Advanced Organic Chemistry. Reactions and Synthesis

Автор(ы):Carey Francis A., Sundberg Richard J.
06.10.2007
Описание: Книга вторая посвящена важнейшим органическим реакциям, применяемым в синтезе. Приведены многочисленные схемы конкретных реакций с указанием выходов продуктов и ссылками на оригинальную литературу. В конце каждой главы даны задачи, помогающие контролировать степень усвоения материала.
Оглавление:
Advanced Organic Chemistry. Reactions and Synthesis — обложка книги.
Chapter 1. Alkylation of Nucleophilic Carbon Intermediates [1]
  1.1. Generation of Carbanions by Deprotonation [1]
  1.2. Regioseiectivity and Stereoselectivity in Enolate Formation [5]
  1.3. Other Means of Generating Enolates [10]
  1.4. Alkylation of Enolates [11]
  1.5. Generation and Alkylation of Dianions [20]
  1.6. Medium Effects in the Alkylation of Enolates [20]
  1.7. Oxygen versus Carbon as the Site of Alkylation [23]
  1.8. Alkylation of Aldehydes, Estejs, Amides, and Nitriles [28]
  1.9. The Nitrogen Analogs of Enols and Enolates—Enamines and Imine (?) [31]
  1.10. Alkylation of Carbon Nucleophiles by Conjugate Addition [39]
  General References [47]
  Problems [47]
Chapter 2. Reaction of Carbon Nucleophiles with Carbonyl Groups [57]
  2.1. Aldol Addition and Condensation Reactions [57]
    2.1.1. The General Mechanism [57]
    2.1.2. Mixed Aldol Condensations with Aromatic Aldehydes [60]
    2.1.3. Control of Regiochemistry and Stereochemistry of Mixed Aldol Reactions of Aliphatic Aldehydes and Ketones [62]
    2.1.4. Intramolecular Aldol Reactions and the Robinson Annulation [89]
  2.2. Addition Reactions of Imines and Iminium Ions [96]
    2.2.1. The Marmich Reaction [96]
    2.2.2. Amine-Catalyzed Condensation Reactions [100]
  2.3. Acylation of Carbanions [101]
  2.4. The Wittig and Related Reactions of Phosphorus-Stabilized Carbon (?) [111]
  2.5. Reactions of Carbonyl Compounds with a-Trimethylsilylcarbanions [120]
  2.6. Sulfur Ylides and Related Nucleophiles [122]
  2.7. Nucleophilic Addition-Cyclization [127]
  General References [128]
  Problems [128]
Chapter 3. Functional Group Interconversion by Nucleophilic Substitution [141]
  3.1. Conversion of Alcohols to Alkylating Agents [141]
    3.1.1. (?) [141]
    3.1.2. (?) Halirfoc [142]
  3.2. Introduction of Functional Groups by Nucleophilic Substitution at (?) [147]
    3.2.1. General Solvent Effects [147]
    3.2.2. (?) [150]
    3.2.3. (?) [150]
    3.2.4. Oxygen Nucleophiles [152]
    3.2.5. Nitrogen Nucleophiles [155]
    3.2.6. Sulfur Nucleophiles [158]
    3.2.7. Phosphorus Nucleophiles [158]
    3.2.8. Summary of Nucleophilic Substitution at Saturated Carbon [159]
  3.3. Nucleophilic Cleavage of Carbon-Oxygen Bonds in Ethers and Esters [159]
  3.4. Interconversion of Carboxylic Acid Derivatives [164]
    3.4.1. Preparation of Reactive Reagents for Acylation [166]
    3.4.2. Preparation of Esters [172]
    3.4.3. Preparation of Amides [172]
  Problems [180]
Chapter 4. Electrophilic Additions to Carbon-Carbon Multiple Bonds [191]
  4.1. Addition of Hydrogen Halides [191]
  4.2. Hydration and Other Acid-Catalyzed Additions of Oxygen Nucleophiles [195]
  4.3. (?)
  4.4. Addition of Halogens to Alkenes [200]
  4.5. Electrophilic Sulfur and Selenium Reagents [209]
  4.6. Addition of Other Electrophilic Reagents [216]
  4.7. Electrophilic Substitution Alpha to Carbonyl Groups [216]
  4.8. Additions to Allenes and Alkynes [222]
  4.9. Addition at Double Bonds via Organoborane Intermediates [226]
    4.9.1. Hydroboration [226]
    4.9.2. Reactions of Organoboranes [232]
    4.9.3. Enantioselective Hydroboration [236]
    4.9.4. Hydroboration of Alkynes [239]
  General References [240]
  Problems [241]
Chapter 5. Reduction of Carbonyl and Other Functional Groups [249]
  5.1. Addition of Hydrogen [249]
    5.1.1. Catalytic Hydrogenation [249]
    5.1.2. Other Hydrogen-Transfer Reagents [262]
  5.2. Group III Hydride-Donor Reagents [262]
    5.2.1. Reduction of Carbonyl Compounds [262]
    5.2.2. Stereoselectivity of Hydride Reduction [273]
    5.2.3. Reduction of Other Functional Groups by Hydride Donors [280]
  5.3. Group IV Hydride Donors [286]
  5.4. Hydrogen-Atom Donors [288]
  5.5. Dissolving-Metal Reductions [290]
    5.5.1. Addition of Hydrogen [292]
    5.5.2. Reductive Removal of Functional Groups [296]
    5.5.3. Reductive Carbon-Carbon Bond Formation [299]
  5.6. Reductive Deoxygenation of Carbonyl Groups [307]
  5.7. Reductive Elimination and Fragmentation [310]
  General References [315]
  Problems [316]
Chapter 6. Cycloadditions, Unimolecular Rearrangements, and Thermal (?) [331]
  6.1. Cycloaddition Reactions [331]
    6.1.1. The Diels-Alder Reaction: General Features [332]
    6.1.2. The Diels-Alder Reaction: Dienophiles [339]
    6.1.3. The Diels-Alder Reaction: Dienes [345]
    6.1.4. Asymmetric Diels-Alder Reactions [349]
    6.1.5. Intramolecular Diels-Alder Reactions [353]
  6.2. Dipolar Cycloaddition Reactions [359]
  6.3. [2 + 2] Cycloadditions and Other Reactions Leading to Cyclobutanes [367]
  6.4. Photochemical Cycloaddition Reactions [370]
  6.5. [3,3] Sigmatropic Rearrangements [376]
    6.5.1. Cope Rearrangements [376]
    6.5.2. Claisen Rearrangements [383]
  6.6. [2,3] Sigmatropic Rearrangements [394]
  6.7. (?) [399]
  6.8. Unimolecular Thermal Elimination Reactions [403]
    6.8.1. Cheletropic Elimination [403]
    6.8.2. Decomposition of Cyclic Azo Compounds [405]
    6.8.3. (?) Eliminations Involving Cyclic Transition States [408]
  General References [414]
  Problems [414]
Chapter 7. Organometallic Compounds of the Group I, II, and III Metals [433]
  7.1. Preparation and Properties [433]
  7.2. Reactions of Organomagnesium and Organolithium Compounds [445]
    7.2.1. Reactions with Alkylating Agents [445]
    7.2.2. Reactions with Carbonyl Compounds [446]
  7.3. Organic Derivatives of Group IIB and Group IIIB Metals [458]
    7.3.1. Organozinc Compounds [459]
    7.3.2. Organocadmium Compounds [463]
    7.3.3. Organomercury Compounds [464]
    7.3.4. Organoindium Reagents [465]
  7.4. Organolanthanide Reagents [467]
  General References [468]
  Problems [468]
Chapter 8. Reactions Involving the Transition Metals [477]
  8.1. Organocopper Intermediates [477]
    8.1.1. Preparation and Structure of Organocopper Reagents [477]
    8.1.2. Reactions Involving Organocopper Reagents and Intermediates [481]
  8.2. Reactions Involving Organopalladiumjntermediates [499]
    8.2.1. Palladium-Catalyzed Nucleophilic Substitution and Alkylation [501]
    8.2.2. (?) [503]
    8.2.3. Palladium-Catalyzed Cross Coupling [507]
    8.2.4. Carbonylation Reactions [521]
  8.3. Reactions Involving Organonickel Compounds [525]
  8.4. Reactions Involving Rhodium and Cobalt [529]
  8.5. Organometallic Compounds with я Bonding [531]
  General References [535]
  Problems [536]
Chapter 9. Carbon-Carbon Bond-Forming Reactions of Compounds of Boron, Silicon, and Tin [547]
  9.1. Organoboron Compounds [547]
    9.1.1. Synthesis of Organoboranes [547]
    9.1.2. Carbon-Carbon Bond-Forming Reactions of Organoboranes [549]
  9.2. Organosilicon Compounds [563]
    9.2.1. Synthesis of Organosilanes [563]
    9.2.2. Carbon-Carbon Bond-Forming Reactions [567]
  9.3. Organotin Compounds [576]
    9.3.1. Synthesis of Organostannanes [576]
    9.3.2. Carbon-Carbon Bond-Forming Reactions [579]
  General References [585]
  Problems [586]
Chapter 10. Reactions Involving Carbocations, Carbenes, and Radicals as Reactive Intermediates [595]
  10.1. Reactions Involving Carbocation Intermediates [595]
    10.1.1. Carbon-Carbon Bond Formation Involving Carbocations [596]
    10.1.2. Rearrangement of Carbocations [602]
    10.1.3. Related Rearrangements [609]
    10.1.4. Fragmentation Reactions [612]
  10.2. Reactions Involving Carbenes and Nitrenes [614]
    10.2.1. Structure and Reactivity of Carbenes [617]
    10.2.2. Generation of Carbenes [620]
    10.2.3. Addition Reactions [625]
    10.2.4. Insertion Reactions [634]
    10.2.5. Generation and Reactions of Ylides by Carbenoid Decomposition [637]
    10.2.6. Rearrangement Reactions [639]
    10.2.7. Related Reactions [641]
    10.2.8. Nitrenes and Related Intermediates [642]
    10.2.9. Rearrangements to Electron-Deficient Nitrogen [646]
  10.3. Reactions Involving Free-Radical Intermediates [651]
    10.3.1. Sources of Radical Intermediates [652]
    10.3.2. Introduction of Functionality by Radical Reactions [654]
    10.3.3. Addition Reactions of Radicals to Substituted Alkenes [657]
    10.3.4. Cyclization of Free-Radical Intermediates [660]
    10.3.5. Fragmentation and Rearrangement Reactions [674]
  General References [679]
  Problems [680]
Chapter 11. Aromatic Substitution Reactions [693]
  11.1. Electrophilic Aromatic Substitution [693]
    11.1.1. [693]
    11.1.2. Halogenation [695]
    11.1.3. Friedel-Crafts Alkylations and Acylations [699]
    11.1.4. Electrophilic Metalation [711]
  11.2. Nucleophilic Aromatic Substitution [714]
    11.2.1. Aryl Diazonium Ions as Synthetic Intermediates [714]
    11.2.2. Substitution by the Addition-Elimination Mechanism [722]
    11.2.3. Substitution by the Elimination-Addition Mechanism [724]
    11.2.4. Transition-Metal-Catalyzed Substitution Reactions [728]
  11.3. Aromatic Radical Substitution Reactions [731]
  11.4. Substitution by the SRN(?) Mechanism [734]
  General References [736]
  Problems [736]
Chapter 12. Oxidations [747]
  12.1. Oxidation of Alcohols to Aldehydes, Ketones, or Carboxylic Acids [747]
    12.1.1. Transition-Metal Oxidants [747]
    12.1.2. (?)[752]
  12.2. Addition of Oxygen at Carbon-Carbon Double Bonds [757]
    12.2.1. Transition-Metal Oxidants [757]
    12.2.2. Epoxides from Aikenes and Peroxidic Reagents [767]
    12.2.3. Transformations of Epoxides [772]
    12.2.4. Reaction of Aikenes with Singlet Oxygen [782]
  12.3. Cleavage of Carbon-Carbon Double Bonds [786]
    12.3.1. Transition-Metal Oxidants [786]
    12.3.2. (?) [788]
  12.4. Selective Oxidative Cleavages at Other Functional Groups [790]
    12.4.1. Cleavage of Glycols [790]
    12.4.2. Oxidative Decarboxylation [792]
  12.5. Oxidation of Ketones and Aldehydes [794]
    12.5.1. Transition-Metal Oxidants [794]
    12.5.2. Oxidation of Ketones and Aldehydes by Oxygen and Peroxidic Compounds [798]
    12.5.3. Oxidation with Other Reagents [802]
  12.6. Allylic Oxidation [803]
    12.6.1. Transition-Metal Oxidants [803]
    12.6.2. Other Oxidants (?) [805]
  12.7. Oxidations at Unfimctionalized Carbon [807]
  General References [809]
  Problems [809]
Chapter 13. Planning and Execution of Mulristep Syntheses [821]
  13.1. Protective Groups [822]
    13.1.1. Hydroxyl-Protecting Groups [822]
    13.1.2. Ammo-Protecting Groups [831]
    13.1.3. Carbonyl-Protecting Groups [835]
    13.1.4. Carboxylic Acid-Protecting Groups [837]
  13.2. Synthetic Equivalent Groups [839]
  13.3. Synthetic Analysis and Planning [845]
  13.4. Control of Stereochemistry [846]
  13.5. Illustrative Syntheses [848]
    13.5.1 [848]
    13.5.2. [859]
    13.5.3. Prelog-Djerassi Lactone [869]
    13.5.4. (?) [881]
    13.5.5. (?) [890]
  13.6. Solid-Phase Synthesis [897]
    13.6.1. Solid-Phase Synthesis of Polypeptides [897]
    13.6.2. Solid-Phase Synthesis of Oligonucleotides [900]
  13.7. Combinatorial Synthesis [903]
  General References [909]
  Problems [910]
References for Problems [923]
Index [947]
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