Organic chemistry features no more useful or strategically critical transformations than rearrangements. These reactions stand apart from simple substitutions or additions because they cause complete structural rearrangements within molecules through the migration of atoms or groups which frequently results in major changes to the carbon backbone or functional group arrangement. Understanding these intricate dances of atoms is crucial for designing complex synthetic routes, accessing valuable intermediates, and constructing intricate molecular architectures found in pharmaceuticals, agrochemicals, and advanced materials.
This page serves as your gateway to detailed insights into some of the most significant named rearrangement reactions. Each reaction is a testament to chemical ingenuity, offering unique pathways to build molecular complexity efficiently. Discover their mechanisms, scope, limitations, and modern applications through our curated resources.
Key Rearrangement Reactions
Baker-Venkataraman Rearrangement
A base-catalyzed intramolecular acyl transfer converting an ortho-acyloxy ketone into a 1,3-diketone, crucial for flavonoid synthesis.
Beckmann Rearrangement
The acid-catalyzed transformation of ketoximes into substituted amides (lactams for cyclic ketoximes), pivotal in nylon-6 production (from cyclohexanone oxime).
Brook Rearrangement
The base-induced 1,2-migration of a silyl group from carbon to oxygen in α-silyl alkoxides, generating silyl ethers and carbanions valuable for further chain elongation.
Carroll Rearrangement
A thermal [3,3]-sigmatropic rearrangement of allyl acetoacetates (or β-keto allyl esters) followed by decarboxylation, producing γ,δ-unsaturated ketones.
Claisen Rearrangement
A powerful thermal [3,3]-sigmatropic rearrangement of allyl vinyl ethers, yielding γ,δ-unsaturated carbonyl compounds, fundamental in forming C-C bonds with predictable stereochemistry.
Cope Rearrangement
A thermal [3,3]-sigmatropic rearrangement of 1,5-dienes, resulting in isomeric 1,5-dienes, a key method for ring expansion, contraction, and stereochemical control in synthesis.
