有机化学中的重排反应.ppt

Chapter 11  Rearrangements Reactions * Bonding weaker than covalent Stereochemistry Carbocations,Carbanions, Free radicals, Carbenes, and Nitrenes Mechanisms and methods of determing them Effects of structure on reactivity Nucleophilic subsitution Electrophilic substitution Free radical substitution Addition reactions Eliminations Rearrangements Oxidations and reductions MECHANISMS Nucleophilic Rearrangements Whitmore 1,2-shift Open sextet Step I. Creation of a system with open sextet: 1. Formation of a Carbocation 2. Formation of a Nitrene Step II. Migration Step III. The migration origin (A) acquires an octet Rearrangement with substitution (combinations with a nucleophile) Rearrangement with elimination (loss of H+) The Actual Nature of the Migration The configeration of W is retained Inversion of B Racimation is found at B: Inversion occurs at B: SN1-like SN2-like When B is a teriary atom or has one aryl group and at least one other alkyl or aryl group SN1-like In other case, SN2-like 1. 2. When R is aryl or vinyl, the intermediate is probably formed When R is alkyl, the intermediate is not formed Inversion at A and B Inversion at A only Migratory Aptitudes Memory effects Longer Nucleophilic Rearrangement Free-Radical Rearrangements Electophilic Rearrangements 例 Reaction 1,2-rearrangements A. Carbon to carbon migrations of R, H, and Ar Wagner-Meerwein and related Reactions: t-BuCl t-BuCl The Pinacol Rearrangement semi-pinacol rearrangement Expansion and contraction of rings Tiffeneau-Demjanov *