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🥼organic chemistry review

Rearrangements

Written by the Fiveable Content Team • Last updated September 2025
Written by the Fiveable Content Team • Last updated September 2025

Definition

Rearrangements are a class of organic reactions where the atoms in a molecule are reorganized, leading to the formation of a new compound with a different structure. This term is particularly relevant in the context of polar reaction mechanisms and the preparation of alkyl halides from alkanes through radical halogenation.

5 Must Know Facts For Your Next Test

  1. Rearrangements often involve the formation of a carbocation intermediate, which can be stabilized through the migration of a neighboring alkyl group.
  2. Curved arrow notation is a crucial tool for depicting the movement of electrons during rearrangement reactions, particularly in the context of polar reaction mechanisms.
  3. Radical halogenation of alkanes can lead to rearrangements, as the formation of a tertiary radical intermediate may be favored over the primary radical.
  4. Sigmatropic rearrangements, such as the Cope and Claisen rearrangements, involve the migration of $\sigma$-bonds within a molecule, often leading to the formation of new ring systems.
  5. The Beckmann rearrangement is an important example of a rearrangement reaction that is commonly used in the synthesis of amides from oximes.

Review Questions

  • Explain how rearrangements can occur during the radical halogenation of alkanes and the significance of this process.
    • During the radical halogenation of alkanes, the formation of a tertiary radical intermediate can be favored over the primary radical. This is because tertiary radicals are more stable due to the greater degree of hyperconjugation and delocalization of the unpaired electron. The formation of the more stable tertiary radical can lead to rearrangements, where the position of the halogen atom is shifted within the molecule. This rearrangement process is significant because it can result in the formation of different alkyl halide products, which can have different reactivity and applications in organic synthesis.
  • Describe the role of curved arrow notation in depicting rearrangement reactions, particularly in the context of polar reaction mechanisms.
    • Curved arrow notation is an essential tool for visualizing the movement of electrons during rearrangement reactions, especially in the context of polar reaction mechanisms. By using curved arrows, you can track the flow of electrons as atoms or functional groups shift within the molecule, leading to the formation of new bonds and the reorganization of the molecular structure. This notation helps you understand the step-by-step mechanism of rearrangement reactions, which is crucial for predicting the products and anticipating potential side reactions.
  • Analyze the significance of carbocation rearrangements and sigmatropic rearrangements in organic synthesis and their applications.
    • Carbocation rearrangements and sigmatropic rearrangements are important classes of rearrangement reactions that have numerous applications in organic synthesis. Carbocation rearrangements, where a neighboring alkyl group migrates to stabilize a carbocation intermediate, can be used to synthesize more complex molecules by creating new carbon-carbon bonds and introducing functional group diversity. Sigmatropic rearrangements, such as the Cope and Claisen rearrangements, allow for the formation of new ring systems and can be used to construct complex natural products and pharmaceuticals. Understanding the mechanisms and stereochemical outcomes of these rearrangement reactions is crucial for designing efficient synthetic routes and predicting the structures of the final products.