高等有机化学-Lecture11介绍.ppt

* * * * * * * * * * * * * * * * * * * * t-BuCl t-BuCl The Pinacol Rearrangement semi-pinacol rearrangement Tiffeneau-Demjanov Overman rearrangement : Novel Catalysts for the Overman Rearrangement Ieva Jaunzeme,a Aigars Jirgensons* SYNLETT 2005, No. 19, pp 2984–298601.12.205 AuCl, AuCl3, and PtCl4 人有了知识，就会具备各种分析能力， 明辨是非的能力。 所以我们要勤恳读书，广泛阅读， 古人说“书中自有黄金屋。 ”通过阅读科技书籍，我们能丰富知识， 培养逻辑思维能力； 通过阅读文学作品，我们能提高文学鉴赏水平， 培养文学情趣； 通过阅读报刊，我们能增长见识，扩大自己的知识面。 有许多书籍还能培养我们的道德情操， 给我们巨大的精神力量， 鼓舞我们前进。 * * * * * * * Baeyer-Villiger Rearrangement Group moved as the following order: tertiary alkyl＞aryl＞H＞secondary alkyl ＞primary alkyl＞methyl The cumene hydroperoxide rearrangement is quite resemble the Baeyer-Villiger Rearrangement Important industrial reaction for manufacturing phenol and acetone Memory effects Longer Nucleophilic Rearrangement Free-Radical Rearrangements Electophilic Rearrangements 例 Favorskii Rearrangement Mechanism of Favorskii Rearrangement For asymmetric cycloprapanone, the stable anion form dominantly Different α- chloroketone form same rearrangement product: Intramolecular SN2 attack(structure maintaining): Stevens Rearrangement Structure maintaining The sulfonium cation does the same Sommelet Rearrangement Wittig Rearrangement Fries Rearrangement Reaction 1,2-rearrangements A. Carbon to carbon migrations of R, H, and Ar Wagner-Meerwein and related Reactions: Advanced Organic Chemistry Lecture 11 Rearrangements Reactions Molecular Rearrangements: It refers those reactions in which the carbon skeleton or the position of functional group changed. 分子中的基团或原子从一个原子迁移到另一个原子上，碳胳或官能团的位置发生变化的一类反应称为分子重排反应。 Rearrangement was classified by the electron property of the moving group, such as Nucleophilic rearrangement, Electrophilic rearrangement, Radical rearrangement, etc. MECHANISMS Nucleophilic Rearrangements Whitmore 1,2-shift Open sextet Step I. Creation of a system with open sextet: Formation of a Carbocation Wagner-Meerwein rearrangement 2. Formation of a Nitrene Ste