【总结】分子重排_图文.ppt

The cumene hydroperoxide rearrangement is quite resemble the Baeyer-Villiger Rearrangement Important industrial reaction for manufacturing phenol and acetone Electrophilic rearrangement is not so common as nucleophilic rearrangement The transition state §2.3 Electrophilic Rearrangement 1. Favorskii Rearrangement Carboxylic esters from ?-haloketones Mechanism of Favorskii Rearrangement For asymmetric cycloprapanone, the stable anion form dominantly Different α- chloroketone form same rearrangement product: Same intermediate Intramolecular SN2 attack(structure maintaining): 2. Stevens Rearrangement Tertiary amines from quaternary ammonium salts by migration of an alkyl group Structure maintaining The sulfonium cation does the same Sommelet Rearrangement 3. Wittig Rearrangement Rearrangement of ethers to yield alcohols Especially suitable substrates are ethers where the intermediate carbanion can be stabilized by one of the substituents 4. Fries Rearrangement Acylphenols from phenyl esters Mechanism of Fries Rearrangement §2.4 Radical Rearrangement In general, alkyl cannot shift Usually the aryl, alkenyl and acetoxy can shift Mechanisms of Organic Reaction Chapter 7 Molecular Rearrangements §2.1 Classification of Rearrangement Reactions Molecular Rearrangements The reactions in which the carbon skeleton or the position of functional group changed. Radical rearrangement Usually, the rearrangement was classified by the electron property of the moving group Nucleophilic rearrangement Electrophilic rearrangement Nucleophilic rearrangement Electrophilic rearrangement Radical rearrangement §2. 2 Nucleophilic Rearrangement 1. Wagner-Meerwein rearrangement Rearrangement of the carbon skeleton via carbenium ions A nucleophilic 1,2-migrations of alkyl groups Addition of a nucleophile Loss of a proton More stable Stable cation Stable cation Migratory order of the migration groups 2 Pinacolic Rearrangement Rearrangement of vicinal diols A special