Name: [3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
Uploaded: 2022-09-29T07:58:57-04:00
Duration: 1 min 24 s
Description: The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds.

Chapter 16: Dienes, Conjugated Pi Systems, and Pericyclic Reactions Back To Chapter

16.26: [3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

TABLE OF
CONTENTS

X

Chapter 1: Covalent Bonding and Structure

30
1.1: What is Organic Chemistry?
30
1.2: Electronic Structure of Atoms
30
1.3: Electron Configurations
30
1.4: Chemical Bonds
30
1.5: Polar Covalent Bonds
30
1.6: Lewis Structures and Formal Charges
30
1.7: VSEPR Theory
30
1.8: Molecular Geometry and Dipole Moments
30
1.9: Resonance and Hybrid Structures
30
1.10: Valence Bond Theory and Hybridized Orbitals
30
1.11: MO Theory and Covalent Bonding
30
1.12: Intermolecular Forces and Physical Properties
30
1.13: Solubility
30
1.14: Introduction to Functional Groups
30
1.15: Overview of Advanced Functional Groups

Chapter 2: Thermodynamics and Chemical Kinetics

30
2.1: Chemical Reactions
30
2.2: Enthalpy and Heat of Reaction
30
2.3: Energetics of Solution Formation
30
2.4: Entropy and Solvation
30
2.5: Gibbs Free Energy and Thermodynamic Favorability
30
2.6: Chemical and Solubility Equilibria
30
2.7: Rate Law and Reaction Order
30
2.8: Effect of Temperature Change on Reaction Rate
30
2.9: Multi-Step Reactions
30
2.10: Bond Dissociation Energy and Activation Energy
30
2.11: Energy Diagrams, Transition States, and Intermediates
30
2.12: Predicting Reaction Outcomes

Chapter 3: Alkanes and Cycloalkanes

30
3.1: Structure of Alkanes
30
3.2: Constitutional Isomers of Alkanes
30
3.3: Nomenclature of Alkanes
30
3.4: Physical Properties of Alkanes
30
3.5: Newman Projections
30
3.6: Conformations of Ethane and Propane
30
3.7: Conformations of Butane
30
3.8: Cycloalkanes
30
3.9: Conformations of Cycloalkanes
30
3.10: Conformations of Cyclohexane
30
3.11: Chair Conformation of Cyclohexane
30
3.12: Stability of Substituted Cyclohexanes
30
3.13: Disubstituted Cyclohexanes: cis-trans Isomerism
30
3.14: Combustion Energy: A Measure of Stability in Alkanes and Cycloalkanes

Chapter 4: Stereoisomerism

30
4.1: Chirality
30
4.2: Isomerism
30
4.3: Stereoisomers
30
4.4: Naming Enantiomers
30
4.5: Properties of Enantiomers and Optical Activity
30
4.6: Molecules with Multiple Chiral Centers
30
4.7: Fischer Projections
30
4.8: Racemic Mixtures and the Resolution of Enantiomers
30
4.9: Stereoisomerism of Cyclic Compounds
30
4.10: Chirality at Nitrogen, Phosphorus, and Sulfur
30
4.11: Prochirality
30
4.12: Chirality in Nature

Chapter 5: Acids and Bases

30
5.1: Brønsted-Lowry Acids and Bases
30
5.2: Lewis Acids and Bases
30
5.3: Acid and Bases: Ka, pKa, and Relative Strengths
30
5.4: Position of Equilibrium in Acid-Base Reactions
30
5.5: Molecular Structure and Acidity
30
5.6: Leveling Effect and Non-Aqueous Acid-Base Solutions
30
5.7: Solvating Effects

Chapter 6: Nucleophilic Substitution and Elimination Reactions of Alkyl Halides

30
6.1: Alkyl Halides
30
6.2: Nucleophilic Substitution Reactions
30
6.3: Nucleophiles
30
6.4: Electrophiles
30
6.5: Leaving Groups
30
6.6: Carbocations
30
6.7: SN2 Reaction: Kinetics
30
6.8: SN2 Reaction: Mechanism
30
6.9: SN2 Reaction: Transition State
30
6.10: SN2 Reaction: Stereochemistry
30
6.11: SN1 Reaction: Kinetics
30
6.12: SN1 Reaction: Mechanism
30
6.13: SN1 Reaction: Stereochemistry
30
6.14: Predicting Products: SN1 vs. SN2
30
6.15: Elimination Reactions
30
6.16: E2 Reaction: Kinetics and Mechanism
30
6.17: E2 Reaction: Stereochemistry and Regiochemistry
30
6.18: E1 Reaction: Kinetics and Mechanism
30
6.19: E1 Reaction: Stereochemistry and Regiochemistry
30
6.20: Predicting Products: Substitution vs. Elimination

Chapter 7: Alkene Structure and Reactivity

30
7.1: Structure and Bonding of Alkenes
30
7.2: Nomenclature of Alkenes
30
7.3: Degree of Unsaturation
30
7.4: Isomerism in Alkenes
30
7.5: Relative Stabilities of Alkenes
30
7.6: Introduction to Electrophilic Addition Reactions of Alkenes
30
7.7: Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule

Chapter 8: Reactions of Alkenes

30
8.1: Regioselectivity of Electrophilic Additions-Peroxide Effect
30
8.2: Free-Radical Chain Reaction and Polymerization of Alkenes
30
8.3: Halogenation of Alkenes
30
8.4: Formation of Halohydrin from Alkenes
30
8.5: Acid-Catalyzed Hydration of Alkenes
30
8.6: Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
30
8.7: Oxymercuration-Reduction of Alkenes
30
8.8: Hydroboration-Oxidation of Alkenes
30
8.9: Regioselectivity and Stereochemistry of Hydroboration
30
8.10: Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
30
8.11: Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate
30
8.12: Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
30
8.13: Oxidative Cleavage of Alkenes: Ozonolysis
30
8.14: Reduction of Alkenes: Catalytic Hydrogenation
30
8.15: Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

Chapter 9: Alkynes

30
9.1: Structure and Physical Properties of Alkynes
30
9.2: Nomenclature of Alkynes
30
9.3: Acidity of 1-Alkynes
30
9.4: Preparation of Alkynes: Alkylation Reaction
30
9.5: Preparation of Alkynes: Dehydrohalogenation
30
9.6: Electrophilic Addition to Alkynes: Halogenation
30
9.7: Electrophilic Addition to Alkynes: Hydrohalogenation
30
9.8: Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
30
9.9: Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
30
9.10: Alkynes to Carboxylic Acids: Oxidative Cleavage
30
9.11: Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
30
9.12: Reduction of Alkynes to trans-Alkenes: Sodium in Liquid Ammonia

Chapter 10: Alcohols and Phenols

30
10.1: Structure and Nomenclature of Alcohols and Phenols
30
10.2: Physical Properties of Alcohols and Phenols
30
10.3: Acidity and Basicity of Alcohols and Phenols
30
10.4: Preparation of Alcohols via Addition Reactions
30
10.5: Preparation of Alcohols via Substitution Reactions
30
10.6: Acid-Catalyzed Dehydration of Alcohols to Alkenes
30
10.7: Alcohols from Carbonyl Compounds: Reduction
30
10.8: Alcohols from Carbonyl Compounds: Grignard Reaction
30
10.9: Protection of Alcohols
30
10.10: Preparation of Diols and Pinacol Rearrangement
30
10.11: Conversion of Alcohols to Alkyl Halides
30
10.12: Oxidation of Alcohols

Chapter 11: Ethers, Epoxides, Sulfides

30
11.1: Structure and Nomenclature of Ethers
30
11.2: Physical Properties of Ethers
30
11.3: Ethers from Alcohols: Alcohol Dehydration and Williamson Ether Synthesis
30
11.4: Ethers from Alkenes: Alcohol Addition and Alkoxymercuration-Demercuration
30
11.5: Ethers to Alkyl Halides: Acidic Cleavage
30
11.6: Autoxidation of Ethers to Peroxides and Hydroperoxides
30
11.7: Crown Ethers
30
11.8: Structure and Nomenclature of Epoxides
30
11.9: Preparation of Epoxides
30
11.10: Sharpless Epoxidation
30
11.11: Acid-Catalyzed Ring-Opening of Epoxides
30
11.12: Base-Catalyzed Ring-Opening of Epoxides
30
11.13: Structure and Nomenclature of Thiols and Sulfides
30
11.14: Preparation and Reactions of Thiols
30
11.15: Preparation and Reactions of Sulfides

Chapter 12: Aldehydes and Ketones

30
12.1: Structures of Aldehydes and Ketones
30
12.3: IUPAC Nomenclature of Aldehydes
30
12.4: IUPAC Nomenclature of Ketones
30
12.5: Common Names of Aldehydes and Ketones
30
12.6: IR and UV–Vis Spectroscopy of Aldehydes and Ketones
30
12.7: NMR Spectroscopy and Mass Spectrometry of Aldehydes and Ketones
30
12.8: Preparation of Aldehydes and Ketones from Alcohols, Alkenes, and Alkynes
30
12.9: Preparation of Aldehydes and Ketones from Nitriles and Carboxylic Acids
30
12.10: Preparation of Aldehydes and Ketones from Carboxylic Acid Derivatives
30
12.13: Nucleophilic Addition to the Carbonyl Group: General Mechanism
30
12.14: Aldehydes and Ketones with Water: Hydrate Formation
30
12.15: Aldehydes and Ketones with Alcohols: Hemiacetal Formation
30
12.18: Protecting Groups for Aldehydes and Ketones: Introduction
30
12.19: Acetals and Thioacetals as Protecting Groups for Aldehydes and Ketones
30
12.20: Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview
30
12.21: Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
30
12.22: Aldehydes and Ketones to Alkenes: Wittig Reaction Overview
30
12.23: Aldehydes and Ketones to Alkenes: Wittig Reaction Mechanism
30
12.24: Aldehydes and Ketones with Amines: Imine and Enamine Formation Overview
30
12.25: Aldehydes and Ketones with Amines: Imine Formation Mechanism
30
12.26: Aldehydes and Ketones with Amines: Enamine Formation Mechanism
30
12.29: Aldehydes and Ketones to Alkanes: Wolff–Kishner Reduction
30
12.30: Oxidations of Aldehydes and Ketones to Carboxylic Acids
30
12.31: Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation
30
12.33: Keto–Enol Tautomerism: Mechanism

Chapter 13: Carboxylic Acids

30
13.1: IUPAC Nomenclature of Carboxylic Acids
30
13.4: Physical Properties of Carboxylic Acids
30
13.5: Acidity of Carboxylic Acids
30
13.6: Substituent Effects on Acidity of Carboxylic Acids
30
13.7: IR and UV–Vis Spectroscopy of Carboxylic Acids
30
13.8: NMR and Mass Spectroscopy of Carboxylic Acids
30
13.9: Preparation of Carboxylic Acids: Overview
30
13.10: Preparation of Carboxylic Acids: Hydrolysis of Nitriles
30
13.11: Preparation of Carboxylic Acids: Carboxylation of Grignard Reagents
30
13.12: Reactions of Carboxylic Acids: Introduction
30
13.13: Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Overview
30
13.14: Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Mechanism
30
13.15: Carboxylic Acids to Methylesters: Alkylation using Diazomethane
30
13.16: Carboxylic Acids to Acid Chlorides
30
13.17: Carboxylic Acids to Primary Alcohols: Hydride Reduction
30
13.18: Loss of Carboxy Group as CO2: Decarboxylation of β-Ketoacids
30
13.19: Loss of Carboxy Group as CO2: Decarboxylation of Malonic Acid Derivatives

Chapter 14: Carboxylic Acid Derivatives

30
14.1: Carboxylic Acid Derivatives: Overview
30
14.2: Nomenclature of Carboxylic Acid Derivatives: Acid Halides, Esters, and Acid Anhydrides
30
14.3: Nomenclature of Carboxylic Acid Derivatives: Amides and Nitriles
30
14.4: Structures of Carboxylic Acid Derivatives
30
14.5: Physical Properties of Carboxylic Acid Derivatives
30
14.6: Acidity and Basicity of Carboxylic Acid Derivatives
30
14.7: Spectroscopy of Carboxylic Acid Derivatives
30
14.8: Relative Reactivity of Carboxylic Acid Derivatives
30
14.9: Nucleophilic Acyl Substitution of Carboxylic Acid Derivatives
30
14.10: Acid Halides to Carboxylic Acids: Hydrolysis
30
14.11: Acid Halides to Esters: Alcoholysis
30
14.12: Acid Halides to Amides: Aminolysis
30
14.13: Acid Halides to Alcohols: LiAlH4 Reduction
30
14.14: Acid Halides to Alcohols: Grignard Reaction
30
14.15: Acid Halides to Ketones: Gilman Reagent
30
14.16: Preparation of Acid Anhydrides
30
14.17: Reactions of Acid Anhydrides
30
14.18: Esters to Carboxylic Acids: Saponification
30
14.19: Esters to Carboxylic Acids: Acid-Catalyzed Hydrolysis
30
14.20: Esters to Alcohols: Hydride Reductions
30
14.21: Esters to Alcohols: Grignard Reaction
30
14.22: Preparation of Amides
30
14.23: Amides to Carboxylic Acids: Hydrolysis
30
14.24: Amides to Amines: LiAlH4 Reduction
30
14.25: Preparation of Nitriles
30
14.26: Nitriles to Carboxylic Acids: Hydrolysis
30
14.27: Nitriles to Ketones: Grignard Reaction
30
14.28: Nitriles to Amines: LiAlH4 Reduction

Chapter 15: α-Carbon Chemistry: Enols, Enolates, and Enamines

30
15.1: Reactivity of Enols
30
15.2: Reactivity of Enolate Ions
30
15.3: Types of Enols and Enolates
30
15.4: Enolate Mechanism Conventions
30
15.5: Regioselective Formation of Enolates
30
15.6: Stereochemical Effects of Enolization
30
15.7: Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
30
15.8: Base-Promoted α-Halogenation of Aldehydes and Ketones
30
15.9: Multiple Halogenation of Methyl Ketones: Haloform Reaction
30
15.10: α-Halogenation of Carboxylic Acid Derivatives: Overview
30
15.11: α-Bromination of Carboxylic Acids: Hell–Volhard–Zelinski Reaction
30
15.12: Reactions of α-Halocarbonyl Compounds: Nucleophilic Substitution
30
15.13: Nitrosation of Enols
30
15.14: C–C Bond Formation: Aldol Condensation Overview
30
15.15: Base-Catalyzed Aldol Addition Reaction
30
15.16: Acid-Catalyzed Aldol Addition Reaction
30
15.17: Dehydration of Aldols to Enals: Base-Catalyzed Aldol Condensation
30
15.18: Dehydration of Aldols to Enones: Acid-Catalyzed Aldol Condensation
30
15.19: Intramolecular Aldol Reaction
30
15.20: C–C Bond Cleavage: Retro-Aldol Reaction
30
15.21: Crossed Aldol Reactions: Overview
30
15.22: Crossed Aldol Reaction Using Weak Bases
30
15.23: Ketones with Nonenolizable Aromatic Aldehydes: Claisen–Schmidt Condensation
30
15.24: Crossed Aldol Reaction Using Strong Bases: Directed Aldol Reaction
30
15.26: Aldol Condensation with β-Diesters: Knoevenagel Condensation
30
15.27: Esters to β-Ketoesters: Claisen Condensation Overview
30
15.28: Esters to β-Ketoesters: Claisen Condensation Mechanism
30
15.29: Aldol Condensation vs Claisen Condensation
30
15.30: Intramolecular Claisen Condensation of Dicarboxylic Esters: Dieckmann Cyclization
30
15.31: β-Dicarbonyl Compounds via Crossed Claisen Condensations
30
15.32: α-Alkylation of Ketones via Enolate Ions
30
15.33: Factors Affecting α-Alkylation of Ketones: Choice of Base
30
15.34: Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis
30
15.35: Alkylation of β-Diester Enolates: Malonic Ester Synthesis
30
15.36: Conjugate Addition to α,β-Unsaturated Carbonyl Compounds
30
15.37: Conjugate Addition (1,4-Addition) vs Direct Addition (1,2-Addition)
30
15.38: Conjugate Addition of Enolates: Michael Addition
30
15.39: Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
30
15.40: Synthesis of α-Substituted Carbonyl Compounds: The Stork Enamine Reaction
30
15.42: Nonenolizable Aldehydes to Acids and Alcohols: The Cannizzaro Reaction

Chapter 16: Dienes, Conjugated Pi Systems, and Pericyclic Reactions

30
16.1: Structure of Conjugated Dienes
30
16.2: Stability of Conjugated Dienes
30
16.3: π Molecular Orbitals of 1,3-Butadiene
30
16.4: π Molecular Orbitals of the Allyl Cation and Anion
30
16.5: π Molecular Orbitals of the Allyl Radical
30
16.6: Electrophilic 1,2- and 1,4-Addition of HX to 1,3-Butadiene
30
16.7: Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene
30
16.8: Electrophilic Addition of HX to 1,3-Butadiene: Thermodynamic vs Kinetic Control
30
16.9: UV–Vis Spectroscopy of Conjugated Systems
30
16.10: UV–Vis Spectroscopy: Woodward–Fieser Rules
30
16.11: Pericyclic Reactions: Introduction
30
16.12: Thermal and Photochemical Electrocyclic Reactions: Overview
30
16.13: Thermal Electrocyclic Reactions: Stereochemistry
30
16.14: Photochemical Electrocyclic Reactions: Stereochemistry
30
16.15: Cycloaddition Reactions: Overview
30
16.16: Cycloaddition Reactions: MO Requirements for Thermal Activation
30
16.17: Cycloaddition Reactions: MO Requirements for Photochemical Activation
30
16.18: [4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
30
16.19: Diels–Alder vs Retro-Diels–Alder Reaction: Thermodynamic Factors
30
16.20: Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
30
16.21: Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
30
16.22: Diels–Alder Reaction: Characteristics of Dienes
30
16.23: Diels–Alder Reaction: Characteristics of Dienophiles
30
16.24: Thermal Sigmatropic Reactions: Overview
30
16.25: [3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
30
16.26: [3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
30
16.27: Woodward–Hoffmann Selection Rules and Microscopic Reversibility

Chapter 17: Aromatic Compounds

30
17.1: Aromatic Compounds: Overview
30
17.2: Nomenclature of Aromatic Compounds with a Single Substituent
30
17.3: Nomenclature of Aromatic Compounds with Multiple Substituents
30
17.4: Structure of Benzene: Kekulé Model
30
17.5: Structure of Benzene: Molecular Orbital Model
30
17.7: Criteria for Aromaticity and the Hückel 4n + 2 Rule
30
17.8: Hückel's Rule Diagram of π MOs: Frost Circle
30
17.9: Frost Circles for Different Conjugated Systems
30
17.13: Aromatic Hydrocarbon Anions: Structural Overview
30
17.14: Aromatic Hydrocarbon Cations: Structural Overview
30
17.15: Five-Membered Heterocyclic Aromatic Compounds: Overview
30
17.19: NMR Spectroscopy of Aromatic Compounds

Chapter 18: Reactions of Aromatic Compounds

30
18.4: NMR Spectroscopy of Benzene Derivatives
30
18.5: Reactions at the Benzylic Position: Oxidation and Reduction
30
18.7: Reactions at the Benzylic Position: Halogenation
30
18.8: Electrophilic Aromatic Substitution: Overview
30
18.9: Electrophilic Aromatic Substitution: Chlorination and Bromination of Benzene
30
18.10: Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
30
18.11: Electrophilic Aromatic Substitution: Nitration of Benzene
30
18.12: Electrophilic Aromatic Substitution: Sulfonation of Benzene
30
18.13: Electrophilic Aromatic Substitution: Friedel–Crafts Alkylation of Benzene
30
18.14: Electrophilic Aromatic Substitution: Friedel–Crafts Acylation of Benzene
30
18.15: Limitations of Friedel–Crafts Reactions
30
18.16: Directing Effect of Substituents: ortho–para-Directing Groups
30
18.17: Directing Effect of Substituents: meta-Directing Groups
30
18.18: ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
30
18.19: ortho–para-Directing Deactivators: Halogens
30
18.20: meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H
30
18.21: Directing and Steric Effects in Disubstituted Benzene Derivatives
30
18.23: Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)
30
18.24: Nucleophilic Aromatic Substitution: Elimination–Addition
30
18.25: Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
30
18.26: Reduction of Benzene to Cyclohexane: Catalytic Hydrogenation
30
18.28: Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism
30
18.29: Hydrolysis of Chlorobenzene to Phenol: Dow Process
30
18.30: Benzene to Phenol via Cumene: Hock Process
30
18.32: Oxidation of Phenols to Quinones

Chapter 19: Amines

30
19.1: Amines: Introduction
30
19.2: Nomenclature of Primary Amines
30
19.3: Nomenclature of Secondary and Tertiary Amines
30
19.4: Nomenclature of Aryl and Heterocyclic Amines
30
19.5: Structure of Amines
30
19.6: Physical Properties of Amines
30
19.7: Basicity of Aliphatic Amines
30
19.8: Basicity of Aromatic Amines
30
19.9: Basicity of Heterocyclic Aromatic Amines
30
19.10: NMR Spectroscopy Of Amines
30
19.12: Mass Spectrometry of Amines
30
19.13: Preparation of Amines: Alkylation of Ammonia and Amines
30
19.14: Preparation of 1° Amines: Azide Synthesis
30
19.15: Preparation of 1° Amines: Gabriel Synthesis
30
19.16: Preparation of Amines: Reduction of Oximes and Nitro Compounds
30
19.17: Preparation of Amines: Reduction of Amides and Nitriles
30
19.18: Preparation of Amines: Reductive Amination of Aldehydes and Ketones
30
19.19: Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview
30
19.20: Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism
30
19.21: Amines to Amides: Acylation of Amines
30
19.22: Amines to Alkenes: Hofmann Elimination
30
19.24: Amines to Alkenes: Cope Elimination
30
19.25: 1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Overview
30
19.26: 1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
30
19.27: 2° Amines to N-Nitrosamines: Reaction with NaNO2
30
19.28: Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
30
19.29: Diazonium Group Substitution: –OH and –H
30
19.30: Aryldiazonium Salts to Azo Dyes: Diazo Coupling
30
19.31: Amines to Sulfonamides: The Hinsberg Test

Chapter 20: Radical Chemistry

30
20.1: Radicals: Electronic Structure and Geometry
30
20.4: Electron Paramagnetic Resonance (EPR) Spectroscopy: Organic Radicals
30
20.5: Radical Formation: Overview
30
20.6: Radical Formation: Homolysis
30
20.7: Radical Formation: Abstraction
30
20.8: Radical Formation: Addition
30
20.9: Radical Formation: Elimination
30
20.10: Radical Reactivity: Overview
30
20.11: Radical Reactivity: Steric Effects
30
20.12: Radical Reactivity: Concentration Effects
30
20.13: Radical Reactivity: Electrophilic Radicals
30
20.14: Radical Reactivity: Nucleophilic Radicals
30
20.15: Radical Reactivity: Intramolecular vs Intermolecular
30
20.16: Radical Autoxidation
30
20.17: Radical Oxidation of Allylic and Benzylic Alcohols
30
20.18: Radical Substitution: Halogenation of Alkanes and Alkyl Substituents
30
20.19: Radical Halogenation: Thermodynamics
30
20.21: Radical Halogenation: Stereochemistry
30
20.22: Radical Substitution: Allylic Chlorination
30
20.23: Radical Substitution: Allylic Bromination
30
20.24: Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
30
20.25: Radical Anti-Markovnikov Addition to Alkenes: Overview
30
20.26: Radical Anti-Markovnikov Addition to Alkenes: Mechanism
30
20.27: Radical Anti-Markovnikov Addition to Alkenes: Thermodynamics
30
20.28: Vicinal Diols via Reductive Coupling of Aldehydes or Ketones: Pinacol Coupling Overview
30
20.30: Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
30
20.31: α-Hydroxy Ketones via Reductive Coupling of Esters: Acyloin Condensation Overview

Chapter 21: Synthetic Polymers

30
21.2: Characteristics and Nomenclature of Homopolymers
30
21.3: Characteristics and Nomenclature of Copolymers
30
21.4: Polymers: Defining Molecular Weight
30
21.5: Polymers: Molecular Weight Distribution
30
21.6: Polymer Classification: Architecture
30
21.7: Polymer Classification: Crystallinity
30
21.8: Polymer Classification: Stereospecificity
30
21.10: Radical Chain-Growth Polymerization: Overview
30
21.11: Radical Chain-Growth Polymerization: Mechanism
30
21.12: Radical Chain-Growth Polymerization: Chain Branching
30
21.13: Anionic Chain-Growth Polymerization: Overview
30
21.14: Anionic Chain-Growth Polymerization: Mechanism
30
21.16: Cationic Chain-Growth Polymerization: Mechanism
30
21.17: Ziegler–Natta Chain-Growth Polymerization: Overview
30
21.19: Step-Growth Polymerization: Overview
30
21.20: Molecular Weight of Step-Growth Polymers
30
21.22: Types of Step-Growth Polymers: Polyesters
30
21.24: Olefin Metathesis Polymerization: Overview
30
21.25: Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
30
21.26: Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)

Full Table of Contents

JoVE Core
Organic Chemistry

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[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

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16.25: [3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement

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TRANSCRIPT

The Claisen rearrangement is an oxy-variant of the Cope reaction in which one of the saturated carbons of a 1,5-diene is replaced by an oxygen atom.

A simple example is the thermal isomerization of allyl vinyl ethers to γ,δ-unsaturated carbonyl compounds.

The equilibrium strongly favors the product since the rearrangement yields a compound with a stable carbon–oxygen bond.

Like the Cope rearrangement, the mechanism follows a concerted reorganization of six electrons, preferably via a chair-like transition state.

The reaction is highly stereoselective. For example, isomerization of substituted allyl vinyl ethers favors the stereoisomer where the double bonds adopt an E configuration.

Note that the product is derived from a chair-like transition state, where the substituent occupies an equatorial position.

In allyl aryl ethers, the rearrangement gives an unsaturated ketone intermediate, which tautomerizes into a stable enol form, restoring aromaticity to the ring.

If both ortho positions are occupied, the reaction proceeds via two sequential Claisen rearrangements to give the p-allyl product.

16.26: [3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.

An aromatic Claisen rearrangement involves the conversion of allyl aryl ethers to an unstable ketone intermediate, which tautomerizes to give ortho-substituted phenols.

However, ortho-substituted allyl aryl ethers exclusively yield para-substituted phenols via two sequential Clasien rearrangements.

Chapter 1: Covalent Bonding and Structure

Chapter 2: Thermodynamics and Chemical Kinetics

Chapter 3: Alkanes and Cycloalkanes

Chapter 4: Stereoisomerism

Chapter 5: Acids and Bases

Chapter 6: Nucleophilic Substitution and Elimination Reactions of Alkyl Halides

Chapter 7: Alkene Structure and Reactivity

Chapter 8: Reactions of Alkenes

Chapter 9: Alkynes

Chapter 10: Alcohols and Phenols

Chapter 11: Ethers, Epoxides, Sulfides

Chapter 12: Aldehydes and Ketones

Chapter 13: Carboxylic Acids

Chapter 14: Carboxylic Acid Derivatives

Chapter 15: α-Carbon Chemistry: Enols, Enolates, and Enamines

Chapter 16: Dienes, Conjugated Pi Systems, and Pericyclic Reactions

Chapter 17: Aromatic Compounds

Chapter 18: Reactions of Aromatic Compounds

Chapter 19: Amines

Chapter 20: Radical Chemistry

Chapter 21: Synthetic Polymers

16.26: [3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

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