Modern Organic Synthesis : An Introduction.

Intro -- Modern Organic Synthesis -- Contents -- About the Authors -- Preface to the Second Edition -- Preface to the First Edition -- 1 Synthetic Design -- 1.1 Retrosynthetic Analysis -- Basic Concepts -- Donor and Acceptor Synthonsc,g -- Alternating Polarity Disconnectionsg,4 -- 1.2 Reversal of the Carbonyl Group Polarity (Umpolung) -- Formyl and Acyl Anions Derived from 1,3-Dithianes5b,c,f -- Acyl Anions Derived from Nitroalkanes -- Acyl Anions Derived from Cyanohydrins -- Acyl Anions Derived from Enol Ethers -- Acyl Anions Derived from Lithium Acetylide -- 1.3 Steps in Planning a Synthesis -- Construction of the Carbon Skeleton -- Functional Group Interconversions (FGI) -- Control of Relative Stereochemistry -- Control of Enantioselectivity -- 1.4 Choice of Synthetic Method -- Linear Synthesis versus Convergent Synthesis3h,j,23 -- 1.5 Domino Reactions (Cascade or Tandem Reactions) -- 1.6 Computer-Assisted Retrosynthetic Analysis -- References -- 2 Stereochemical Considerations in Planning Syntheses -- 2.1 Conformational Analysis1 -- Acyclic Systems3 -- Ring Systems -- 2.2 Evaluation of Non-Bonded Interactions -- Monosubstituted Cyclohexane -- Disubstituted Cyclohexanes -- Evaluation of Destabilization Energies (ED) -- Atypical Disubstituted Cyclohexanes -- 2.3 Six-Membered Heterocyclic Systems -- Tetrahydropyrans -- Anomeric Effect13 -- 2.4 Polycyclic Ring Systems -- Hydrindane -- Decalin-Bicyclo4.4.0decane -- Bridged Bicyclic Systems -- Tricyclic Systems -- 2.5 Cyclohexyl Systems with sp2-Hybridized Atoms -- Cyclohexanones -- Cyclohexenes -- 2.6 Significant Energy Difference25 -- 2.7 Computer-Assisted Molecular Modeling -- 2.8 Reactivity and Product Determination as a Function of Conformation -- Terminology of Selectivity34 -- Esterification and Saponification -- SN2-Type Reactions -- Michael-Type Additions -- E2 Elimination Reactions.

Addition Reactions to Double Bonds -- A1,3 Strain as a Control Element -- Oxidation of Alcohols -- References -- 3 The Concept of Protecting Functional Groups -- 3.1 Protection of N-H Groups -- N-Benzylamines -- Amides -- Carbamates -- N-(p-Methoxyphenyl)amines -- 3.2 Protection of OH Groups -- Alkyl Ethers -- Benzylic Ethers -- Trityl Ethers -- Silyl Ethers -- Alkoxylalkyl Ethers (Acetals) -- Esters -- 3.3 Protection of Diols as Acetals -- 1,2-Diols -- 1,3-Diols -- 3.4 Protection of Carbonyl Groups in Aldehydes and Ketones -- Via O,O-Acetals -- Via S,S-Acetals -- 3.5 Protection of the Carboxyl Group -- Alkyl Esters -- Aryl Esters -- Silyl Esters -- Protection of the Carboxyl Group as an Oxazoline -- Protection of the Carboxyl Group as an Orthoester -- 3.6 Protection of Double Bonds -- 3.7 Protection of Triple Bonds -- References -- 4 Functional Group Transformations -- 4.1 Oxidation of Alcohols to Aldehydes and Ketones -- 4.2 Reagents and Procedures for Alcohol Oxidation -- Jones Reagent -- Collins-Ratcliff Reagent -- Pyridinium Chlorochromate (PCC) py-H+ CrO3Cl- -- Pyridinium Dichromate (PDC) py-H+2Cr2O7−2 -- Swern Oxidation -- Dess-Martin Periodinane (DMP) Oxidation -- Tetrapropylammonium Perruthenate (TPAP) Pr4N+ RuO4- -- 4.3 Chemoselective Oxidizing Agents -- Activated Manganese Dioxide -- Barium Manganate -- Silver Carbonate on Celite-Fetizons Reagent -- 2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO) -- Ceric Ammonium Nitrate -- Triphenylcarbenium Tetrafluoroborate -- 4.4 Oxidation of Acyloins -- 4.5 Oxidation of Tertiary Allylic Alcohols (The Babler Oxidation) -- 4.6 Oxidative Procedures to Carboxylic Acids -- Oxidation of Aldehydes to Carboxylic Acids -- Oxidation of Aldehydes to Carboxylic Esters -- Oxidation of Terminal Alkynes -- 4.7 Allylic Oxidation of Alkenes -- Selenium Dioxide -- Chromium and Manganese Reagents for Allylic Oxidation.

Copper-Catalyzed Allylic Oxidation -- Palladium-Catalyzed C-H Activation -- 4.8 Terminology for Reduction of Carbonyl Compounds -- 4.9 Nucleophilic Reducing Agents -- Aluminum Hydrides -- Borohydrides , -- 4.10 Electrophilic Reducing Agents -- Diisobutylaluminum Hydride- i-Bu2AlH -- Borane Tetrahydrofuran and Borane Dimethylsulfide74a,c,e-BH3THF, BH3SMe2 -- 4.11 Regio- and Chemoselective Reductions -- Reductions of α, β-Unsaturated Aldehydes and Ketones -- Reduction of Aldehydes in the Presence of Ketones, -- Reduction of Ketones in the Presence of Aldehydes -- Reduction of Ketones in the Presence of Esters -- Reduction of Carboxylic Acids in the Presence of Ketones or Esters -- Reduction of Esters in the Presence of Amides or Nitriles -- 4.12 Diastereoselective Reductions of Cyclic Ketones -- 4.13 Inversion of Secondary Alcohol Stereochemistry (The Mitsunobu Reaction) -- 4.14 Diastereofacial Selectivity in Acyclic Systems -- Enantiotopicity -- Diastereotopicity-Asymmetric Induction -- 4.15 Enantioselective Reductions -- Alpine-Borane-Ipc-9-BBN -- B-Chlorodiisopinocampheylborane-(Ipc)2BCl -- Oxazaborolidines-CBS Reduction -- BINAL-H -- Enzymatic Approaches to Enantioenriched Alcohols -- References -- 5 Functional Group Transformations -- 5.1 Reactions of Carbon-Carbon Double Bonds -- Hydrogenation of Carbon-Carbon Double Bonds -- Dissolving Metal Reductions -- Hydration of Alkenes -- Epoxidation of Alkenes -- Epoxidation of Allylic Alcohols -- Dihydroxylation of Alkenes-Formation of 1,2-Diols -- Cleavage of Carbon-Carbon Double Bonds -- 5.2 Reactions of Carbon-Carbon Triple Bonds -- Catalytic Semi-Reduction of Alkynes -- Reduction of Alkynes via Protonolysis of Alkenylboranes -- Preparation of trans-Alkenes -- Hydration of Alkynes -- References -- 6 Formation of Carbon-Carbon Single Bonds via Enolate Anions -- 6.1 1,3-Dicarbonyl Compounds.

Malonates -- b-Keto Esters -- 1,3-Diketones -- 6.2 Direct Alkylation of Enolates -- Ester Enolates -- Enolates Derived From Carboxylic Acids, Amides, and Nitriles -- Ketone Enolatesa,c,g, -- 6.3 Cyclization Reactions-Baldwins Rules for Ring Closure -- Intramolecular Aldol Condensations -- Intramolecular Alkylation of Enolates -- 6.4 Stereochemistry of Cyclic Ketone Alkylation -- 6.5 Imine and Hydrazone Anionsb -- Imine Alkylation -- Hydrazone Alkylation -- 6.6 Enamines, -- Preparation of Enamines -- Alkylation of Enamines -- Stereoselective Alkylation of Enamines -- Acylation -- 6.7 The Aldol Reaction -- Intermolecular Aldol Reactions -- Intramolecular Aldol Reactions -- Mixed Aldol Reactions -- Stereoselective Aldol Reactions -- Enantioselective Aldol Reactions -- 6.8 Condensation Reactions of Enols and Enolates -- The Mannich Reaction -- Michael Addition -- 6.9 Robinson Annulation -- References -- 7 Formation of Carbon-Carbon Bonds via Organometallic Reagents -- 7.1 Organolithium Reagents -- Organolithiums from Alkyl Halides and Lithium Metal -- Organolithiums via Lithium-Halogen Exchange -- Organolithiums via Lithium-Metal Exchange (Transmetalation) -- Organolithiums via Lithium-Hydrogen Exchange (Metalation) -- Reagents, Solvents, and Conditions for Efficient Metalation -- Conjugate Addition Reactions of Lithium Reagents -- 7.2 Organomagnesium Reagents -- Preparation of Grignard Reagents -- Reactions of Grignard Reagents with Carbonyl Compounds -- Cross-coupling and Substitution Reactions -- 7.3 Organotitanium Reagents -- 7.4 Organocerium Reagents -- 7.5 Organocopper Reagents -- Preparation of Organocuprates -- Reactions of Organocuprates -- Tandem 1,4-Addition-Enolate Trapping -- Stereochemistry of 1,4-Addition Reactions -- Preparation of Enones: Substrates for Conjugate Additions -- 7.6 Organochromium Reagents -- 7.7 Organozinc Reagents.

Preparation of Organozinc Compounds -- Reactions of Organozinc Compounds -- 7.8 Organoboron Reagents -- Carbonylation -- Cyanidation -- Dichloromethyl Methyl Ether Reaction -- Mattesons Boronic Ester Homologation -- Asymmetric Allyl- and Crotylboration -- 7.9 Organosilicon Reagents -- Properties of Bonds to Silicon -- Preparation and Reactions of Alkynylsilanes, Alkenylsilanes, and Allylsilanes -- Acylsilanes -- 7.10 Organogold Chemistry -- Nucleophilic Addition to Alkynes, Alkenes, and Allenes -- Cycloisomerizations -- References -- 8 Palladium-Catalyzed Coupling Reactions -- 8.1 Palladium Oxidation State -- 8.2 Organic Synthesis with Palladium(0) Complexes -- Oxidative Addition-Reductive Elimination -- 8.3 The Heck Reaction-Palladium(0)-Catalyzed Olefin Insertion Reactions.1h,k,15 -- 8.4 Palladium-Catalyzed Cross-Coupling with Organometallic Reagents -- The Negishi Reaction -- The Suzuki Reaction -- The Stille Reaction -- 8.5 Cross-Coupling Reactions Involving sp-Carbons -- The Castro-Stephens Reaction -- Preparation of Conjugated Enediynes -- Preparation of 1,3-Diynes -- 8.6 The Trost-Tsuji Reaction -- References -- 9 Formation of Carbon-Carbon π-Bonds -- 9.1 Formation of Carbon-Carbon Double Bonds -- b-Elimination Reactions -- Pyrolytic syn-Elimination Reactions -- Syntheses of Stereodefined Alkenes from Alkynes -- The Wittig, Peterson, and Julia Olefination Reactions -- The Shapiro Reaction -- 9.2 Formation of Carbon-Carbon Triple Bonds -- Elimination Reactions -- Alkylation, -- Isomerization -- One-Step, One-Carbon Homologation-Seyferth-Gilbert Reagent -- References -- 10 Syntheses of Carbocyclic Systems -- 10.1 Intramolecular Free Radical Cyclizations -- Acyloin Condensation -- Pinacol Coupling -- The McMurry Reaction-Synthesis of Alkenesa, -- 10.2 Cation- Cyclizations -- 10.3 Pericyclic Reactions -- The Diels-Alder Reaction,.

Intramolecular Diels-Alder Reactions.

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