Electron Rearrangement

Electron rearrangement is the redistribution of electrons within or between atoms as a chemical reaction proceeds, enabling molecules to change structure and form new substances. In organic chemistry, curved-arrow notation tracks the movement of electron pairs from electron-rich sites, such as lone pairs or pi bonds, toward electron-deficient atoms, while existing bonds may break as new bonds form. These shifts underlie substitution, addition, elimination, and rearrangement reactions and help explain reaction mechanisms, intermediate stability, and product formation. Understanding electron rearrangement allows chemists to predict reaction pathways, interpret experimental results, and design more efficient syntheses of pharmaceuticals, materials, and other molecular products.

Electron Rearrangement - Related Videos

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JoVE Core - Organic Chemistry

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

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2023

The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state. From a molecular orbital perspective, the rearrangement can be viewed as the interaction between the ground state frontier orbitals of the allyl anion and cation. Under thermal conditions, the two π...

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

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2023

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...

Preparation of Diols and Pinacol Rearrangement

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2023

Compounds bearing two hydroxyl groups are known as diols. When the hydroxyl groups are located on adjacent carbon atoms, the diols are called vicinal diols or glycols. Under acidic conditions, vicinal diols undergo a specific reaction called pinacol rearrangement. The reaction begins with transferring a proton from the acid catalyst to one of the hydroxyl groups, producing an oxonium ion. In the second step, the oxonium ion loses H2O, forming a tertiary carbocation intermediate. In the...

Electron Carriers

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2019

Electron carriers can be thought of as electron shuttles. These compounds can easily accept electrons (i.e., be reduced) or lose them (i.e., be oxidized). They play an essential role in energy production because cellular respiration is contingent on the flow of electrons. Over the many stages of cellular respiration, glucose breaks down into carbon dioxide and water. Electron carriers pick up electrons lost by glucose in these reactions, temporarily storing and releasing them into the electron...

Preparation of 1° Amines: Hofmann and Curtius Rearrangement Overview

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2025

In the presence of an aqueous base and a halogen, primary amides can lose the carbonyl (as carbon dioxide) and undergo rearrangement to form primary amines. This reaction, called the Hofmann rearrangement, can produce primary amines (aryl and alkyl) in high yields without contamination by secondary and tertiary amines. In the Curtius rearrangement, acyl azides are converted into primary amines under thermal conditions, accompanied by the loss of gaseous N2 and CO2. The loss of nitrogen acts as...

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