Rotational (Torsional)
              Barrier in Ethane and Other Small Molecules ...... 78
Topic 1.2.    Heteroatom Hyperconjugation (Anomeric Effect)
              in Acyclic Molecules ............................. 81
Topic 1.3.    Bonding in Cyclopropane and Other Small Ring
              Compounds ........................................ 85
Topic 1.4.    Representation of Electron Density by the
              Laplacian Function ............................... 92
Topic 1.5.    Application of Density Functional Theory
              to Chemical Properties and Reactivity ............ 94
              Т.1.5.1.  DFT Formulation of Chemical
                        Potential, Electronegativity,
                        Hardness and Softness, and Covalent
                        and van der Waal Radii ................. 95
              T.l.5.2.  DFT Formulation of Reactivity-The
                        Fukui Function ......................... 97
              Т.1.5.З.  DFT Concepts of Substituent Groups
                        Effects ............................... 100
General References ............................................ 106
Problems ...................................................... 106

Chapter 2.  Stereochemistry, Conformation, and
            Stereoselectivity ................................. 119

Introduction .................................................. 119
2.1.  Configuration ........................................... 119
      2.1.1.  Configuration at Double Bonds ................... 119
      2.1.2.  Configuration of Cyclic Compounds ............... 121
      2.1.3.  Configuration at Tetrahedral Atoms .............. 122
      2.1.4.  Molecules with Multiple Stereogenic Centers ..... 126
      2.1.5.  Other Types of Stereogenic Centers .............. 128
      2.1.6.  The Relationship between Chirality and
              Symmetry ........................................ 131
      2.1.7.  Configuration at Prochiral Centers .............. 133
      2.1.8.  Resolution-The Separation of Enantiomers ........ 136
2.2.  Conformation ............................................ 142
      2.2.1.  Conformation of Acyclic Compounds ............... 142
      2.2.2.  Conformations of Cyclohexane Derivatives ........ 152
      2.2.3.  Conformations of Carbocyclic Rings of Other
              Sizes ........................................... 161
2.3.  Molecular Mechanics ..................................... 167
2.4.  Stereoselective and Stereospecific Reactions ............ 169
      2.4.1.  Examples of Stereoselective Reactions ........... 170
      2.4.2.  Examples of Stereospecific Reactions ............ 182
2.5.  Enantioselective Reactions .............................. 189
      2.5.1.  Enantioselective Hydrogenation .................. 189
      2.5.2.  Enantioselective Reduction of Ketones ........... 193
      2.5.3.  Enantioselective Epoxidation of Allylic
              Alcohols ........................................ 196
      2.5.4.  Enantioselective Dihydroxylation of Alkenes ..... 200
2.6.  Double Stereodifferentiation: Reinforcing and
      Competing Stereoselectivity ............................. 204

Topic 2.1.    Analysis and Separation of Enantiomeric
              Mixtures ........................................ 208
              T.2.1.1.  Chiral Shift Reagents and Chiral
                        Solvating Agents ...................... 208
              T.2.1.2.  Separation of Enantiomers ............. 211
Topic 2.2.    Enzymatic Resolution and Desymmetrization ....... 215
              T.2.2.1.  Lipases and Esterases ................. 216
              T.2.2.2.  Proteases and Acylases ................ 222
              T.2.2.3.  Epoxide Hydrolases .................... 224
Topic 2.3.    The Anomeric Effect in Cyclic Compounds ......... 227
Topic 2.4.    Polar Substituent Effects in Reduction
              of Carbonyl Compounds ........................... 234
General References ............................................ 239
Problems ...................................................... 240

Chapter 3.  Structural Effects on Stability and Reactivity .... 253

Introduction .................................................. 253
3.1.  Thermodynamic Stability ................................. 254
      3.1.1.  Relationship between Structure and
              Thermodynamic Stability for Hydrocarbons ........ 256
      3.1.2.  Calculation of Enthalpy of Formation and
              Enthalpy of Reaction ............................ 257
3.2.  Chemical Kinetics ....................................... 270
      3.2.1.  Fundamental Principles of Chemical Kinetics ..... 270
      3.2.2.  Representation of Potential Energy Changes in
              Reactions ....................................... 273
      3.2.3.  Reaction Rate Expressions ....................... 280
      3.2.4.  Examples of Rate Expressions .................... 283
3.3.  General Relationships between Thermodynamic Stability
      and Reaction Rates ...................................... 285
      3.3.1.  Kinetic versus Thermodynamic Control of
              Product Composition ............................. 285
      3.3.2.  Correlations between Thermodynamic and Kinetic
              Aspects of Reactions ............................ 287
      3.3.3.  Curtin-Hammett Principle ........................ 296
3.4.  Electronic Substituent Effects on Reaction
      Intermediates ........................................... 297
      3.4.1.  Carbocations .................................... 300
      3.4.2.  Carbanions ...................................... 307
      3.4.3.  Radical Intermediates ........................... 311
      3.4.4.  Carbonyl Addition Intermediates ................. 319
3.5.  Kinetic Isotope Effects ................................. 332
3.6.  Linear Free-Energy Relationships for Substituent
      Effects ................................................. 335
      3.6.1.  Numerical Expression of Linear Free-Energy
              Relationships ................................... 335
      3.6.2.  Application of Linear Free-Energy
              Relationships to Characterization of Reaction
              Mechanisms ...................................... 342
3.7.  Catalysis ............................................... 345
      3.7.1.  Catalysis by Acids and Bases .................... 345
      3.7.2.  Lewis Acid Catalysis ............................ 354
3.8.  Solvent Effects ......................................... 359
      3.8.1.  Bulk Solvent Effects ............................ 359
      3.8.2.  Examples of Specific Solvent Effects ............ 362
Topic 3.1.    Acidity of Hydrocarbons ......................... 368
General References ............................................ 376
Problems ...................................................... 376

Chapter 4.  Nucleophilic Substitution ......................... 389

Introduction .................................................. 389
4.1.  Mechanisms for Nucleophilic Substitution ................ 389
      4.1.1.  Substitution by the Ionization (SNl)
              Mechanism ....................................... 391
      4.1.2.  Substitution by the Direct Displacement (SN2)
              Mechanism ....................................... 393
      4.1.3.  Detailed Mechanistic Description and
              Borderline Mechanisms ........................... 395
      4.1.4.  Relationship between Stereochemistry and
              Mechanism of Substitution ....................... 402
      4.1.5.  Substitution Reactions of Alkyldiazonium Ions ... 405
4.2.  Structural and Solvation Effects on Reactivity .......... 407
      4.2.1.  Characteristics of Nucleophilicity .............. 407
      4.2.2.  Effect of Solvation on Nucleophilicity .......... 411
      4.2.3.  Leaving-Group Effects ........................... 413
      4.2.4.  Steric and Strain Effects on Substitution and
              Ionization Rates ................................ 415
      4.2.5.  Effects of Conjugation on Reactivity ............ 417
4.3.  Neighboring-Group Participation ......................... 419
4.4.  Structure and Reactions of Carbocation Intermediates .... 425
      4.4.1.  Structure and Stability of Carbocations ......... 425
      4.4.2.  Direct Observation of Carbocations .............. 436
      4.4.3.  Competing Reactions of Carbocations ............. 438
      4.4.4.  Mechanisms of Rearrangement of Carbocations ..... 440
      4.4.5.  Bridged (Nonclassical) Carbocations ............. 447
Topic 4.1.    The Role Carbocations and Carbonium Ions in
              Petroleum Processing ............................ 454
General References ............................................ 459
Problems ...................................................... 459

Chapter 5.  Polar Addition and Elimination Reactions .......... 473

Introduction .................................................. 475
5.1.  Addition of Hydrogen Halides to Alkenes ................. 476
5.2.  Acid-Catalyzed Hydration and Related Addition
      Reactions ............................................... 482
5.3.  Addition of Halogens .................................... 485
5.4.  Sulfenylation and Selenenylation ........................ 497
      5.4.1.  Sulfenylation ................................... 498
      5.4.2.  Selenenylation .................................. 500
5.5.  Addition Reactions Involving Epoxides ................... 503
      5.5.1.  Epoxides from Alkenes and Peroxidic Reagents .... 503
      5.5.2.  Subsequent Transformations of Epoxides .......... 511
5.6.  Electrophilic Additions Involving Metal Ions ............ 515
      5.6.1.  Solvomercuration ................................ 515
      5.6.2.  Argentation-the Formation of Silver Complexes ... 520
5.7.  Synthesis and Reactions of Alkylboranes ................. 521
      5.7.1.  Hydroboration ................................... 522
      5.7.2.  Reactions of Organoboranes ...................... 526
      5.7.3.  Enantioselective Hydroboration .................. 529
5.8.  Comparison of Electrophilic Addition Reactions .......... 531
5.9.  Additions to Alkynes and Allenes ........................ 536
      5.9.1.  Hydrohalogenation and Hydration of Alkynes ...... 538
      5.9.2.  Halogenation of Alkynes ......................... 540
      5.9.3.  Mercuration of Alkynes .......................... 544
      5.9.4.  Overview of Alkyne Additions .................... 544
      5.9.5.  Additions to Allenes ............................ 545
5.10. Elimination Reactions ................................... 546
      5.10.1. The E2, El and E1cb Mechanisms .................. 548
      5.10.2. Regiochemistry of Elimination Reactions ......... 554
      5.10.3. Stereochemistry of E2 Elimination Reactions ..... 558
      5.10.4. Dehydration of Alcohols ......................... 563
      5.10.5. Eliminations Reactions Not Involving С-Н
              Bonds ........................................... 564
General References ............................................ 569
Problems ...................................................... 569

Chapter 6.  Carbanions and Other Carbon Nucleophiles .......... 579

Introduction .................................................. 559
6.1.  Acidity of Hydrocarbons ................................. 579
6.2.  Carbanion Character of Organometallic Compounds ......... 588
6.3.  Carbanions Stabilized by Functional Groups .............. 591
6.4.  Enols and Enamines ...................................... 601
6.5.  Carbanions as Nucleophiles in 5N2 Reactions ............. 609
      6.5.1.  Substitution Reactions of Organometallic
              Reagents ........................................ 609
      6.5.2.  Substitution Reactions of Enolates .............. 611
General References ............................................ 619
Problems ...................................................... 619

Chapter 7.  Addition, Condensation and Substitution
            Reactions of Carbonyl Compounds ................... 629

Introduction .................................................. 629
7.1.  Reactivity of Carbonyl Compounds toward Addition ........ 632
7.2.  Hydration and Addition of Alcohols to Aldehydes and
      Ketones ................................................. 638
7.3.  Condensation Reactions of Aldehydes and Ketones with
      Nitrogen Nucleophiles ................................... 645
7.4.  Substitution Reactions of Carboxylic Acid Derivatives ... 654
      7.4.1.  Ester Hydrolysis and Exchange ................... 654
      7.4.2.  Aminolysis of Esters ............................ 659
      7.4.3.  Amide Hydrolysis ................................ 662
      7.4.4.  Acylation of Nucleophilic Oxygen and Nitrogen
              Groups .......................................... 664
      7.4.1.  Intramolecular Catalysis of Carbonyl
              Substitution Reactions .......................... 668
7.5.  Intramolecular Catalysis of Carbonyl Substitution
      Reactions ............................................... 668
7.6.  Addition of Organometallic Reagents to Carbonyl
      Groups .................................................. 676
      7.6.1.  Kinetics of Organometallic Addition Reactions ... 677
      7.6.2.  Stereoselectivity of Organometallic Addition
              Reactions ....................................... 680
7.7.  Addition of Enolates and Enols to Carbonyl Compounds:
      The Aldol Addition and Condensation Reactions ........... 682
      7.7.1.  The General Mechanisms .......................... 682
      7.7.2.  Mixed Aldol Condensations with Aromatic
              Aldehydes ....................................... 685
      7.7.3.  Control of Regiochemistry and Stereochemistry
              of Aldol Reactions of Ketones ................... 687
      7.7.4.  Aldol Reactions of Other Carbonyl Compounds ..... 692
General References ............................................ 698
Problems ...................................................... 698

Chapter 8.  Aromaticity ....................................... 713

Introduction .................................................. 713
8.1.  Criteria of Aromaticity ................................. 715
      8.1.1.  The Energy Criterion for Aromaticity ............ 715
      8.1.2.  Structural Criteria for Aromaticity ............. 718
      8.1.3.  Electronic Criteria for Aromaticity ............. 720
      8.1.4.  Relationship among the Energetic, Structural,
              and Electronic Criteria of Aromaticity .......... 724
8.2.  The Annulenes ........................................... 725
      8.2.1.  Cyclobutadiene .................................. 725
      8.2.2.  Benzene ......................................... 727
      8.2.3.  1,3,5,7-Cyclooctatetraene ....................... 727
      8.2.4.  [10]Annulenes-1,3,5,7,9-Cyclodecapentaene
              Isomers ......................................... 728
      8.2.5.  [12], [14], and [16]Annulenes ................... 730
      8.2.6.  [18]Annulene and Larger Annulenes ............... 733
      8.2.7.  Other Related Structures ........................ 735
8.3.  Aromaticity in Charged Rings ............................ 738
8.4.  Homoaromaticity ......................................... 743
8.5.  Fused-Ring Systems ...................................... 745
8.6.  Heteroaromatic Systems .................................. 758
General References ............................................ 760
Problems ...................................................... 760

Chapter 9. Aromatic Substitution .............................. 771

Introduction .................................................. 771
9.1.  Electrophilic Aromatic Substitution Reactions ........... 771
9.2.  Structure-Reactivity Relationships for Substituted
      Benzenes ................................................ 779
      9.2.1.  Substituent Effects on Reactivity ............... 779
      9.2.2.  Mechanistic Interpretation of the Relationship
              between Reactivity and Selectivity .............. 787
9.3.  Reactivity of Polycyclic and Heteroaromatic Compounds ... 791
9.4.  Specific Electrophilic Substitution Reactions ........... 796
      9.4.1.  Nitration ....................................... 796
      9.4.2.  Halogenation .................................... 800
      9.4.3.  Protonation and Hydrogen Exchange ............... 804
      9.4.4.  Friedel-Crafts Alkylation and Related
              Reactions ....................................... 805
      9.4.5.  Friedel-Crafts Acylation and Related
              Reactions ....................................... 809
      9.4.6.  Aromatic Substitution by Diazonium Ions ......... 813
      9.4.7.  Substitution of Groups Other than Hydrogen ...... 814
9.5.  Nucleophilic Aromatic Substitution ...................... 816
      9.5.1.  Nucleophilic Aromatic Substitution by the
              Addition-Elimination Mechanism .................. 817
      9.5.2.  Nucleophilic Aromatic Substitution by the
              Elimination-Addition Mechanism .................. 821
General References ............................................ 824
Problems ...................................................... 824

Chapter 10. Concerted Pericyclic Reactions .................... 833

Introduction .................................................. 833
10.1. Cycloaddition Reactions ................................. 834
10.2. The Diels-Alder Reaction ................................ 839
      10.2.1. Stereochemistry of the Diels-Alder Reaction ..... 839
      10.2.2. Substituent Effects on Reactivity,
              Regioselectivity and Stereochemistry ............ 843
      10.2.3. Catalysis of Diels-Alder Reactions by Lewis
              Acids ........................................... 848
      10.2.4. Computational Characterization of Diels-Alder
              Transition Structures ........................... 851
      10.2.5. Scope and Synthetic Applications of the Diels-
              Alder Reaction .................................. 860
      10.2.6. Enantioselective Diels-Alder Reactions .......... 865
      10.2.7. Intramolecular Diels-Alder Reactions ............ 868
10.3. 1,3-Dipolar Cycloaddition Reactions ..................... 873
      10.3.1. Relative Reactivity, Regioselectivity,
              Stereoselectivity, and Transition Structures .... 874
      10.3.2. Scope and Applications of 1,3-Dipolar
              Cycloadditions .................................. 884
      10.3.3. Catalysis of 1,3-Dipolar Cycloaddition
              Reactions ....................................... 886
10.4. [2 + 2] Cycloaddition Reactions ......................... 888
10.5. Electrocyclic Reactions ................................. 892
      10.5.1. Overview of Electrocyclic Reactions ............. 892
      10.5.2. Orbital Symmetry Basis for the
              Stereospecificity of Electrocyclic Reactions .... 894
      10.5.3. Examples of Electrocyclic Reactions ............. 903
      10.5.4. Electrocyclic Reactions of Charged Species ...... 906
      10.5.5. Electrocyclization of Heteroatomic Trienes ...... 910
10.6. Sigmatropic Rearrangements .............................. 911
      10.6.1. Overview of Sigmatropic Rearrangements .......... 911
      10.6.2. [1,3]-, [1,5]-, and [l,7]-Sigmatropic Shifts
              of Hydrogen and Alkyl Groups .................... 912
      10.6.3. Overview of [3,3]-Sigmatropic Rearrangements .... 919
      10.6.4. [2,3]-Sigmatropic Rearrangements ................ 939
Topic 10.1.   Application of DFT Concepts to Reactivity
              and Regiochemistry of Cycloaddition Reactions ... 945
Problems ...................................................... 951

Chapter 11. Free Radical Reactions ............................ 965

Introduction .................................................. 965
11.1. Generation and Characterization of Free Radicals ........ 967
      11.1.1. Background ...................................... 967
      11.1.2. Long-Lived Free Radicals ........................ 968
      11.1.3. Direct Detection of Radical Intermediates ....... 970
      11.1.4. Generation of Free Radicals ..................... 976
      11.1.5. Structural and Stereochemical Properties of
              Free Radicals ................................... 980
      11.1.6. Substituent Effects on Radical Stability ........ 986
      11.1.7. Charged Radicals ................................ 988
11.2. Characteristics of Reactions Involving Radical
      Intermediates ........................................... 992
      11.2.1. Kinetic Characteristics of Chain Reactions ...... 992
      11.2.2. Determination of Reaction Rates ................. 995
      11.2.3. Structure-Reactivity Relationships ............. 1000
11.3. Free Radical Substitution Reactions .................... 1018
      11.3.1. Halogenation ................................... 1018
      11.3.2. Oxygenation .................................... 1024
11.4. Free Radical Addition Reactions ........................ 1026
      11.4.1. Addition of Hydrogen Halides ................... 1026
      11.4.2. Addition of Halomethanes ....................... 1029
      11.4.3. Addition of Other Carbon Radicals .............. 1031
      11.4.4. Addition of Thiols and Thiocarboxylic Acids .... 1033
      11.4.5. Examples of Radical Addition Reactions ......... 1033
11.5. Other Types of Free Radical Reactions .................. 1037
      11.5.1. Halogen, Sulfur, and Selenium Group Transfer
              Reactions ...................................... 1037
      11.5.2. Intramolecular Hydrogen Atom Transfer
              Reactions ...................................... 1040
      11.5.3. Rearrangement Reactions of Free Radicals ....... 1041
11.6. 5RN1 Substitution Processes ............................ 1044
      11.6.1. SRN1 Substitution Reactions of Alkyl Nitro
              Compounds ...................................... 1045
      11.6.2. SRN1 Substitution Reactions of Aryl and Alkyl
              Halides ........................................ 1048
Topic 11.1.   Relationships between Bond and Radical
              Stabilization Energies ......................... 1052
Topic 11.2.   Structure-Reactivity Relationships in
              Hydrogen Abstraction Reactions ................. 1056
General References ........................................... 1062
Problems ..................................................... 1063

Chapter 12. Photochemistry ................................... 1073

Introduction ................................................. 1073
12.1. General Principles ..................................... 1073
12.2. Photochemistry of Alkenes, Dienes, and Polyenes ........ 1081
      12.2.1. cis-trans Isomerization ........................ 1081
      12.2.2. Photoreactions of Other Alkenes ................ 1091
      12.2.3. Photoisomerization of 1,3-Butadiene ............ 1096
      12.2.4. Orbital Symmetry Considerations for
              Photochemical Reactions of Alkenes and
              Dienes ......................................... 1097
      12.2.5. Photochemical Electrocyclic Reactions .......... 1100
      12.2.6. Photochemical Cycloaddition Reactions .......... 1109
      12.2.7. Photochemical Rearrangements Reactions of
              1,4-Dienes ..................................... 1112
12.3. Photochemistry of Carbonyl Compounds ................... 1116
      12.3.1. Hydrogen Abstraction and Fragmentation
              Reactions ...................................... 1118
      12.3.2. Cycloaddition and Rearrangement Reactions of
              Cyclic Unsaturated Ketones ..................... 1125
      12.3.3. Cycloaddition of Carbonyl Compounds and
              Alkenes ........................................ 1132
12.4. Photochemistry of Aromatic Compounds ................... 1134
Topic 12.1.   Computational Interpretation of Diene and
              Polyene Photochemistry ......................... 1137
General References ........................................... 1145
Problems ..................................................... 1146

References to Problems ....................................... 1155

Index ........................................................ 1171


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