高等有机化学课件第九章 节 分子重排.ppt

Chap.9 Molecular Rearrangements;I Classification of Rearrangement Reactions ;Usually the rearrangement was classified by the electron property of the moving group, such as 1. Nucleophilic rearrangement, 2. Electrophilic rearrangement, 3. Radical rearrangement, etc.;1. Nucleophilic rearrangement;* 重排过程中,往往发生邻基的参与而形成桥式中 间体或过渡态,迁移基团与迁移始点和迁移终点相结 合,与环丙烷正离子相似.;2) 迁移基团往往是从离去基团的背面进攻迁移终点, 因此, 从立体化学来看, 发生的常常是反式重排. 3) 对迁移的终点而言, 可以是SN1类型, 也可以是SN2 类型的同步反应. 一般迁移终点为叔碳或至少连有 一个芳基时为SN1历程, 其它的则为SN2历程.;远距离的重排:;几种重要的亲核重排反应;Wagner-Meerwein重排最早是在双萜类化合物的反应中发现的.;Stable cation;脂肪族伯胺与亚硝酸作用发生脱氮重排, 也是Wagner-Meerwein重排的扩展, 叫做Demyanov重排.;脂环族伯胺在亚硝酸作用下发生的重排反应, 常常伴随着环的扩大或缩小. 例如:;;;2 Pinacol Rearrangement;The stable cation formed superior; 至于不同取代基中究竟哪个发生迁移, 情况比较复杂, 除了考虑迁移基团的亲核能力外, 迁移后形成的碳正离子的稳定性也有关系. 一般说, 主要决定于两个迁移基团的中心原子的电子云密度. 通常迁移趋势的顺序为: Ph- R- H- ;;Under HNO2, the amino alcohol rearranges as that of pinacol ;频哪醇重排的立体化学特征:;3. α-Ethandione Rearrangement;α-Ethandione with α- hydrogen will proceed condensation;4 Beckmann Rearrangement;The shift will keep the stereostructure of chiral center;5 Baeyer-Villiger Rearrangement;Group moved as the following order: tertiary alkyl ＞ aryl secondary alkyl ＞primary alkyl ＞ methyl;醛在过氧酸作用下, 则发生氢的迁移,而重排为酸.; The cumene hydroperoxide rearrangement is quite resemble the Baeyer-Villiger Rearrangement;Important industrial reaction for manufacturing phenol and acetone ;III. Electrophilic Rearrangement Electrophilic rearrangement is not so common as nucleophilic rearrangement ;Electrophilic rearrangement;1. Favorskii Rearrangement;Mechanism of Favorskii Rearrangement;For asymmetric cyclopropanone, the stable anion form dominantly;Different α- chloroketone form same rearrangement product:;Intramolecular SN2 attack (structure maintaining):;2. Stevens Rearrangement;The sulfonium cation does the same ;Sommelet Rearrangement;3 Wittig Rearrangement;4 Fries Rearrangement;IV Radi